CN109350991A - A kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy - Google Patents
A kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy Download PDFInfo
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- CN109350991A CN109350991A CN201811461104.7A CN201811461104A CN109350991A CN 109350991 A CN109350991 A CN 109350991A CN 201811461104 A CN201811461104 A CN 201811461104A CN 109350991 A CN109350991 A CN 109350991A
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- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0004—Crystallisation cooling by heat exchange
Abstract
The invention discloses a kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy, the present invention promotes concentrated solution to crystallize in setting regions using spiral tube exchanger, the temperature for reducing concentrated solution is realized quickly simultaneously, promote solution rapid crystallization, crystallization can be effectively reduced in bottom and the production quantity of the vertical wall surface of tank body.Failure caused by the crystallization of solution circulation line is reduced, equipment overall structure and operational efficiency have been advanced optimized.The device can be applied preferably in the development and utilization of low-grade energy.
Description
Technical field
The present invention relates to a kind of active crystallization apparatus based on absorption-type chemical accumulation of energy, belong to refrigeration, heating and accumulation of energy neck
Domain.
Background technique
Absorption accumulation of energy has energy storage density height, and the small advantage of heat loss is a kind of with hair in Refrigeration & Air-Conditioning field
The application technology for opening up potentiality all has the utilization and environmental protection of the low-grade energies such as industrial exhaust heat and renewable energy important
Meaning.
The thermal energy used in the past stores in technology, and sensible heat and latent heat accumulator technology are widely used, and technology is more mature.
Absorption-type chemical energy accumulating technique can make the renewable energy such as solar energy and the industrial exhaust heat energy within the system and can obtain compared with
Good application, the technical research are started late, and some problems are still had.
After evaporation and concentration heated containing solution of the working medium to (refrigerant, absorbent), the concentration of solution increases, and can be improved
The energy storage density and energy storage efficiency of absorption energy storage equipment.However, after accumulation of energy, if not needing to release energy, high concentration at once
Solution inevitably needs to store a period of time, if storage time is longer, solution will after being influenced by environment Slow cooling
Will appear two Risks: 1) heat in NaOH solution tank NaOH is passed by tank skin and pot bottom, and the solution after cooling can be in temperature
Lower tank skin and pot bottom precipitate crystal, thus can be piled up in solution pot bottom this partial crystals be difficult to release can the stage it is complete
Dissolution, the later period, which runs accumulation of energy and releases energy efficiency, constantly to be declined；2) crystalline substance can be precipitated in highly concentrated solution on solution pump, circulation line
Body influences the normal operation of solution recycle system.Above description is shown in that Fig. 1 is relatively sharp.
To pursue the problems such as long period of highly concentrated solution stores and avoids blocking caused by crystallizing, French LOCIE experiment
Room is when studying absorption energy storage equipment and being used for solar energy seasonality problem (see paper: N'Tsoukpoe K E, Le Pierre
s N, and Luo L. Experimentation of a LiBr–H2O absorption process for long-
term solar thermal storage: Prototype design and first results. Energy, 2013,
53 (1): 179-198.), propose absorption accumulation of energy liquid storage tank structure as shown in Figure 2.Change traditional accumulation of energy NaOH solution tank NaOH the bottom of from
Portion takes the mode of liquid, which takes liquid using a floating ball with solution liquid taking port above fluid reservoir.This floating ball takes
Liquid mode is always ensured that can take out is supernatant, avoids the crystal blocking solution pump for depositing to bottom.But the structure is deposited
In two problems: if still can precipitate crystal in solution pump and spray pipeline after 1) standing for a long time, causing work can not be into
Row；2) since the crystal layer of solution pot bottom accumulation is very fine and close, crystal can not all be dissolved in exoergic process, by repeatedly storing
After energy capable of being released, the solution concentration for participating in circulation is gradually decreased, and is gradually deviated from design operating conditions.
Summary of the invention
The problems of absorption accumulation of energy of above description is used for reference, the invention proposes one kind to be used for absorption-type chemical accumulation of energy
Solution active crystallization apparatus.
A kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy, including refrigerant tank, NaOH solution tank NaOH, refrigerant tank
It is connected between NaOH solution tank NaOH by refrigerant vapour pipeline, and is controlled by open and close valve,
Inside refrigerant tank, it is located at tank body bottommost containing refrigerant, First Heat Exchanger is located at centre, refrigerant spray equipment position
It above First Heat Exchanger, is pumped outside refrigerant tank containing refrigerant circulation, refrigerant liquid circulation loop, connects refrigerant liquid
Body and refrigerant spray equipment；
Inside NaOH solution tank NaOH, the working medium containing absorbent and refrigerant composition is located at tank base to solution, and the second heat exchanger is located at
Among tank body, solution spraying device is located at the second heat exchanger top, and liquid barrier is imported and exported in refrigerant vapour pipeline, outside NaOH solution tank NaOH
Solution circulation pump is contained in portion, and solution circulation loop connects aqueous liquids and solution spraying device；
It include spiral tube exchanger inside NaOH solution tank NaOH, spiral tube exchanger immerses working medium to solution inside, solution circulation loop
Upper winding electricity auxiliary heating brings solution heating；Cooling water inlet connects spiral tube exchanger subsequently into cooling water outlet, spiral shell
Filter screen is placed in coil heat exchanger lower part, and solution circulation pipe lower openings are lower than filter screen.
The filter screen is supported by filter screen stand.
Filter screen structure is placed on solution pot bottom in NaOH solution tank NaOH of the invention, and filter screen can prevent vertical wall surface works
Solution pot bottom is fallen to, pot bottom crystallization content is reduced, in order to avoid the operational efficiency of energy effect and circulating pump is released in influence, prevents from blocking
Circulation line.
The auxiliary electric heater unit used on NaOH solution tank NaOH circulation line of the invention, to prevent from precipitating crystal on circulation line
And blocking pipeline, heat-preservation cotton and auxiliary electrical heater silk are wrapped around solution circulation line, when lower than 50 DEG C electric heating wires startings,
It stops working when being higher than 60 DEG C of electric heating wires.Auxiliary electrical heater can also accelerate crystallization dissolution.
NaOH solution tank NaOH of the invention, solution circulation loop outer surface are all kept the temperature using flexible rubber-plastic foamed thermal insulating.
Spiral tube exchanger in NaOH solution tank NaOH of the invention, it is molten under the conditions of solution concentration reaches maximum at a set temperature
When liquid slow cooling, crystallization readily occurs in solution pot bottom and wall surface, is setting to make the concentrated solution quickly form crystallization
Region, using spiral tube exchanger, inside is passed through cooling water and is quickly cooled down concentrated solution.Spiral tube exchanger surface conduct simultaneously
The nuclei of crystallization of crystallization process.After being passed through cooling water, the concentration of solution declines, and crystallization increases, and is promoted using the cooling solution of cooling water
Energy loss caused by into crystallization process is smaller relative to energy solution and crystallization institute's accumulation of energy amount.
Solution absorbent and refrigerant working medium used in NaOH solution tank NaOH of the invention are to can be LiBr/H2O, H2O/
NH3, LiCl/H2O, LiNO3/H2O, NaBr/H2O, CaCl2/H2O, MgBr2/H2O etc., or one of or several substances
Mixture.And it needs to be added in solution and equipment is delayed to corrode and improve the additive of solubility.
The technology of the present invention can be applied to the renewable energy such as solar energy, geothermal energy, and industrial afterheat recovery and the energy, which are allied the communists, is
System.It is particularly adapted to electric power areas of well-being and intermittent accumulation of energy place.
The present invention promotes concentrated solution to crystallize in setting regions using spiral tube exchanger, at the same realize quickly reduce it is dense
The temperature of solution promotes solution rapid crystallization, can effectively reduce crystallization in bottom and the production quantity of the vertical wall surface of tank body.It reduces molten
Failure caused by liquid circulation line crystallizes, has advanced optimized equipment overall structure and operational efficiency.The device can preferably exist
It is applied in the development and utilization of low-grade energy.
Detailed description of the invention
Fig. 1 is traditional absorption storage energy release device schematic diagram.
Fig. 2 is the France laboratory LOCIE to the improved structural schematic diagram of the NaOH solution tank NaOH of absorption energy storage equipment.
Fig. 3 actively crystallizes absorption energy storage equipment NaOH solution tank NaOH structural schematic diagram to be proposed by the present invention.
Specific embodiment
Content is introduced with above-mentioned with reference to the accompanying drawing, technical solution of the present invention is described in further detail.
As Fig. 1 gives traditional absorption storage energy release device schematic diagram.The device contains: refrigerant tank 01, NaOH solution tank NaOH
02, it is connected between refrigerant tank 01 and NaOH solution tank NaOH 02 by refrigerant vapour pipeline 20, and controlled by open and close valve 21.
Inside refrigerant tank 01, it is located at tank body bottommost containing refrigerant 03, First Heat Exchanger 05 is located at centre, refrigerant
Spray equipment 07 is located above First Heat Exchanger 05, and First Heat Exchanger import 13 and First Heat Exchanger outlet 14 can be used as cooling
Water/freezing water entrance.Outside connects 03 liquid of refrigerant containing refrigerant circulation pump 09, refrigerant liquid circulation loop 11
With refrigerant spray equipment 07.
Inside NaOH solution tank NaOH 02, the working medium containing absorbent and refrigerant composition is located at tank base, second changes to solution 04
Hot device 06 is located among tank body, and solution spraying device 08 is located at the second heat exchanger top, and liquid barrier 19 is in refrigerant vapour pipeline
Near 20 inlet and outlet.Solution circulation pump 10 is contained in outside, and solution circulation loop 12 connects 04 liquid of solution and solution spraying device
08。
Liquid barrier 19 is near refrigerant vapour pipeline 12 is imported and exported.Open and close valve 21 is used to control the flowing of gas.
The device is able to achieve intermittent energy storage and release process.
Accumulation of energy process is with the working medium in NaOH solution tank NaOH 02 to the refrigerant evaporation of solution 04 and and in refrigerant tank 01
It is cooled to liquid refrigerant 03, solution 04 or its crystal energy store process in NaOH solution tank NaOH 02.Solution 04 is recycled by solution
Pump 10 and solution circulation line 12 enter solution spraying device 08.Solar energy, the renewable energy such as geothermal energy, industrial afterheat recovery
Low grade heat energy heat exchange after fluid generator is equivalent to by the second heat exchanger 06(by heat source import 15), heating is by molten
Dilute working medium that liquid spray equipment 08 sprays flows out generator by thermal source outlet 16 to solution 04, heat source heat exchanging fluid.
The refrigerant of heating evaporation passes through refrigerant vapour pipeline 20(opening valve 21), enter steam in refrigerant tank 01.In solution
Refrigerant constantly evaporates, and the concentration of absorbent is continuously increased, and is finally reached the solution concentration limit of set temperature and pressure condition
Value.Condenser is equivalent to by First Heat Exchanger 05(into the refrigerant vapour in refrigerant tank 01) cooling become refrigerant liquid
Body is deposited to tank base.What is walked in First Heat Exchanger 05 is cooling water, and First Heat Exchanger import 13 is cooling water inlet, first
Heat exchanger exit 14 is cooling water outlet.Since the absorbent working medium concentration in NaOH solution tank NaOH 02 increases, when solution concentration reaches most
When big, continuing heating just will appear crystallization.The increase of the concentration of solution and the formation of absorbent crystal save external heat
In the solution.In addition, spiral tube exchanger 22 can also be used as the inside heating generator of solution 04, heat source fluid need to be only passed through
Cooling water inlet 17 can accelerate solution accumulation of energy process.
Exoergic process is with the reduction of the liquid refrigerant 03 in refrigerant tank 01, and solution 04 absorbs refrigeration in NaOH solution tank NaOH 02
Agent, solution concentration is thinning, the process that contained energy discharges in working medium.Refrigerant tank 01 and NaOH solution tank NaOH 02 are all in vacuum state.
Valve 21 is opened, enables refrigerant vapour by refrigerant vapour pipeline 20 from refrigerant tank 01 to NaOH solution tank NaOH 02.Concentrated solution
04 enters solution spraying device 08 by solution circulation pump 10 and solution circulation loop 12, absorbs the system to come from refrigerant tank 01
Refrigerant vapour, absorption process are cooled down with the release of heat by the second heat exchanger 06, and life or heating heat can be produced
Water.The water being heated enters from heat source import 15, comes out from thermal source outlet 16.04 concentration of concentrated solution in NaOH solution tank NaOH 02 constantly subtracts
It is few.In refrigerant tank 01, refrigerant liquid 03 enters refrigerant by refrigerant circulation pump 09 and refrigerant circulation line 11
Spray equipment 07, refrigerant liquid are sprayed onto First Heat Exchanger 05, and 03 liquid absorption heat of vaporization of refrigerant becomes refrigerant
Gas, the release of 05 circulation line internal flow heat of First Heat Exchanger become cold water, this process can produce chilled water.At this time first
Heat exchanger 05 is equivalent to evaporator.05 internal flow of First Heat Exchanger is flowed into from First Heat Exchanger import 13, from First Heat Exchanger
14 outflow of outlet.Refrigerant liquid 03 in refrigerant tank 01 is constantly reduced, and solution 04 is continuously increased in NaOH solution tank NaOH 02, and concentration is not
Disconnected to reduce, concentrated solution becomes the release of weak solution energy.
If Fig. 2 is the structural schematic diagram that the France laboratory LOCIE improves the NaOH solution tank NaOH of absorption energy storage equipment.For
It avoids being stored in blocking solution circulation line in bottom after crystallization is cooling for a long time, influence system effectiveness, in the knot of Fig. 1 NaOH solution tank NaOH 02
On the basis of structure, floating ball liquid absorption device is increased.Floating ball 27 floats on 04 liquid level of solution, and the top that pipette nozzle is located at solution is inhaled
Solution supernatant fraction is received, then solution circulation pump 10 is passed through by following circulation tube road 29, is recycled back to by external solution
Road 12 is squeezed into solution spraying device 08.This mode can reduce energy solution or crystal grain 25 enters circulation line, reduce
Crystal forms accumulation on pipeline and circulating pump, increases the service life of circulating pump.But since this method does not avoid crystalline substance
Grain tends to the trend of 02 bottom of NaOH solution tank NaOH, and by the operation of long period, permanent crystal is formed on the bottom that solution concentrates at jar
Layer.This kind of mode does not tackle the problem at its root.It needs to design crystallization process in the region of setting, and can quickly tie
Brilliant and dissolution is reduced or avoided crystallization and occurs in liquid heat exchange and flow dead zone.
For the deficiency of above method, NaOH solution tank NaOH is further improved in this patent.As Fig. 3 gives active knot
The NaOH solution tank NaOH structural schematic diagram of brilliant absorption energy storage equipment.Spiral tube exchanger 22 immerse working medium to solution 04 inside.Outside contains
There are solution circulation pump 10, solution circulation loop 12, electricity auxiliary heating band 24 winds solution circulation loop 12 and adds to circulation solution 04
Heat.
Spiral tube exchanger 22 is as the critical component for actively crystallizing accumulation of energy.Cooling water inlet 17 connects spiral tube exchanger
22 are connected with heat source outlet 16 with the second heat exchanger 06 subsequently into cooling water outlet 18, heat source 15.When being stored
When energy, heat source hot water heating is used in the second heat exchanger 06, when carrying out releasing energy, due to exoergic process heat release, the second heat exchanger
It is cooled down in 06 using cooling water.Spiral tube exchanger 22 enters in solution 04, places filter screen 23 in its underpart, passes through
Filter screen stand 26 is supported, and filter screen 23 is prevented to be deposited to bottom, is influenced circulating for solution and is released energy effect with accumulation of energy.
NaOH solution tank NaOH is connected with refrigerant vapour pipeline 20.12 lower openings of solution circulation loop are lower than filter screen 23, solution circulation loop
Wrap up electricity auxiliary heating band 24 in 12 outsides.
The active crystallization process of absorption energy storage equipment and the specific embodiment of exoergic process described in this patent
It is as follows:
Embodiment one: accumulation of energy process is actively crystallized
Under the vacuum pressure and heating temperature condition of setting, 04 concentration of solution can be reached the limit values, when continuing heating, in solution
Absorbent can be crystallized in the vertical wall surface of tank body and the lower region of bottom temp, crystal heat exchange dead zone accumulate,
The final energy storage and release effect for influencing system.Therefore, it is necessary to crystallize absorbent working medium in the area of the setting of good effect of heat exchange
Domain.Accordingly, it is considered to spiral tube exchanger 22 be immersed among solution 04,22 rough surface of spiral tube exchanger, containing crystallizing
The required a large amount of nuclei of crystallization of journey.(there is crystal grain) when the concentration of solution accumulation of energy Process liquor 04 reaches capacity, it can be fast
Speed is passed through cooling water inside spiral tube exchanger 22, flows into from cooling water inlet 17, and cooling water outlet 18 flows out, this process is molten
Liquid crystallization process will be on cold 22 wall surface of spiral tube exchanger and its near zone is crystallized, reduce tank body wall surface and
Tank base crystallization content.It is further reduced crystal underneath with filter screen 23 in spiral tube exchanger 22 simultaneously and falls to tank
Body bottom.Cooling down lost heat relative to the energy that crystallization process is stored using cooling water is very little.After actively crystallizing
Solution concentration reduces, and low grade heat energy is stored as the chemical energy of absorbent working medium (concentrated solution and crystallization).Similarly, when solution is dense
Degree is when reaching the limit values, generating process and solution 04 active on spiral tube exchanger 22 of the solution 04 in the second heat exchanger 06
Crystallization process can carry out simultaneously, can further improve the crystallization content in NaOH solution tank NaOH.
Embodiment two: fast instant crystal exoergic process
During concentrated solution and exergonic absorbent crystal in NaOH solution tank NaOH 02, crystal can be made quick there are two types of method
Dissolution is heated circulating liquid, makes the temperature liter of solution first is that electricity auxiliary heating band 24 is added in solution circulation loop 12
Height, crystalloid solution.Second is that hot fluid can be passed through in spiral tube exchanger 22, dissolve crystal quickly.This process needs to open
Valve 21 enables refrigerant gas to be absorbed agent absorption into NaOH solution tank NaOH 02 from refrigerant tank 01.
Case study on implementation
In a case, the diameter of NaOH solution tank NaOH 02 and high respectively 0.35 m and 0.37 m, maximum capacity is 30 L, stores matter
The solution that amount is 41 kg, concentration is 64.1%.Promote brilliant device (spiral heat exchanger 22) to use caliber for 16 mm, material to be stainless steel
The heat exchanger of 304 L.Using the form of inside and outside two heat exchanger coils.External disk loop diameter is 240 mm, and inner disc is 140 mm, is indulged
It each 6 encloses upwards, at a distance of 30 mm between two adjacent rings.Using the spray thrower of stainless steel L304 material, big disk spray thrower (above)
It has been evenly arranged the aperture of 24 and 14 3 mm respectively with roundel spray thrower (following), has been used for spray solution.Bottom surface filtering
Net 23 is 50 mesh, and side filter screen is 25 mesh.Select the solution pump of 32 m of H-Max and 32 L/min of maximum stream flow.
During promoting brilliant, promote the formation of localised crystal using 17 DEG C of means that cool, after promoting brilliant about 1 hour,
Solution temperature around spiral tube exchanger 22 is about 22 DEG C, and 02 bottom solution temperature of NaOH solution tank NaOH is about 30 DEG C.As the result is shown absolutely
Most of crystal is attached on spiral tube exchanger 22, and loose gill shape is presented.Solution quality is 24.5 kg, and solution is dense
Degree is 61.0%.The quality for forming crystal is 13.3 kg, and percent crystallization in massecuite is about 32.4%.
The above is a kind of specific embodiment of the absorption energy storage equipment actively crystallized based on chemical solution, finally
It is noted that embodiment of above and energy storage system are part of reasonable manners, protection scope of the present invention not with
Above-mentioned energy storage system and embodiment are limited, and the technology contents those skilled in the relevant arts should be appreciated that technical idea, all
It is the equivalent modification and modification replacement that revealed active crystallization technique is made according to the present invention, all without departing from the technology of the present invention
Intension, and should bring into the protection scope of patent.
Claims (4)
1. a kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy, including refrigerant tank (01), NaOH solution tank NaOH (02), system
It is connected between cryogen tank (01) and NaOH solution tank NaOH (02) by refrigerant vapour pipeline (20), and is controlled by open and close valve (21), system
Cryogen tank (01) is internal, is located at tank body bottommost containing refrigerant (03), First Heat Exchanger (05) is located at centre, refrigerant spray
Device (07) is located at First Heat Exchanger (05) above, and refrigerant circulation pump (09), refrigerant liquid are contained outside refrigerant tank (01)
Body circulation circuit (11) connects refrigerant (03) liquid and refrigerant spray equipment (07)；
NaOH solution tank NaOH (02) is internal, and the working medium containing absorbent and refrigerant composition is located at tank base, second changes to solution (04)
Hot device (06) is located among tank body, and solution spraying device (08) is located at the second heat exchanger top, and liquid barrier (19) is steamed in refrigerant
Vapor pipeline (12) inlet and outlet, NaOH solution tank NaOH (02) is external to contain solution circulation pump (10), and solution circulation loop (12) connects solution
(04) liquid and solution spraying device (08)；It is characterized in that, it includes spiral tube exchanger (22), spiral shell that NaOH solution tank NaOH (02) is internal
Coil heat exchanger (22) immersion working medium is internal to solution (04), and winding electricity auxiliary heating band (24) is given in solution circulation loop (12)
Solution (04) heating；Cooling water inlet (17) connects spiral tube exchanger (22) subsequently into cooling water outlet (18), helix tube
Filter screen (23) are placed in heat exchanger (22) lower part, and solution circulation loop (12) lower openings are lower than filter screen (23).
2. a kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy according to claim 1, which is characterized in that
The filter screen (23) is supported by filter screen stand (26).
3. a kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy according to claim 1, which is characterized in that
Solution absorbent and refrigerant working medium used in NaOH solution tank NaOH are to for LiBr/H2O, H2O/NH3, LiCl/H2O, LiNO3/
The mixture of H2O, NaBr/H2O, CaCl2/H2O, MgBr2/H2O one of which or several substances.
4. a kind of solution active crystallization apparatus for absorption-type chemical accumulation of energy according to claim 1, which is characterized in that
NaOH solution tank NaOH, solution circulation loop outer surface are all kept the temperature using flexible rubber-plastic foamed thermal insulating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113663348A (en) * | 2021-09-01 | 2021-11-19 | 西安交通大学 | Device for strengthening salt spray dehydration by using air heat exchange tube and working method |
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| CN109350991B (en) | 2023-09-26 |
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