CN108148555B - Refrigeration absorbent and waste heat driven absorption type deep refrigeration method - Google Patents
Refrigeration absorbent and waste heat driven absorption type deep refrigeration method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
- F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
- F25B15/04—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas the refrigerant being ammonia evaporated from aqueous solution
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B27/00—Machines, plants or systems, using particular sources of energy
- F25B27/02—Machines, plants or systems, using particular sources of energy using waste heat, e.g. from internal-combustion engines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
- Y02A30/274—Relating to heating, ventilation or air conditioning [HVAC] technologies using waste energy, e.g. from internal combustion engine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/62—Absorption based systems
- Y02B30/625—Absorption based systems combined with heat or power generation [CHP], e.g. trigeneration
Abstract
The invention discloses a refrigeration absorbent and a waste heat driven absorption type deep refrigeration method thereof, wherein the components of the refrigeration absorbent comprise ammonia, lithium chromate, sodium iodide, potassium hydroxide and dimethylformamide, compared with the prior art, the refrigeration absorbent has the thermodynamic characteristics of low specific heat capacity, high thermal conductivity and the like, effectively overcomes the defects that a lithium bromide unit is easy to crystallize and cannot prepare working conditions below zero degree, and the continuous operation cannot be realized due to the entrainment of water vapor of an ammonia single working medium refrigeration unit, has the characteristics of stable and efficient work, no working medium entrainment, difficult crystallization and the like, is suitable for being applied in the industries such as chemical industry, oil refining, metallurgy, electric power and the like, and converts the low-grade waste heat recovery application in the industrial process into effective cold energy.
Description
Technical Field
The invention relates to the technical field of energy recycling, in particular to a refrigeration absorbent and a waste heat driven absorption type deep refrigeration method.
Background
At present, a large amount of low-grade waste heat exists in the industrial production process, the low-grade waste heat mainly exists in the form of byproduct low-pressure steam, steam condensate or flue gas, and the waste heat is difficult to recycle through the prior art due to the characteristics of low temperature and low pressure, cannot be directly discharged into the environment, and can be only treated in a circulating cooling water cooling mode. On the other hand, the industrial production process often has a large amount of refrigerating capacity demands below zero, and the existing process often adopts an electrically driven screw compressor unit to refrigerate to meet the process demands, consumes a large amount of electric energy, and simultaneously, the freon refrigerant adopted by the screw compressor has serious damage to the environment and is not in line with the development direction of future green environmental protection.
Patent document No. CN107339822A discloses a system and method for utilizing waste heat of steam condensate, in which multiple waste heat utilization technologies are provided, one of which is a waste heat deep refrigeration technology, but the heat utilization efficiency is low, and only refrigerating fluid at-20 ℃ to-25 ℃ can be prepared. The reasons for the low heat utilization efficiency are: in the implementation of waste heat deep refrigeration, liquid ammonia is evaporated from an evaporator to achieve the purpose of refrigeration and then directly returns to an absorber, so that the temperature of the liquid ammonia is lower after the liquid ammonia is converted into ammonia vapor through heat exchange in the evaporator, the transmission efficiency is lower, and the fusion rate with lean solution is low; in addition, an important reason is that the solution of the multi-element ammonia salt is prepared by a traditional formula, the specific heat capacity of the solution is high, the thermal conductivity of the solution is low, and finally the heat recovery efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a refrigeration absorbent and a waste heat driven absorption type deep refrigeration method so as to solve the technical problems of high energy consumption, environmental pollution and general refrigeration effect in the traditional refrigeration technology.
The invention is realized by the following technical scheme:
the invention provides a refrigeration absorbent, which is used in the deep refrigeration technology and comprises the following components: ammonia (NH)3) Lithium chromate (L i)2CrO4) Sodium iodide (NaI), potassium hydroxide (KOH) and dimethylformamide (C)3H7NO)。
Further, the composition of the refrigeration absorbent further comprises water (H)2O) and lithium nitrate (L iNO)3)。
Further, the refrigeration absorbent consists of the following components in percentage by mass: 30-60% ammonia (NH)3) 0-20% of water (H)2O), 0-40% lithium nitrate (L iNO)3) 5-30% of lithium chromate (L i)2CrO4) 5-25% sodium iodide (NaI), 10-55% potassium hydroxide (KOH), 3-10% dimethylformamide (C)3H7NO); the refrigeration absorbent is combined in a multi-working-medium multi-element mixing mode, the proportion of each component is determined by a specific application scene, and the optimal concentration ratio can be selected in a limited range according to different heat source conditions, environment temperature and refrigeration temperature requirements and other specific requirements of specific application fields.
The invention also provides a waste heat driven absorption type deep refrigeration method, which is carried out based on a deep refrigeration system and is a cyclic process, wherein the deep refrigeration system comprises an absorber, a generator, a condenser and an evaporator, and the waste heat driven absorption type deep refrigeration method comprises the following steps:
the rich solution output end of the absorber is connected with the rich solution input end of the generator through a rich solution pipeline, a solution pump is arranged on the rich solution pipeline, the lean solution output end of the generator is connected with the lean solution input end of the absorber through a lean solution pipeline to form a solution loop, and a throttle valve is arranged on the lean solution pipeline; the ammonia output end of the generator is connected with the ammonia input end of the condenser through a high-temperature ammonia pipeline, the ammonia liquid output end of the condenser is connected with the ammonia liquid input end of the evaporator through an ammonia liquid pipeline, a pressure reducing valve is arranged on the ammonia liquid pipeline, and the ammonia output end of the condenser is connected with the ammonia input end of the absorber through a low-temperature ammonia pipeline to form an ammonia loop;
the circulation process comprises the following steps:
(1) heating the refrigeration absorbent transported from the absorber in a generator by using industrial waste heat to ensure that most of ammonia in the refrigeration absorbent is changed into ammonia vapor to be evaporated, wherein the ammonia vapor enters a condenser through a high-temperature ammonia pipeline, and the rest refrigeration absorbent flows back into the absorber through a poor solution pipeline under the control of a throttle valve;
(2) cooling the ammonia vapor in the condenser into saturated liquid (ammonia liquid) by using circulating cooling water, reducing the pressure to evaporation pressure by using a pressure reducing valve on an ammonia liquid pipeline, and inputting the ammonia vapor into an evaporator;
(3) the liquid ammonia after pressure reduction absorbs the heat of a cooled medium in the evaporator, cold energy is output through the cooled medium, the liquid ammonia is vaporized into ammonia vapor under evaporation pressure in the evaporator, and the ammonia vapor flows back into the absorber through a low-temperature ammonia pipeline and is absorbed by the rest refrigeration absorbent;
(4) the absorption process is often an exothermic process, so that a mixed solution of ammonia gas and the rest of refrigeration absorbent is cooled in an absorber by using cooling water, and the solution with the concentration recovered in the absorber is boosted by a solution pump, enters a lean-rich solution heat exchanger, exchanges heat with lean solution and then is sent to a generator for continuous circulation.
Furthermore, the deep refrigeration system also comprises a lean-rich liquid heat exchanger, and the rich solution pipeline and the lean solution pipeline realize heat exchange through the lean-rich liquid heat exchanger, so that the heat utilization efficiency of the whole cycle can be improved.
Further, the deep refrigeration system also comprises a gas-liquid heat exchanger, and the ammonia liquid pipeline and the low-temperature ammonia gas pipeline exchange heat through the gas-liquid heat exchanger, so that ammonia steam can be reheated by using waste heat of ammonia liquid, and the transmission efficiency of the ammonia steam and the fusion rate of the ammonia steam and the lean solution are improved.
Further, the temperature of the industrial waste heat is above 80 ℃, and the temperature of the flue gas can reach above 200 ℃.
Further, the cooled medium is a low-temperature coolant, such as an aqueous glycol solution, but is not limited thereto.
Compared with the prior art, the invention has the following advantages: the invention provides a refrigeration absorbent and a waste heat driven absorption type deep refrigeration method, wherein the refrigeration absorbent is a mixed refrigeration absorbent composed of a plurality of components, has the thermodynamic characteristics of low specific heat capacity, high thermal conductivity and the like, and ensures that a system can maintain the heat recovery efficiency of 40-75%; the refrigeration absorbent effectively overcomes the defects that a lithium bromide unit is easy to crystallize, the refrigeration temperature is high, the working condition below zero can not be prepared, and the continuous operation can not be realized due to the entrainment of the water vapor of the ammonia single working medium refrigeration unit, has the characteristics of stable and efficient work, no working medium entrainment, difficult crystallization and the like, is suitable for being applied in the industries such as chemical industry, oil refining, metallurgy, electric power and the like, and converts the recovery and application of low-grade waste heat and waste heat (steam, condensate water, flue gas conversion heat and the like) in the industrial process into effective cold energy.
Drawings
FIG. 1 is an implementation schematic of a single stage system;
FIG. 2 is a schematic diagram of an implementation of a multi-stage system;
the system comprises an absorber 1, a lean-rich liquid heat exchanger 2, a generator 3, a condenser 4, a gas-liquid heat exchanger 5, an evaporator 6, a rich solution pipeline 7, a lean solution pipeline 8, a high-temperature ammonia pipeline 9, an ammonia liquid pipeline 10, a low-temperature ammonia pipeline 11, a pressure reducing valve 12, a throttle valve 13, a solution pump 14, a coolant circulating pipeline 15, a circulating pump 16 and a heat source pipeline 17.
Detailed Description
Example 1
The mixed refrigerant absorbent provided by the embodiment comprises the components of 30% of ammonia (NH) by mass percentage3) 20% water (H)2O), 30% lithium chromate (L i)2CrO4) 5% sodium iodide (NaI), 10% potassium hydroxide (KOH), 5% dimethylformamide (C)3H7NO)。
Example 2
The mixed refrigerant absorbent provided by the embodiment comprises 60% of ammonia (NH) by mass percent3) 5% lithium chromate (L i)2CrO4) 22% sodium iodide (NaI), 10% potassium hydroxide (KOH), 3% dimethylformamide (C)3H7NO)。
Example 3
The mixed refrigerant absorbent provided by the embodiment comprises the components of 30% of ammonia (NH) by mass percentage3) 5% lithium chromate (L i)2CrO4) 5% sodium iodide (NaI), 55% potassium hydroxide (KOH), 5% dimethylformamide (C)3H7NO)。
Example 4
The mixed refrigerant absorbent provided by the embodiment comprises the components of 30% of ammonia (NH) by mass percentage3) 40% lithium nitrate (L iNO)3) 5% lithium chromate (L i)2CrO4) 5% sodium iodide (NaI), 10% potassium hydroxide (KOH), 10% dimethylformamide (C)3H7NO)。
Example 5
The mixed refrigerant absorbent provided by the embodiment comprises the components of 35% of ammonia (NH) by mass percentage3) 5% water (H)2O), 10% lithium nitrate (L iNO)3) 10% lithium chromate (L i)2CrO4) 25% sodium iodide (NaI), 12% potassium hydroxide (KOH), 3% dimethylformylAmine (C)3H7NO)。
The thermodynamic parameters of the working fluid mixture (average), ammonia-water (30% by mass of ammonia) and ammonia-lithium nitrate (30% by mass of ammonia) of examples 1 to 5 were compared under the same refrigeration condition, as shown in table 1 below:
table 1: and (3) comparing the properties of the working substances under the same refrigeration working condition:
the refrigeration effect of the refrigeration absorbent of the present example was verified by taking the refrigeration absorbents of examples 3 and 4 as examples.
The system adopts a waste heat driven absorption type deep refrigeration system (single-stage system) as shown in fig. 1, and comprises an absorber 1, a lean-rich solution heat exchanger 2, a generator 3, a condenser 4, a gas-liquid heat exchanger 5 and an evaporator 6, wherein a rich solution output end of the absorber 1 is connected with a rich solution input end of the generator 3 through a rich solution pipeline 7, a solution pump 14 is arranged on the rich solution pipeline 7, a lean solution output end of the generator 3 is connected with a lean solution input end of the absorber 1 through a lean solution pipeline 8 to form a solution loop, a throttle valve 13 is arranged on the lean solution pipeline 8, and the rich solution pipeline 7 and the lean solution pipeline 8 realize heat exchange through the lean-rich solution heat exchanger 2, so that the heat utilization efficiency of the whole cycle can be improved; the ammonia output of generator 3 is connected with the ammonia input of condenser 4 through high temperature ammonia pipeline 9, the ammonia liquid output of condenser 4 passes through ammonia liquid pipeline 10 and is connected with the ammonia liquid input of evaporimeter 6, be equipped with relief pressure valve 12 on the ammonia liquid pipeline 10, the ammonia output of condenser 4 passes through low temperature ammonia pipeline 11 and is connected with the ammonia input of absorber 1, forms the ammonia return circuit, ammonia liquid pipeline 10 and low temperature ammonia pipeline 11 pass through gas-liquid heat exchanger 5 carries out the heat exchange, makes ammonia steam can utilize the waste heat of ammonia liquid to reheat to improve the efficiency of the transmission of ammonia steam, and the speed that fuses with poor solution thereof.
The process of utilizing the system to carry out waste heat driven absorption type deep refrigeration comprises the following steps:
(1) heating the refrigeration absorbent (rich solution) transported from the absorber 1 in the generator 3 by using a working heat source (industrial waste heat) with the temperature of more than 80 ℃ to change most of ammonia in the refrigeration absorbent into ammonia vapor to be evaporated, wherein the ammonia vapor enters the condenser 4 through a high-temperature ammonia gas pipeline 9, and the rest refrigeration absorbent (lean solution) flows back into the absorber 1 through a lean solution pipeline 8 under the control of a throttle valve 13;
(2) the ammonia vapor in the condenser 4 is cooled into saturated liquid (ammonia liquid) by using circulating cooling water, and the saturated liquid (ammonia liquid) is decompressed to evaporation pressure by a pressure reducing valve 12 on an ammonia liquid pipeline 10 and then is input into the evaporator 6;
(3) the liquid ammonia after pressure reduction absorbs the heat of a cooled medium (such as ethylene glycol aqueous solution) in the evaporator 6, cold energy is output through the cooled medium, the liquid ammonia is vaporized into ammonia vapor under evaporation pressure in the evaporator 6, and the ammonia vapor flows back into the absorber 1 through the low-temperature ammonia pipeline 11 and is absorbed by the rest refrigeration absorbent;
(4) the absorption process is often an exothermic process, so that the mixed solution of ammonia gas and the rest of the refrigeration absorbent is cooled in the absorber 1 by using cooling water, and the solution with the concentration recovered in the absorber 1 is boosted by the solution pump 14, enters the lean-rich solution heat exchanger 2, exchanges heat with the lean solution, and is sent to the generator 3 for continuous circulation.
Meanwhile, a control group A, B is set, and the refrigeration effect comparison and verification are respectively carried out on the refrigeration absorbent of the ammonia-water (the ammonia content is 30 mass percent) working medium pair and the ammonia-lithium nitrate (the ammonia content is 30 mass percent) working medium pair.
The results are shown in table 2 below:
as can be seen from tables 1 and 2, compared with the conventional ammonia-water working medium pair or ammonia-lithium nitrate working medium pair, the refrigeration absorbent provided by the invention has the thermodynamic characteristics of low specific heat capacity, high thermal conductivity and the like, and the refrigeration coefficient is high under the same refrigeration working condition, so that the system can be ensured to maintain the heat recovery efficiency of 40-75%, and the refrigeration absorbent has the characteristics of stable and efficient work, no working medium entrainment, difficulty in crystallization and the like.
As shown in fig. 2, the system is a waste heat driven absorption type deep refrigeration multistage system (three-stage system), which includes three industrial waste heat driven absorption type deep refrigeration single-stage systems, which are respectively denoted as system a, system B and system C, wherein an evaporator 6 of the system a and a condenser 4 of the system B, and an evaporator 6 of the system B and a condenser 4 of the system C are connected through a coolant circulation pipeline 15, a circulation pump 16 is disposed on the coolant circulation pipeline 15, and is used for driving coolant to be transmitted between upper and lower stages of systems, and heat source pipelines 17 are further connected between generators 3 of the system a and the system B, and between generators 3 of the system B and the system C. By utilizing the circulation of the multi-stage system and combining the refrigeration absorbent, the low-temperature refrigeration capacity of fifty-five ℃ below zero can be finally prepared.
The above is a detailed embodiment and a specific operation process of the present invention, which are implemented on the premise of the technical solution of the present invention, but the protection scope of the present invention is not limited to the above-mentioned examples.
Claims (6)
1. The refrigeration absorbent is characterized by comprising the following components in percentage by mass: 30-60% of ammonia, 0-20% of water, 0-40% of lithium nitrate, 5-30% of lithium chromate, 5-25% of sodium iodide, 10-55% of potassium hydroxide and 3-10% of dimethylformamide.
2. A waste heat driven absorption type deep refrigeration method is characterized by comprising the following steps:
(1) heating the refrigerated absorbent of claim 1 transported from the absorber through the rich solution line in a generator using industrial waste heat to cause a substantial portion of the ammonia in the refrigerated absorbent to become ammonia vapor to evaporate, wherein the ammonia vapor enters the condenser through the high temperature ammonia line and the remaining refrigerated absorbent flows back into the absorber through the lean solution line under the control of the throttle valve;
(2) cooling the ammonia vapor in the condenser into saturated liquid by using circulating cooling water, reducing the pressure to evaporation pressure by using a pressure reducing valve on an ammonia liquid pipeline, and inputting the saturated liquid into an evaporator;
(3) the liquid ammonia after pressure reduction absorbs the heat of a cooled medium in the evaporator, cold energy is output through the cooled medium, the liquid ammonia is vaporized into ammonia vapor under evaporation pressure in the evaporator, and the ammonia vapor flows back into the absorber through a low-temperature ammonia pipeline and is absorbed by the rest refrigeration absorbent;
(4) cooling the mixed solution of ammonia gas and the rest refrigerating absorbent by using cooling water in the absorber, boosting the solution with the concentration recovered in the absorber by using a solution pump, then feeding the solution into a lean-rich solution heat exchanger to exchange heat with a lean solution, and then feeding the solution into a generator to continue circulation.
3. The method as claimed in claim 2, wherein the refrigerant absorbent in the rich solution line exchanges heat with the refrigerant absorbent remaining in the lean solution line through the lean rich heat exchanger.
4. The waste heat driven absorption type deep refrigeration method according to claim 2, wherein the ammonia liquid in the ammonia liquid pipeline exchanges heat with the ammonia gas in the low-temperature ammonia gas pipeline through the gas-liquid heat exchanger to reheat the ammonia gas in the low-temperature ammonia gas pipeline.
5. The waste heat driven absorption type deep refrigeration method according to claim 2, wherein the temperature of the industrial waste heat is 80 ℃ or higher.
6. The waste heat driven absorption type deep refrigeration method according to claim 2, wherein the cooled medium is a low temperature coolant.
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| CN108726536A (en) * | 2018-08-08 | 2018-11-02 | 安徽沃特普尔节能科技有限公司 | A kind of system and method for producing liquefied ammonia using soda manufacture process steam condensation fluid residual heat |
| CN111895677A (en) * | 2020-08-21 | 2020-11-06 | 五邑大学 | Refrigerating system |
| CN112283982B (en) * | 2020-10-09 | 2021-10-22 | 安徽普泛能源技术有限公司 | Evaporation type absorber and absorption type refrigerating system thereof |
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| GB411522A (en) * | 1932-11-29 | 1934-06-08 | Siemens Ag | Improvements in or relating to absorption systems for cooling, heating and heat-exchange purposes |
| DE3246554A1 (en) * | 1982-12-16 | 1984-06-20 | Dieter Dipl.-Ing. 7000 Stuttgart Seher | Working mixtures for sorption heat pumps, sorption refrigerators and sorption heat transformers |
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Address after: 230000 building 6, shuimuyuan, Yanhu hi tech R & D base (Tsinghua Science and Technology City, Hefei), West Xiyou Road, North Jinxiu Avenue, Hefei Economic and Technological Development Zone, Anhui Province Patentee after: Anhui pupan Energy Technology Co.,Ltd. Address before: 230000 building 17, alumni Innovation Park, Luyang Economic Development Zone, Hefei City, Anhui Province Patentee before: Anhui pupan Energy Technology Co.,Ltd. |
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