CN114484914A - Two-stage refrigeration liquefier and organic solvent recovery method and system - Google Patents
Two-stage refrigeration liquefier and organic solvent recovery method and system Download PDFInfo
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- CN114484914A CN114484914A CN202210091974.XA CN202210091974A CN114484914A CN 114484914 A CN114484914 A CN 114484914A CN 202210091974 A CN202210091974 A CN 202210091974A CN 114484914 A CN114484914 A CN 114484914A
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- 238000005057 refrigeration Methods 0.000 title claims abstract description 107
- 239000003960 organic solvent Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000011084 recovery Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 98
- 238000001179 sorption measurement Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000009833 condensation Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000003507 refrigerant Substances 0.000 claims description 101
- 239000007789 gas Substances 0.000 claims description 93
- 239000002912 waste gas Substances 0.000 claims description 52
- 239000012528 membrane Substances 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 abstract description 21
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 239000002274 desiccant Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 230000006835 compression Effects 0.000 description 12
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/06—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point using expanders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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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
- F25B41/00—Fluid-circulation arrangements
- F25B41/20—Disposition of valves, e.g. of on-off valves or flow control valves
-
- 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
- F25B41/00—Fluid-circulation arrangements
- F25B41/40—Fluid line arrangements
-
- 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
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
-
- 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
- F25B5/00—Compression machines, plants or systems, with several evaporator circuits, e.g. for varying refrigerating capacity
- F25B5/02—Compression machines, plants or systems, with several evaporator circuits, e.g. for varying refrigerating capacity arranged in parallel
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Power Engineering (AREA)
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to a secondary refrigeration liquefier and an organic solvent recovery method and system, wherein the secondary refrigeration liquefier comprises a compressor, a condenser, a primary evaporator, a secondary evaporator, a gas-liquid separator, a throttle valve and an ejector, the primary evaporator and the secondary evaporator are connected in parallel and are positioned between the gas-liquid separator and the ejector, the gas-liquid separator, the compressor, the condenser, the ejector and the primary evaporator are sequentially connected into a first circulation loop, and the gas-liquid separator, the throttle valve, the secondary evaporator, the ejector and the primary evaporator are sequentially connected into a second circulation loop. The main treatment method of the organic solvent recovery method adopts a secondary refrigeration liquefier with an ejector to realize secondary refrigeration temperature. The pretreatment comprises pressurization, water cooling, drying and precooling, the post-treatment comprises dehydration of condensed liquid, adsorption and discharge of uncondensed gas, and desorbed gas returns to condensation circulation, so that the method is truly fully recovered and zero-discharged, and the recovered organic solvent is directly reused.
Description
Technical Field
The invention belongs to the technical field of organic solvent-containing waste gas treatment in related industries such as coating machines, printing industry and the like, and particularly relates to a secondary refrigeration liquefier and an organic solvent recovery method and system.
Background
At present, industrial production discharges a large amount of waste gas containing organic solvent, such as printing and coating machine industries, and the emission pollution of the waste gas containing organic solvent is not small. During coating and printing, a large amount of organic substances, such as hydrocarbons, alcohols, esters, ethers, nitriles and the like, are volatilized, and the organic solvents are discharged in the form of waste gas through air entrainment. And the waste water is discharged after reaching the standard due to the requirement of environmental protection. From the aspect of treatment process, domestic methods for treating the organic waste gas mainly comprise an adsorption method, a gas membrane separation method, a condensation method and the like, unit combinations are different, and the final effect can be completely different due to different sequences. The commercialization of the gas membrane separation technology is not mature, and the defects of low gas concentration after separation, easy blockage of a gas separation membrane and the like exist; the adsorption method has lower cost and is simpler, but can not completely adsorb; the condensation method adopts normal-temperature water for cooling, the efficiency is low, or a refrigeration system is adopted, but the single temperature is single, and a plurality of refrigeration systems have high cost and large energy consumption. Therefore, the current mainstream organic solvent waste gas treatment takes an adsorption method as a main treatment unit, after the adsorption unit is adopted for treatment, the waste gas is directly discharged, or is combined with incineration treatment, or is combined with a condensation method, or is combined with gas membrane separation, but the adsorption is only limited adsorption, and is combined with other methods to achieve the emission standard, and once the standard is improved, the method is difficult to meet the requirement.
In conclusion, the organic solvent treatment method in the existing printing and coating machine industry cannot realize the full recovery of the organic solvent and cannot realize the reutilization of the organic solvent. In the carbon neutralization background, the emission standard of the organic solvent is improved based on the change of the environmental protection policy, the indexes are gradually tightened, zero emission of organic solvent gas is required, and the existing treatment method based on the adsorption unit as a main part cannot meet the environmental protection policy and the requirement.
Disclosure of Invention
In order to solve the technical problems that the treatment method based on the adsorption unit as a main method cannot realize the full recovery of the organic solvent, cannot realize the reutilization of the organic solvent and cannot meet the tightened environmental protection policy and requirements, the invention provides a secondary refrigeration liquefier. The invention further provides an organic solvent recovery method adopting the secondary refrigeration liquefier, and the invention also provides an organic solvent recovery system adopting the secondary refrigeration liquefier.
The technical scheme of the invention is as follows:
a second-stage refrigeration liquefier comprises a compressor, a condenser, an evaporator, a gas-liquid separator, a throttle valve and an ejector, wherein the evaporator comprises a first-stage evaporator and a second-stage evaporator, the first-stage evaporator and the second-stage evaporator are connected in parallel and are positioned between the gas-liquid separator and the ejector, the gas-liquid separator, the compressor, the condenser, the ejector and the first-stage evaporator are sequentially connected to form a first circulation loop, and the gas-liquid separator, the throttle valve, the second-stage evaporator, the ejector and the first-stage evaporator are sequentially connected to form a second circulation loop;
the ejector is a Laval nozzle and comprises a nozzle, a mixing chamber and a diffuser, the nozzle is provided with a refrigerant condensate inlet and a refrigerant evaporation gas inlet, the diffuser is provided with a refrigerant outlet, the refrigerant condensate inlet of the ejector is communicated with the condenser outlet, the refrigerant evaporation gas inlet is communicated with the secondary evaporator outlet, the refrigerant outlet is communicated with the primary evaporator inlet, and the primary evaporator outlet is communicated with the gas-liquid separator; the gas-liquid separator comprises a refrigerant inlet, a vapor refrigerant outlet and a liquid refrigerant outlet, the refrigerant inlet is communicated with the outlet of the primary evaporator, the liquid refrigerant outlet is connected with the throttling valve, the throttling valve is communicated with the inlet of the secondary evaporator, the vapor refrigerant outlet is communicated with the inlet of the compressor, and the outlet of the compressor is communicated with the inlet of the condenser;
the refrigeration temperature of the primary evaporator is-15 to-25 ℃, and the refrigeration temperature of the secondary evaporator is-50 to-60 ℃.
The throttle valve is an electromagnetic expansion valve.
The refrigerant is a low-temperature refrigerant which can cope with the low temperature below 60 ℃ below zero or an environment-friendly mixed refrigerant with the low temperature below 60 ℃ below zero.
The compressor adopts a low-temperature piston compressor, and the capacity is 5P/10P or the combination thereof.
The first-stage evaporator and the second-stage evaporator adopt finned tube type or wound tube type evaporators.
The primary evaporator is arranged at the lower part, the secondary evaporator is arranged at the upper part, and an arc-shaped sieve plate for liquid collection and airflow distribution is arranged between the primary evaporator and the secondary evaporator.
A method for recovering organic solvent comprises the steps of condensing and liquefying waste gas containing organic solvent by using the secondary refrigeration liquefier, sequentially exchanging heat with the primary evaporator and the secondary evaporator to perform primary refrigeration and secondary refrigeration respectively to obtain condensed liquid, and recovering the organic solvent; the refrigeration temperature of the primary evaporator is-15 to-25 ℃, and the refrigeration temperature of the secondary evaporator is-50 to-60 ℃.
The method comprises the steps of carrying out condensation circulation on the condensed liquid, carrying out pre-treatment and post-treatment, wherein the pre-treatment comprises pressurization, water cooling, drying and pre-cooling, and the post-treatment comprises the steps of dewatering the condensed liquid, adsorbing a small amount of uncondensed gas, emptying after reaching the standard, returning desorbed gas to the pressurization step, and carrying out condensation circulation again.
And during precooling, precooling the dried waste gas by exchanging heat with the exhaust gas of the secondary refrigeration liquefier, wherein the temperature of the precooled waste gas is 0-5 ℃.
The pressure of the exhaust gas after undergoing the pressure increasing step is 0.13-0.17 MPa.
The water cooling is normal-temperature water cooling, and the temperature of the cooled waste gas is reduced to 30-40 ℃.
The water content of the waste gas after drying is 0.02-0.03 g/m3。
An organic solvent recovery system is used for realizing the organic solvent recovery method, and comprises a booster fan, a normal-temperature water cooling heat exchanger, a dryer, a heat regenerator, a secondary refrigeration liquefier, a liquid membrane separator and a gas adsorption tower which are sequentially connected; the regenerator comprises a dry waste gas inlet, a dry waste gas outlet, an uncondensed gas inlet and an uncondensed gas outlet, the dry waste gas inlet is communicated with the outlet of the dryer, the dry waste gas outlet is communicated with the primary evaporator of the secondary refrigeration liquefier, the gas outlet of the secondary evaporator of the secondary refrigeration liquefier is communicated with the uncondensed gas inlet of the regenerator, the uncondensed gas outlet of the regenerator is communicated with the gas adsorption tower, the desorption gas outlet of the adsorption tower is communicated with the inlet of the booster fan, and the booster fan is positioned on an organic solvent-containing waste gas collecting pipeline; and a condensed liquid outlet of the secondary refrigeration liquefier is communicated with the liquid membrane separator.
The dryer is a double-layer dryer, the lower-layer dryer is a high-temperature-resistant dryer, the upper-layer dryer is a high-water-absorption dryer, and a buffer layer is arranged between the upper-layer dryer and the lower-layer dryer.
The heat regenerator adopts a two-flow plate type heat exchanger.
The invention has the beneficial technical effects that:
the invention relates to a two-stage refrigeration liquefier, which is characterized in that on the basis of a vapor compression refrigeration system with an ejector, a first-stage evaporator is additionally arranged between a gas-liquid separator and the ejector, and the original evaporator is used as a second-stage evaporator to realize the two-stage refrigeration temperature of a refrigeration system, so that the two-stage refrigeration temperature is integrated in one liquefier, namely the two-stage refrigeration temperature is realized by a single machine. The refrigeration temperature of the primary evaporator is-15 to-25 ℃, and the refrigeration temperature of the secondary evaporator is-50 to-60 ℃. The first-stage refrigeration realizes the first-stage refrigeration temperature after being mixed with the refrigerant steam of the second-stage evaporator through the throttling of the nozzle of the ejector, and the second-stage refrigeration temperature is realized by further throttling and cooling the liquid in the gas-liquid separator through the throttling valve. The secondary low-temperature refrigerant vapor is mixed with the refrigerant vapor injected by the ejector to adjust the suction pressure and temperature of the compressor, so that the proper pressure ratio and pressure difference of the compressor are realized.
Preferably, the compressor is a low-temperature piston compressor, the capacity is 5P/10P or the combination thereof, the low temperature below minus 60 ℃ can be met, and the high pressure ratio and the pressure difference can be borne. The refrigerant is a low-temperature refrigerant which can cope with the low temperature below 60 ℃ below zero or an environment-friendly mixed refrigerant with the low temperature below 60 ℃ below zero. The throttle valve adopts an electromagnetic expansion valve, and automatic opening control is carried out according to the required temperature and flow so as to realize matching and coordination of refrigerating capacity and refrigerating temperature. The first-stage evaporator and the second-stage evaporator are the same in refrigerant, and two stages of different temperatures can be formed because of different throttling pressure differences.
On the basis, the secondary refrigeration temperature is realized by adopting the vapor compression refrigeration liquefier with the ejector, and the secondary cooling is constructed by matching the gas components of the organic solvent, so that most of the organic solvent is condensed, liquefied and recycled in a condensation and liquefaction mode. The organic solvent used in the coater or the printer is generally an organic substance having a carbon number of C4 or more, and is composed of a plurality of components including light carbon having C4 to C7 and heavy carbon having a carbon number of C8 or more. Because the liquefaction temperature difference between the heavy carbon and the light carbon is great, the heavy carbon component is liquefied at about-20 ℃, and the light carbon can be liquefied only at about-50 ℃. If a single refrigeration temperature is used, complete liquefaction cannot be achieved. Therefore, the heavy carbon component is condensed by adopting secondary refrigeration, the heavy carbon component is liquefied and recovered by a primary evaporator (the refrigeration temperature is-15 to-25 ℃), the light carbon component is liquefied and recovered by a secondary evaporator (the refrigeration temperature is-50 to-60 ℃), the theoretical liquefaction ratio is one hundred percent, but the actual liquefaction ratio is about 98 percent due to impurities; and the secondary gradual cooling not only realizes the saving of temperature and cold source, namely energy saving, but also reduces the cold load of the secondary evaporator after the primary evaporation and condensation, thereby being beneficial to reducing the system capacity, saving the investment and reducing the energy consumption. Compared with two-stage compression of two compressors, the two-stage compression has the advantages that the cost of one compressor is reduced, the operation cost of two-stage compression is reduced, and the commercial feasibility is realized.
In the organic solvent recovery method, the main treatment method is to realize the secondary refrigeration temperature by a secondary refrigeration liquefier with an ejector. Pretreatment is performed before condensation to increase the condensation temperature and reduce the cooling load. First, the organic solvent off-gas is first pressurized because increasing the gas pressure is beneficial in reducing the condensation temperature of some of the components; the pressurized gas enters a normal-temperature water cooling heat exchanger, can be cooled to 30-40 ℃ through water cooling, and can remove a part of water; further, moisture in the exhaust gas is removed through a dryer, and the refrigeration load is reduced; and introducing the dried gas into a heat regenerator to exchange heat with the gas exhausted by the liquefier (-50 to-60 ℃) for precooling, and sending the gas into a primary evaporator of a secondary refrigeration liquefier after the temperature is reduced to 0-5 ℃ so as to reduce the refrigerating capacity of the primary evaporator. The most of the organic solvent is liquefied by condensation and temperature reduction of a first-stage evaporator and a second-stage evaporator. A small amount of non-liquefied waste gas containing an organic solvent enters an adsorption unit for treatment, the discharged waste gas is adsorbed clean air, the desorbed gas returns to a booster fan, continues to/participates in liquefaction again, and is still liquefied after being accumulated to a certain concentration, so that zero emission of the organic solvent is realized, and emission of carcinogens by organic solvent emission and incineration is avoided; the condensed liquid also contains a small amount of water, and then the condensed liquid is sent to a liquid membrane separator for water separation, so that the pure recovery of the organic solvent liquid is realized. In conclusion, the organic solvent treatment method is truly full recovery and zero emission, the recovered organic solvent is directly reused, and no solvent gas is emitted.
Compared with the prior art, the invention has the following advantages:
1. the vapor compression refrigeration cycle with the ejector is adopted, the cycle efficiency is high, the secondary refrigeration temperature is obtained, and for gas cooling, the gradual cooling is favorable for improving the cycle efficiency, the cooling time is prolonged, and the gas liquefaction is promoted.
2. An independently designed double-layer desiccant dryer is adopted. To cope with occasional high temperatures (relative to normal temperatures).
3. Separating with liquid separation membrane based on liquefied liquid to remove water and CO2And the pure organic solvent is obtained, so that the recycling of the organic solvent is really realized.
4. A small amount of organic gas which is not condensed is collected by the adsorption tower, so that the organic solvent can be collected and captured by more than 99 percent, and meanwhile, no gas of the organic solvent is discharged. And mixing the desorbed gas with the gas in the waste gas pipe, and performing secondary circulation through a booster fan.
Drawings
FIG. 1 is a schematic diagram of a conventional vapor compression refrigeration system with an ejector;
1 ' -compressor, 2 ' -condenser, 3 ' -evaporator, 4 ' -gas-liquid separator, 41 ' -refrigerant inlet, 42 ' -gaseous refrigerant outlet, 43 ' -liquid refrigerant outlet, 5 ' -throttle valve, 6 ' -ejector;
FIG. 2 is a schematic structural view of an embodiment of an injector;
61 '-nozzle, 62' -mixing chamber, 63 '-diffuser, 64' -refrigerant condensate inlet, 65 '-refrigerant boil-off gas inlet, 66' -refrigerant outlet;
FIG. 3 is a schematic diagram of a two-stage refrigeration liquefier in accordance with an embodiment of the present invention;
1-compressor, 2-condenser, 31-first evaporator, 32-second evaporator, 4-gas-liquid separator, 5-throttle valve, 6-ejector;
FIG. 4 is a schematic flow diagram of an embodiment of a method of organic solvent recovery according to the present invention;
FIG. 5 is a schematic view of an embodiment of an organic solvent recovery system of the present invention;
1-a compressor, 2-a condenser, 31-a first evaporator, 32-a second evaporator, 4-a gas-liquid separator, 5-a throttle valve, 6-an ejector, 7-a booster fan, 8-a normal-temperature water cooling heat exchanger, 9-a dryer, 10-a heat regenerator, 11-an organic solvent storage tank, 12-a liquid membrane separator, 131-a 1# adsorption tower and 132-a 2# adsorption tower;
FIG. 6 is a schematic structural view of an embodiment of a double-deck dryer;
91-upper layer drying agent, 92-lower layer drying agent and 93-buffer layer.
Detailed Description
In order to facilitate understanding of the technical solutions of the present application, the following detailed descriptions will be provided with reference to fig. 1 to 6 by specific embodiments.
As shown in fig. 1, the conventional vapor compression refrigeration system with an ejector includes a compressor 1 ', a condenser 2', an evaporator 3 ', a gas-liquid separator 4', a throttle valve 5 'and an ejector 6'. The gas-liquid separator 4 ', the compressor 1', the condenser 2 ', the ejector 6' and the gas-liquid separator 4 'are sequentially connected to form a first circulation loop, and the gas-liquid separator 4', the throttle valve 5 ', the evaporator 3', the ejector 6 'and the gas-liquid separator 4' are sequentially connected to form a second circulation loop. As shown in fig. 2, the ejector 6 'is a laval nozzle comprising a contracted pipe 7' and an expanded pipe 8 ', and a nozzle 61', a mixing chamber 62 'and a diffuser 63' are sequentially formed in a direction from the contracted pipe 7 'to the expanded pipe 8', the nozzle 61 'is located at a section of the contracted pipe 7', the mixing chamber 62 'is located at a front section of the expanded pipe 8', and the diffuser 63 'is located at a rear section of the expanded pipe 8'. The nozzle of the nozzle 61 'is a refrigerant condensate inlet 64', the refrigerant evaporation gas inlet 65 'is arranged at the side of the nozzle 61', and the end of the diffuser 63 'is a refrigerant outlet 66'. The inlet of the condenser 2 ' is communicated with the compressor 1 ', and the outlet of the condenser 2 ' is communicated with the refrigerant condensate inlet 64 ' of the ejector 6 '; the outlet of the evaporator 3 'is communicated with the refrigerant evaporation gas inlet 65' of the ejector 6 ', and the refrigerant outlet 66' of the ejector 6 'is communicated with the gas-liquid separator 4'; the gas-liquid separator 4 ' includes a refrigerant inlet 41 ', a gaseous refrigerant outlet 42 ' and a liquid refrigerant outlet 43 ', the refrigerant inlet 41 ' communicates with the refrigerant outlet 66 ' of the ejector 6 ', the liquid refrigerant outlet 43 ' communicates with the inlet of the evaporator 3 ', the gaseous refrigerant outlet 42 ' communicates with the inlet of the compressor 1 ', and the outlet of the compressor 1 ' communicates with the inlet of the condenser 2 '. A throttle valve 5 ' is provided in a pipe between the gas-liquid separator 4 ' and the evaporator 3 '.
The refrigeration cycle principle of the conventional vapor compression refrigeration system with the ejector is as follows:
the compressor 1' compresses a refrigerant; the condenser 2 'cools the high-pressure refrigerant discharged from the compressor 1'; the evaporator 3' evaporates the refrigerant; the ejector 6 ' reduces and expands the pressure of the high-pressure refrigerant supplied from the condenser 2 ' to extract the vapor-state refrigerant evaporated in the evaporator 3 ', so that the ejector 6 ' converts the expansion energy of the refrigerant into pressure energy to increase the intake pressure of the compressor 1 '. Specifically, the nozzle 61 'of the ejector 6' converts the pressure energy of the high-pressure refrigerant discharged from the condenser 2 'into velocity energy in such a manner that the nozzle 61' performs isentropic decompression and expansion of the refrigerant. In the mixing chamber 62 ', the high-speed refrigerant flow discharged from the nozzle 61' draws the gaseous refrigerant that has been evaporated in the evaporator 3 'into the mixing chamber 62' and mixes with the gaseous refrigerant. In the diffuser 63 ', the refrigerant discharged from the nozzle 61 ' and the refrigerant drawn from the evaporator 3 ' are further mixed in such a manner that the velocity energy of the refrigerant is converted into the pressure energy to increase the pressure of the refrigerant. The refrigerant discharged from the diffuser 63 'is separated by the gas-liquid separator 4', and then the gaseous refrigerant is delivered to the compressor 1 ', and the liquid refrigerant is delivered to the evaporator 3', thereby realizing one cycle.
The conventional vapor compression refrigeration system with the ejector can only realize single refrigeration temperature, cannot meet different condensation temperatures required by organic solvent waste gas containing heavy carbon and light carbon components, and has low condensation efficiency on organic solvents.
As shown in fig. 3, the two-stage refrigeration liquefier of the present invention is based on a conventional vapor compression refrigeration system with an ejector, and a first-stage evaporator 31 is additionally arranged between the ejector 6 and the gas-liquid separator 4, and the original evaporator is used as a second-stage evaporator 32 to establish two evaporation temperatures. The compressor 1 adopts a low-temperature piston compressor, can cope with low temperature below minus 60 ℃, and bears larger pressure ratio and pressure difference. The refrigerant is a low-temperature refrigerant capable of coping with the low temperature below-60 ℃, such as R508B, or an environment-friendly mixed refrigerant with the low temperature below-60 ℃, such as a propane-based mixed refrigerant. The throttle valve 5 adopts an electromagnetic expansion valve, and automatic opening control is carried out according to the required temperature and flow so as to realize matching and coordination of refrigerating capacity and refrigerating temperature. The refrigerant in the first-stage evaporator 31 and the refrigerant in the second-stage evaporator 32 are the same, and because the throttle pressure difference is different, two different temperatures can be formed. In this embodiment, the refrigeration temperature of the first-stage evaporator 31 is-15 to-25 ℃ to recover the heavy carbon components, and the refrigeration temperature of the second-stage evaporator 32 is-50 to-60 ℃ to recover the light carbon components.
The structure of the embodiment of the two-stage refrigeration liquefier comprises a compressor 1, a condenser 2, an evaporator, a gas-liquid separator 4, a throttle valve 5 and an ejector 6, wherein the evaporator comprises a first-stage evaporator 31 and a second-stage evaporator 32, the first-stage evaporator 31 and the second-stage evaporator 32 are connected in parallel and are respectively positioned between the gas-liquid separator 4 and the ejector 6, the gas-liquid separator 4, the compressor 1, the condenser 2, the ejector 6 and the first-stage evaporator 31 are sequentially connected to form a first circulation loop, and the gas-liquid separator 4, the throttle valve 5, the second-stage evaporator 32, the ejector 6 and the first-stage evaporator 31 are sequentially connected to form a second circulation loop. As shown in fig. 2, the ejector 6 is a laval nozzle composed of a contraction pipe and an expansion pipe, and a nozzle, a mixing chamber and a diffuser are arranged in the direction from the contraction pipe to the expansion pipe, the nozzle has a refrigerant condensate inlet and a refrigerant evaporation gas inlet, the diffuser has a refrigerant outlet, the refrigerant condensate inlet of the ejector 6 is communicated with the outlet of the condenser 2, the refrigerant evaporation gas inlet is communicated with the outlet of the secondary evaporator 32, the refrigerant outlet is communicated with the inlet of the primary evaporator 31, and the outlet of the primary evaporator 31 is communicated with the gas-liquid separator 4; the gas-liquid separator 4 comprises a refrigerant inlet, a vapor refrigerant outlet and a liquid refrigerant outlet, the refrigerant inlet is communicated with the outlet of the primary evaporator 31, the liquid refrigerant outlet is connected with the throttle valve 5, the throttle valve 5 is communicated with the inlet of the secondary evaporator 32, the vapor refrigerant outlet is communicated with the inlet of the compressor 1, and the outlet of the compressor 1 is communicated with the inlet of the condenser 2.
The liquefier employs a two-stage vapor compression refrigeration cycle with an ejector, with a first-stage evaporator 31 disposed at a lower portion and a second-stage evaporator 32 disposed at an upper portion. The first-stage evaporator 31 and the second-stage evaporator 32 both adopt finned tube evaporators, and the finned tube heat exchanger needs to have a certain height in the gas flowing direction so that gas has enough residence condensation time and gas liquefaction is facilitated. The primary evaporator 31 and the secondary evaporator 32 may also be wound-tube evaporators.
There is the curved screen hole board that is used for album liquid and air current distribution between one-level evaporimeter 31, the second grade evaporimeter 32, through the curved screen hole board, has both realized not gaseous equipartition once more of condensation behind the one-level evaporimeter 31, has also collected the liquid that the second grade evaporimeter 32 condensation got off, and the liquid after the collection mixes with the liquid that the one-level evaporimeter 31 condensation got off in flowing to lower part liquid tank through the liquid pipe.
The refrigeration cycle principle of the two-stage refrigeration liquefier is as follows: the exhaust gas of the compressor 1 is condensed by the condenser 2 to obtain the normal-temperature high-pressure refrigerant liquid, and the refrigerant liquid is sprayed by the ejector 6 and then mixed with the refrigerant vapor sucked into the secondary evaporator 32, and then enters the primary evaporator 31 for refrigeration to obtain the primary evaporation temperature. The evaporated refrigerant gas enters the gas-liquid separator 4, and the refrigerant liquid in the gas-liquid separator 4 further passes through the throttle valve 5 and enters the secondary evaporator 32 to obtain a secondary refrigeration temperature. The refrigerant gas in the secondary evaporator 32 is brought into the ejector 6 by the vacuum of the ejector 6 and is mixed with the normal-temperature high-pressure refrigerant from the condenser 2 after being ejected, and the mixed refrigerant enters the primary evaporator 31. The refrigerant gas in the gas-liquid separator 4 returns to the compressor 1, completing a refrigeration cycle.
An embodiment of the method for recovering the organic solvent by using the secondary refrigeration liquefier is shown in fig. 4, and the preferred technological process is as follows:
and S1, pressurizing the organic solvent waste gas by a booster fan.
The pressure of the pressurized waste gas is 0.13-0.17 MPa. The gas pressure is improved, so that the condensation temperature of some components is reduced, the liquefaction effect is improved, and the higher the pressurization is, the better the liquefaction effect is.
And S2, the pressurized waste gas enters a normal-temperature water cooling heat exchanger for water cooling.
Through normal temperature water cooling, can remove a part of moisture in the waste gas, improve organic solvent gas share. For example, the temperature of the gas exhausted from a coating machine or a printing factory is 60-80 ℃, the volume proportion of the organic solvent gas in the gas is less than 10%, and the temperature is cooled to 30-40 ℃ by water cooling.
And S3, removing moisture in the waste gas through a dryer.
After drying, the water content of the waste gas is 0.02-0.03 g/m3. The purpose of drying is to reduce the refrigeration load.
Preferably, the dryer is a double-layer dryer, as shown in fig. 6, in order to cope with the complexity of organic solvent carrying water vapor, the double-layer dryer is designed, the lower layer desiccant 93 is a high temperature resistant desiccant such as alumina, and the like, and the upper layer desiccant 91 is a high water absorption desiccant such as silica gel, and the like. A buffer layer 92 is reserved between the upper layer drying agent 91 and the lower layer drying agent 93, and gas reforming and uniform distribution are facilitated.
Meanwhile, in order to facilitate the replacement of the drying agent, the drying agent tank is designed into a structure which is easy to disassemble, so that the drying agent in the tank body can be replaced conveniently.
And S4, introducing the heat regenerator to exchange heat with the exhaust gas of the secondary refrigeration liquefier for precooling.
After precooling, the temperature is reduced to 0-5 ℃. The heat regenerator adopts a two-flow plate type heat exchanger, so that higher heat transfer coefficient and system compactness are realized.
And S5, feeding the precooled waste gas into a secondary refrigeration liquefier, and respectively carrying out primary refrigeration and secondary refrigeration to obtain condensed liquid.
Two-stage refrigerating evaporators are arranged in the liquefier, wherein the refrigerating temperature of the first-stage evaporator is-15 to-25 ℃, the organic solvent above C8 can be condensed, and the refrigerating temperature of the second-stage evaporator is-50 to-60 ℃, the organic solvent between C4 and C7 can be condensed.
S6, carrying out liquid membrane separation on the condensed liquid to remove water and CO2And obtaining the pure organic solvent.
Preferably, the condensed liquid enters the organic solvent storage tank and then undergoes liquid membrane separation. The pure organic solvent separated by the liquid membrane is reused.
And S7, introducing a small amount of uncondensed gas into the heat regenerator, adsorbing by the adsorption tower to reach the standard, and then emptying.
The temperature of a small amount of non-condensed gas passing through the secondary refrigeration liquefier is lower, so that the exhaust gas of the secondary refrigeration liquefier and the gas entering the liquefier are sent into the adsorption tower for adsorption after heat exchange through the heat regenerator, the temperature is about 0-5 ℃, isothermal adsorption is facilitated in the adsorber, the effective adsorption capacity is improved, and the adsorption is exhausted after reaching the standard.
Meanwhile, one or two or even more adsorption towers can be adopted according to the waste gas treatment capacity. For example, 2 adsorption towers are conventionally used for continuous-operation coaters or printing plants.
And S8, returning the desorption gas to the pressurization step, and carrying out the condensation cycle again.
After the adsorption is saturated, the adsorber is regenerated, the exhaust gas dried in the step S3 is introduced into the adsorption tower to blow out the adsorbed organic gas, the organic gas is introduced into the pressurization step, and the condensation cycle is carried out again.
An organic solvent recovery system using the secondary refrigeration liquefier comprises a booster fan 7, a normal temperature water cooling heat exchanger 8, a dryer 9, a heat regenerator 10, a secondary refrigeration liquefier, a liquid membrane separator 12 and a gas adsorption tower which are connected in sequence as shown in fig. 5. The heat regenerator 10 comprises a dry waste gas inlet, a dry waste gas outlet, an uncondensed gas inlet and an uncondensed gas outlet, the dry waste gas inlet is communicated with the outlet of the dryer 9, the dry waste gas outlet is communicated with the primary evaporator 31 of the secondary refrigeration liquefier, the gas outlet of the secondary evaporator 32 of the secondary refrigeration liquefier is communicated with the uncondensed gas inlet of the heat regenerator 10, the uncondensed gas outlet of the heat regenerator 10 is communicated with the No. 1 adsorption tower 131 and the No. 2 adsorption tower 132 of the gas adsorption tower, the adsorption is exhausted after reaching the standard, after the adsorption is saturated, the adsorber is regenerated, the desorption gas is communicated with the inlet of the booster fan 7, and the booster fan 7 is positioned on a waste gas collecting pipeline containing an organic solvent; the liquid outlet of the secondary evaporator 32 of the secondary refrigeration liquefier communicates with the liquid membrane separator 12.
An organic solvent storage tank 11 can also be arranged between the secondary refrigeration liquefier and the liquid membrane separator 12 for temporarily storing the condensed liquid. The inlet of the organic solvent storage tank is communicated with the condensed liquid outlet of the secondary refrigeration liquefier, and the outlet of the organic solvent storage tank 11 is communicated with the inlet of the liquid membrane separator 12.
The dryer 9 is a double-layer dryer, as shown in fig. 6, which is designed to cope with the complexity of organic solvent carrying water vapor, and the lower layer dryer 93 is a high temperature resistant dryer such as alumina, and the upper layer dryer 91 is a high water absorption dryer such as silica gel. A buffer layer 92 is reserved between the upper layer drying agent 91 and the lower layer drying agent 93, and gas reforming and uniform distribution are facilitated.
Meanwhile, in order to facilitate the replacement of the drying agent, the drying agent tank is designed into a structure which is easy to disassemble, so that the drying agent in the tank body can be replaced conveniently.
The heat regenerator 10 uses a two-flow plate heat exchanger to achieve a high heat transfer coefficient and system compactness.
Example 1
The organic solvent recovery method is used for treating the waste gas containing the organic solvent in a coating machine or a printing factory and comprises the following steps:
step S1, installing a axial flow booster fan on the waste gas collecting pipeline of the coating machine or the printing plant, and boosting the waste gas to 0.15 MPa;
step S2, the supercharged waste gas enters a normal-temperature water cooling heat exchanger, and the temperature is reduced from 60-80 ℃ to 30-40 ℃;
step S3, further removing moisture in the waste gas through a double-layer dryer until the moisture content is 0.02-0.03 g/m3；
Step S4, introducing the dried waste gas into a heat regenerator to perform exhaust heat exchange with a secondary refrigeration liquefier for precooling, and reducing the temperature to 0-5 ℃;
step S5, feeding the precooled waste gas into a secondary refrigeration liquefier, and respectively carrying out primary refrigeration and secondary refrigeration to obtain condensed liquid; wherein the refrigeration temperature of the first-stage evaporator is between-15 ℃ and-25 ℃, the organic solvent above C8 can be condensed, the refrigeration temperature of the second-stage evaporator is between-50 ℃ and-60 ℃, and the organic solvent between C4 ℃ and C7 can be condensed;
step S6, the liquid obtained after passing through the secondary refrigeration liquefier enters an organic solvent storage tank and then enters a liquid membrane separator for liquid membrane separation, and water and CO are separated2Removing to obtain pure organic solvent for recycling;
and step S7, the temperature of the gas which is little and is not condensed after passing through the secondary refrigeration liquefier is lower, the gas exchanges heat with the gas entering the liquefier through the heat regenerator and then is sent into the adsorption tower for adsorption, the temperature is about 0-5 ℃, isothermal adsorption is facilitated in the adsorber, the effective adsorption quantity is improved, and the gas is exhausted after reaching the adsorption standard.
And step S8, regenerating the absorber after the adsorption is saturated, introducing the dried waste gas into the adsorption tower to blow out the adsorbed organic gas, and recycling before introducing the organic gas into the booster fan.
By adopting the method, the collection and the capture of more than 99 percent of the organic solvent can be realized, the full recovery and the zero discharge are realized in the true sense, and the recovered organic solvent is directly reused.
In addition to being used for treating the waste gas containing organic solvent of coating machine or printing factory, the method can also be used for removing any waste gas containing organic solvent above C4.
While the representative embodiments and test examples of the present invention have been described in detail, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical concept of the present invention, and modifications and combinations obvious to those skilled in the art are included in the scope of the present invention.
Claims (10)
1. A second-stage refrigeration liquefier is characterized by comprising a compressor, a condenser, an evaporator, a gas-liquid separator, a throttle valve and an ejector, wherein the evaporator comprises a first-stage evaporator and a second-stage evaporator, the first-stage evaporator and the second-stage evaporator are connected in parallel and are positioned between the gas-liquid separator and the ejector, the gas-liquid separator, the compressor, the condenser, the ejector and the first-stage evaporator are sequentially connected to form a first circulation loop, and the gas-liquid separator, the throttle valve, the second-stage evaporator, the ejector and the first-stage evaporator are sequentially connected to form a second circulation loop;
the ejector is a Laval nozzle and comprises a nozzle, a mixing chamber and a diffuser, the nozzle is provided with a refrigerant condensate inlet and a refrigerant evaporation gas inlet, the diffuser is provided with a refrigerant outlet, the refrigerant condensate inlet of the ejector is communicated with the condenser outlet, the refrigerant evaporation gas inlet is communicated with the secondary evaporator outlet, the refrigerant outlet is communicated with the primary evaporator inlet, and the primary evaporator outlet is communicated with the gas-liquid separator; the gas-liquid separator comprises a refrigerant inlet, a vapor refrigerant outlet and a liquid refrigerant outlet, the refrigerant inlet is communicated with the outlet of the primary evaporator, the liquid refrigerant outlet is connected with the throttling valve, the throttling valve is communicated with the inlet of the secondary evaporator, the vapor refrigerant outlet is communicated with the inlet of the compressor, and the outlet of the compressor is communicated with the inlet of the condenser;
the refrigeration temperature of the primary evaporator is-15 to-25 ℃, and the refrigeration temperature of the secondary evaporator is-50 to-60 ℃.
2. The two-stage refrigeration liquefier of claim 1, wherein the throttling valve is an electromagnetic expansion valve.
3. The two-stage refrigeration liquefier of claim 1, wherein the refrigerant is a low-temperature refrigerant capable of handling a low temperature below-60 ℃ or an environmentally-friendly mixed refrigerant with a low temperature below-60 ℃.
4. The two-stage refrigeration liquefier of claim 1, wherein the compressor is a cryogenic piston compressor having a capacity of 5P/10P or a combination thereof.
5. The two-stage refrigeration liquefier of claim 1, wherein the primary evaporator and the secondary evaporator are fin-tube evaporators or wound-tube evaporators.
6. The two-stage refrigeration liquefier of any of claims 1-5, wherein the primary evaporator is disposed at a lower portion and the secondary evaporator is disposed at an upper portion, and wherein a curved orifice plate is disposed between the primary evaporator and the secondary evaporator for liquid collection and gas flow distribution.
7. A method for recovering organic solvent is characterized in that a secondary refrigeration liquefier as claimed in any one of claims 1 to 6 is adopted to condense and liquefy waste gas containing organic solvent, and the waste gas is sequentially subjected to primary refrigeration and secondary refrigeration by heat exchange with a primary evaporator and a secondary evaporator respectively to obtain condensed liquid so as to recover the organic solvent; the refrigeration temperature of the primary evaporator is-15 to-25 ℃, and the refrigeration temperature of the secondary evaporator is-50 to-60 ℃.
8. The method according to claim 7, further comprising pre-treatment and post-treatment, wherein the pre-treatment comprises pressurization, water cooling, drying and pre-cooling, and the post-treatment comprises water removal of the condensed liquid, adsorption of a small amount of non-condensed gas, evacuation after reaching standards, return of desorbed gas to the pressurization step, and re-condensation cycle.
9. The method according to claim 8, wherein during precooling, the dried waste gas is precooled through heat exchange with the exhaust gas of the secondary refrigeration liquefier, and the temperature of the precooled waste gas is 0-5 ℃.
10. An organic solvent recovery system, which is characterized by being used for realizing the organic solvent recovery method of any one of claims 7 to 9, and comprising a booster fan, a normal temperature water cooling heat exchanger, a dryer, a heat regenerator, a secondary refrigeration liquefier, a liquid membrane separator and a gas adsorption tower which are connected in sequence; the regenerator comprises a dry waste gas inlet, a dry waste gas outlet, an uncondensed gas inlet and an uncondensed gas outlet, the dry waste gas inlet is communicated with the outlet of the dryer, the dry waste gas outlet is communicated with the primary evaporator of the secondary refrigeration liquefier, the gas outlet of the secondary evaporator of the secondary refrigeration liquefier is communicated with the uncondensed gas inlet of the regenerator, the uncondensed gas outlet of the regenerator is communicated with the gas adsorption tower, the desorption gas outlet of the adsorption tower is communicated with the inlet of the booster fan, and the booster fan is positioned on an organic solvent-containing waste gas collecting pipeline; and a condensed liquid outlet of the secondary refrigeration liquefier is communicated with the liquid membrane separator.
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