CN111036083B - Three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol - Google Patents
Three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol Download PDFInfo
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- CN111036083B CN111036083B CN201911398588.XA CN201911398588A CN111036083B CN 111036083 B CN111036083 B CN 111036083B CN 201911398588 A CN201911398588 A CN 201911398588A CN 111036083 B CN111036083 B CN 111036083B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 445
- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 230000018044 dehydration Effects 0.000 title claims abstract description 76
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000926 separation method Methods 0.000 title claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 106
- 230000008020 evaporation Effects 0.000 claims abstract description 106
- 239000002994 raw material Substances 0.000 claims abstract description 82
- 230000000694 effects Effects 0.000 claims abstract description 24
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims description 272
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000011084 recovery Methods 0.000 claims description 54
- 238000004458 analytical method Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 8
- 238000005373 pervaporation Methods 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 24
- 238000005265 energy consumption Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol. Raw material alcohol enters three alcohol evaporation dehydration systems respectively for dehydration and purification, and a finished product of absolute alcohol is obtained. The steam heat is used in series among the three systems in turn. The invention adopts the three-effect thermal coupling dehydration technology to utilize the absolute alcohol steam of the former effect as the heat source of the raw alcohol evaporator of the latter effect, thereby realizing the recycling of heat and concentrating and recycling the light alcohol without consuming extra energy. The consumption of alcohol vapor is not more than 0.2 ton, and compared with the single-effect pervaporation membrane separation dehydration process, the energy is saved by more than 55%.
Description
Technical Field
The invention relates to the technical field of alcohol production processes, in particular to a three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol.
Background
In recent years, the nations greatly popularize fuel ethanol, and the aim of realizing the nationwide basic coverage of ethanol gasoline by 2020 is proposed in the 'embodiments for expanding the production of biofuel ethanol and popularizing and using ethanol gasoline for vehicles' of the combined printout of 15 groups of Commission of national Committee for improvement of China, 2017 and the like. The national institute of 22 days of 8.2018 holds a frequent conference, and the state at that time often decides to "sequentially expand the use of ethanol gasoline for vehicles and popularize 26 provinces and cities in the country". At present, the production capacity of the fuel ethanol in China is less than 300 ten thousand tons, the consumption of the domestic gasoline is about 1.3 hundred million tons, and the national basic coverage is realized in 2020 according to the addition proportion of 10 percent, the fuel ethanol demand is 1300 ten thousand tons, the gap is 1000 ten thousand tons, and the market potential is huge.
At present, there are four main methods for alcohol dehydration at home and abroad:
(1) The method adopts benzene or cyclohexane azeotropic distillation to dehydrate, the energy consumption of the method is higher, and benzene or cyclohexane residues are easy to be remained in the product, so that the method is eliminated.
(2) The method has no residue, good product quality, but high energy consumption.
(3) The molecular sieve adsorption method is adopted for dehydration, the method has no residue, the product concentration is high, and the energy consumption is relatively low.
(4) The method has no residue and low energy consumption by adopting the pervaporation membrane separation technology.
In the current day of increasingly shortage of energy sources, the requirements on energy consumption are higher and higher, and alcohol dehydration technology with lower energy consumption is required.
Disclosure of Invention
The invention provides a three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol aiming at the defects of the prior art. The three-effect thermal coupling dehydration technology is adopted, and the anhydrous alcohol vapor of the former effect is used as the heat source of the raw alcohol evaporator of the latter effect, so that the heat can be reused.
The invention is realized by the following technical scheme:
The first aspect of the invention provides a three-way membrane separation dehydration energy-saving device for preparing absolute alcohol, which comprises a raw material preheater; the raw material preheater is connected with a first alcohol evaporation and dehydration system through a first alcohol feeding pipe, the raw material preheater is connected with a second alcohol evaporation and dehydration system through a second alcohol feeding pipe, and the raw material preheater is connected with a third alcohol evaporation and dehydration system through a third alcohol feeding pipe; the reboiler is connected with a first alcohol evaporation and dehydration system through a first reboiler pipe, and the first alcohol evaporation and dehydration system is connected with a second alcohol evaporation and dehydration system through a first anhydrous alcohol vapor pipe; the second alcohol evaporation and dehydration system is connected with a third alcohol evaporation and dehydration system through a second anhydrous alcohol steam pipe; the second alcohol evaporation and dehydration system is sequentially connected with the first alcohol evaporation and dehydration system and the finished product cooler through a first alcohol discharging pipe, the third alcohol evaporation and dehydration system is sequentially connected with the second alcohol evaporation and dehydration system and the finished product cooler through a second alcohol discharging pipe, and the third alcohol evaporation and dehydration system is connected with the finished product cooler through a third anhydrous alcohol steam pipe;
The first alcohol evaporation and dehydration system comprises an effective evaporation recovery tower and an effective membrane component; the upper part of the first-effect evaporation recovery tower is sequentially connected with a first-effect feeding second-stage preheater, a first-effect feeding first-stage preheater and a raw material preheater through a first alcohol feeding pipe, and the top of the first-effect evaporation recovery tower is connected with a first-effect membrane component; the bottom of the first-effect evaporation recovery tower is connected with a light alcohol secondary preheater;
the second alcohol evaporation dehydration system comprises a two-effect evaporator and a two-effect membrane assembly; the middle part of the second-effect evaporator is sequentially connected with the second-effect feeding second-stage preheater, the second-effect feeding first-stage preheater and the raw material preheater through a second alcohol feeding pipe, and the top of the second-effect evaporator is connected with the second-effect membrane component;
The third alcohol evaporation dehydration system comprises a triple-effect evaporator and a triple-effect membrane component; the middle part of the triple effect evaporator is connected with the triple effect feed preheater and the raw material preheater in sequence through a third alcohol feed pipe, and the top of the triple effect evaporator is connected with the triple effect membrane component.
Preferably, the top of the first-effect evaporation recovery tower is connected with the first-effect membrane component through a first-effect superheater; the top of the second-effect evaporator is connected with the second-effect membrane component through a second-effect superheater; the top of the triple-effect evaporator is connected with the triple-effect membrane component through a triple-effect superheater.
Preferably, the first-effect membrane component is connected with the upper part of the second-effect evaporator through a first anhydrous alcohol vapor pipe; the second-effect membrane component is connected with the upper part of the three-effect evaporator through a second absolute alcohol steam pipe; the three-effect membrane component is sequentially connected with the raw material preheater, the three-effect condenser and the finished product cooler through a third absolute alcohol pipe.
Preferably, the lower part of the second-effect evaporator is sequentially connected with a first-effect feeding primary preheater, a weak alcohol primary preheater and a finished product cooler through a first alcohol discharging pipe; the lower part of the triple-effect evaporator is sequentially connected with a double-effect feeding primary preheater and a finished product cooler through a second alcohol discharging pipe.
Preferably, the first-effect membrane component is sequentially connected with a first-effect analysis condenser, a light alcohol primary preheater and a light alcohol secondary preheater through pipelines and then connected with the middle part of the first-effect evaporation recovery tower; the second-effect membrane component is connected with the first-stage light alcohol preheater through a second-effect analysis condenser; the three-effect membrane component is connected with the light alcohol primary preheater through a three-effect analysis condenser.
Preferably, the reboiler and the first-effect evaporation recovery tower are respectively connected through a first reboiler pipe and a water return pipe, and the reboiler is sequentially connected with the first-effect feeding secondary preheater, the second-effect feeding secondary preheater and the third-effect feeding preheater through a second reboiler pipe.
A second aspect of the present invention provides an energy saving method for preparing absolute alcohol, comprising the steps of:
(1) The steam enters a reboiler, water flowing back from the one-effect evaporation recovery tower is heated to 160 ℃ under the pressure of 0.6MPa, and then enters the one-effect evaporation recovery tower to become hot water at 153 ℃, so that heat is provided for the one-effect evaporation recovery tower to evaporate raw alcohol; condensed water in the shell pass of the reboiler enters a first-effect feeding secondary preheater, heat is provided for the first-effect feeding secondary preheater to enable the temperature to reach 125 ℃, hot water after heating the first-effect secondary preheater enters the second-effect feeding secondary preheater, heat is provided for the second-effect feeding secondary preheater to enable the temperature to reach 113 ℃, hot water after heating the second-effect feeding secondary preheater enters a third-effect feeding preheater, and heat is provided for the third-effect feeding preheater to enable the temperature to reach 100 ℃;
(2) The raw material alcohol enters a raw material preheater to be preheated to 80 ℃, and then is divided into three parts: a first raw material alcohol, a second raw material alcohol, and a third raw material alcohol;
(3) The method comprises the steps that first raw material alcohol enters an effective feeding primary preheater to be heated to 115 ℃, then enters an effective feeding secondary preheater to be heated to 125 ℃, finally enters an effective evaporation recovery tower to be evaporated to obtain alcohol vapor at 125 ℃, the alcohol vapor at 125 ℃ is changed into superheated alcohol vapor through an effective superheater, the superheated alcohol vapor enters an effective membrane assembly to be dehydrated to obtain first anhydrous alcohol vapor, the first anhydrous alcohol vapor enters a secondary evaporator to provide heat for the secondary evaporator, the temperature of the secondary evaporator is kept at 118 ℃, then enters the effective feeding primary preheater to maintain the temperature of the effective feeding primary preheater, then enters a light alcohol primary preheater to provide heat for the light alcohol primary preheater, and finally enters a finished product cooler to be cooled to obtain anhydrous alcohol;
The second raw material alcohol enters a second-effect feeding primary preheater to be heated to 108 ℃, then enters a second-effect feeding secondary preheater to be heated to 113 ℃, finally enters a second-effect evaporator to be evaporated to obtain alcohol steam at 118 ℃, the alcohol steam at 118 ℃ is changed into superheated alcohol steam through the second-effect superheater and enters a second-effect membrane module to be dehydrated to obtain second absolute alcohol steam, the second absolute alcohol steam enters a third-effect evaporator to provide heat for the third-effect evaporator, the temperature of the third-effect evaporator is kept at 112 ℃, then enters the second-effect feeding primary preheater to maintain the temperature of the second-effect feeding primary preheater, and finally enters a finished product cooler to be cooled to obtain absolute alcohol;
the third raw material alcohol enters a three-effect feed preheater to be heated to 100 ℃, then enters a three-effect evaporator to be evaporated to obtain alcohol steam at 112 ℃, the alcohol steam at 112 ℃ is changed into superheated alcohol steam through the three-effect superheater, enters a three-effect membrane module to be dehydrated to obtain third absolute alcohol steam, and the third absolute alcohol steam enters the raw material preheater to provide heat for the raw material preheater, is condensed by the three-effect condenser and enters a finished product cooler to be cooled to obtain absolute alcohol;
(4) The first-effect membrane component is used for dehydrating alcohol steam and then separating water vapor containing a small amount of absolute ethyl alcohol, the water vapor enters the first-effect analysis condenser to be changed into light alcohol, the light alcohol enters the first-stage light alcohol preheater and the second-stage light alcohol preheater and then is gradually heated, finally, the light alcohol enters the middle part of the first-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the first-effect evaporation recovery tower and enters the reboiler through a water return pipe to be heated to 160 ℃ for recycling;
The vapor containing a small amount of absolute ethyl alcohol, which is separated by the second-effect membrane component, enters the second-effect resolving condenser to be changed into the absolute ethyl alcohol, the absolute ethyl alcohol enters the first-stage absolute ethyl alcohol preheater and the second-stage absolute ethyl alcohol preheater and then is gradually heated, finally enters the middle part of the first-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the first-effect evaporation recovery tower and enters the reboiler through a water return pipe to be heated to 160 ℃ for recycling;
The vapor containing a small amount of absolute ethyl alcohol, which is separated by the three-effect membrane component, enters the three-effect analysis condenser to be changed into the absolute ethyl alcohol, the absolute ethyl alcohol enters the absolute ethyl alcohol primary preheater and the absolute ethyl alcohol secondary preheater and then is gradually heated, finally enters the middle part of the one-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the one-effect evaporation recovery tower and enters the reboiler through the water return pipe to be heated to 160 ℃ for recycling.
Preferably, in the step (1), the concentration of the raw material alcohol is 95% (v/v); the first raw material alcohol accounts for 42% of the raw material alcohol in mass percent, the second raw material alcohol accounts for 33% of the raw material alcohol in mass percent, and the third raw material alcohol accounts for 25% of the raw material alcohol in mass percent.
Preferably, in step (2), the first-effect membrane module, the second-effect membrane module and the third-effect membrane module are all a plurality of shell-and-tube membrane structures connected in series, each shell-and-tube membrane structure comprises a shell and an inner tube positioned inside the shell, and the inner tube comprises a ceramic tube and a molecular sieve membrane covered on the outer surface of the ceramic tube.
Preferably, the reboiler, the two-effect evaporator and the three-effect evaporator are all of shell-and-tube structures, and comprise a shell and an inner tube positioned in the shell; the raw material preheater, the first-effect feeding primary preheater, the second-effect feeding secondary preheater, the third-effect feeding preheater, the light alcohol primary preheater and the light alcohol secondary preheater are all spiral plate type heat exchangers.
The water flowing out of the first-effect evaporation recovery tower is led into the tube side of the reboiler, the steam is led into the shell side, and the steam heats the water in the tube side and simultaneously the steam becomes condensation water.
The shell side of the two-effect evaporator is internally provided with first anhydrous alcohol vapor, the tube side is internally provided with raw material alcohol, and the raw material alcohol is heated into alcohol vapor by the heat of the first anhydrous alcohol;
the second absolute alcohol steam is introduced into the shell pass of the triple-effect evaporator, raw material alcohol is introduced into the tube pass, and the raw material alcohol is changed into alcohol steam through the heat of the second absolute alcohol;
The raw material preheater, the first-effect feeding primary preheater, the first-effect feeding secondary preheater, the second-effect feeding primary preheater, the second-effect feeding secondary preheater, the third-effect feeding preheater, the light alcohol primary preheater and the light alcohol secondary preheater are all spiral plate type heat exchangers. Because each preheater and pipeline are operated above saturation pressure, under the action of pressure, the raw material alcohol and water (water heated by reboiler) are all higher than 100 deg.C, but still exist in liquid form.
The raw material alcohol and the third absolute alcohol vapor exchange heat (preheating to 80 ℃) in the raw material preheater;
The first-effect feeding primary preheater is internally provided with a condensate heat exchange (preheated to 115 ℃) after the raw material alcohol and the first anhydrous alcohol vapor are condensed;
the primary feed secondary preheater is internally provided with heat exchange between raw material alcohol and condensed water flowing out of the reboiler (preheated to 125 ℃);
the second-effect feeding primary preheater is internally provided with a condensate heat exchange (preheated to 108 ℃) after the raw material alcohol and the second absolute alcohol vapor are condensed;
The heat exchange between the raw material alcohol and the condensed water flowing out of the reboiler (preheating to 113 ℃) is carried out in the secondary preheater of the secondary feeding;
The three-effect feed preheater is internally provided with heat exchange between raw material alcohol and condensed water flowing out of the reboiler (preheating to 100 ℃);
the light alcohol first-stage preheater exchanges heat with condensate after the light alcohol and the first anhydrous alcohol vapor are condensed;
the light alcohol secondary preheater exchanges heat (preheats to 153 ℃) with the waste water discharged from the bottom of the first-effect evaporation recovery tower.
The beneficial effects of the invention are as follows:
1. Compared with the single-effect pervaporation membrane separation technology, the method adopts a three-effect thermal coupling dehydration technology, utilizes the absolute alcohol vapor of the former effect as the heat source of the raw alcohol evaporator of the latter effect, realizes the recycling of heat, and saves more than 55 percent of energy compared with the single-effect pervaporation membrane separation dehydration technology because the absolute alcohol vapor consumption per ton is not more than 0.2 ton.
2. Compared with the single-effect pervaporation membrane separation technology, the method provided by the invention has the advantages that the light alcohol generated by dehydration is not abandoned or is recycled and purified, and the purification of the light alcohol can be completed under the condition of no extra energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a three-effect membrane separation dehydration energy-saving process flow chart for preparing absolute alcohol.
In the figure: 1. raw material preheater, 2. First-effect evaporation recovery tower, 3. Second-effect evaporator, 4. Third-effect evaporator, 5. Finished product cooler, 6. Reboiler, 7. First-effect feed primary preheater, 8. Second-effect feed primary preheater, 9. First-effect feed secondary preheater, 10. Second-effect feed secondary preheater, 11. Third-effect feed preheater, 12. Light alcohol primary preheater, 13. Light alcohol secondary preheater, 14. First-effect superheater, 15. First-effect membrane assembly, 16. First-effect resolution condenser, 17. Second-effect superheater, 18. Second-effect membrane assembly, 19. Second-effect resolution condenser, 20. Third-effect superheater, 21. Third-effect membrane assembly, 22. Third-effect resolution condenser, 23. Third-effect condenser, 24. First reboiler pipe, 25. Return pipe, 26. Second reboiler pipe, 27. First anhydrous alcohol refined steam pipe, 28. Second anhydrous alcohol steam pipe, 29, third anhydrous alcohol steam pipe, 30. First alcohol, 31, third feed pipe, 32, third feed pipe, 34. First feed pipe, 34.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In the description of the present invention, it should be noted that the positional or positional relationship indicated by the terms such as "upper", "lower", "inner", "outer", etc. are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
As described in the background art, the energy consumption is lowest in the existing alcohol dehydration technology by adopting a pervaporation membrane separation technology, namely raw alcohol is firstly sent into a distillation tower for distillation, then sent into an effective membrane component for purification to obtain absolute alcohol steam, and the absolute alcohol is obtained after cooling. However, in this process, much heat is only used once, and the purified light alcohol is generally discarded or additionally recovered, so that not only is heat wasted, but also additional energy is consumed for recovering the light alcohol.
Based on the method, the invention provides a three-effect membrane separation dehydration energy-saving method and device for preparing absolute alcohol, which can repeatedly utilize heat generated by distillation of raw material alcohol and separate, recover and purify the light alcohol without consuming extra energy.
The invention relates to a three-effect membrane separation dehydration energy-saving device for preparing absolute alcohol, which comprises a raw material preheater 1, a reboiler 6, a finished product cooler 5, a first alcohol evaporation dehydration system, a second alcohol evaporation dehydration system and a third alcohol evaporation dehydration system; the raw material preheater 1 is connected with a first alcohol evaporation and dehydration system through a first alcohol feeding pipe 30, the raw material preheater 1 is connected with a second alcohol evaporation and dehydration system through a second alcohol feeding pipe 31, and the raw material preheater 1 is connected with a third alcohol evaporation and dehydration system through a third alcohol feeding pipe 32; the reboiler 6 is connected with a first alcohol evaporation and dehydration system through a first reboiler pipe 24, and the first alcohol evaporation and dehydration system is connected with a second alcohol evaporation and dehydration system through a first anhydrous alcohol vapor pipe 27; the second alcohol evaporation and dehydration system is connected with a third alcohol evaporation and dehydration system through a second absolute alcohol steam pipe 28; the second alcohol evaporation and dehydration system is sequentially connected with the first alcohol evaporation and dehydration system and the finished product cooler 5 through a first alcohol discharge pipe 33, the third alcohol evaporation and dehydration system is sequentially connected with the second alcohol evaporation and dehydration system and the finished product cooler 5 through a second alcohol discharge pipe 34, and the third alcohol evaporation and dehydration system is connected with the finished product cooler 5 through a third absolute alcohol steam pipe 29;
The first alcohol evaporation and dehydration system comprises an effective evaporation recovery tower 2 and an effective membrane component 15; the upper part of the first-effect evaporation recovery tower 2 is sequentially connected with a first-effect feeding second-stage preheater 9, a first-effect feeding first-stage preheater 7 and a raw material preheater 1 through a first alcohol feeding pipe 30, and the top of the first-effect evaporation recovery tower 2 is connected with a first-effect membrane assembly 15; the bottom of the first-effect evaporation recovery tower 2 is connected with a light alcohol secondary preheater 13;
The second alcohol evaporation dehydration system comprises a two-effect evaporator 3 and a two-effect membrane component 18; the middle part of the second-effect evaporator 3 is sequentially connected with the second-effect feeding second-stage preheater 10, the second-effect feeding first-stage preheater 8 and the raw material preheater 1 through a second alcohol feeding pipe 31, and the top of the second-effect evaporator 3 is connected with the second-effect membrane component 18;
The third alcohol evaporation dehydration system comprises a triple-effect evaporator 4 and a triple-effect membrane component 21; the middle part of the triple effect evaporator 4 is sequentially connected with the triple effect feed preheater 11 and the raw material preheater 1 through a third alcohol feed pipe 32, and the top of the triple effect evaporator 4 is connected with the triple effect membrane module 21.
Further, the top of the first-effect evaporation recovery tower 2 is connected with a first-effect membrane component 15 through a first-effect superheater 14; the top of the second-effect evaporator 3 is connected with the second-effect membrane component 18 through a second-effect superheater 17; the top of the triple effect evaporator 4 is connected with a triple effect membrane module 21 through a triple effect superheater 20.
Further, the first-effect membrane component 15 is connected with the upper part of the second-effect evaporator 3 through a first anhydrous alcohol vapor pipe 27; the second-effect membrane component 18 is connected with the upper part of the three-effect evaporator 4 through a second absolute alcohol steam pipe 28; the three-effect membrane assembly 21 is sequentially connected with the raw material preheater 1, the three-effect condenser 23 and the finished product cooler 5 through a third absolute alcohol steam pipe 29.
Further, the lower part of the second-effect evaporator 3 is sequentially connected with a first-effect feeding primary preheater 7, a weak alcohol primary preheater 12 and a finished product cooler 5 through a first alcohol discharging pipe 33; the lower part of the triple-effect evaporator 4 is sequentially connected with a double-effect feeding primary preheater 8 and a finished product cooler 5 through a second alcohol discharging pipe 34.
Further, the first-effect membrane component 15 is sequentially connected with a first-effect analysis condenser 16, a light alcohol primary preheater 12 and a light alcohol secondary preheater 13 through pipelines, and is further connected with the middle part of the first-effect evaporation recovery tower 2; the second-effect membrane component 18 is connected with the first-stage light alcohol preheater 12 through a second-effect analysis condenser 19; the three-way membrane component 21 is connected with the first-stage light alcohol preheater 12 through a three-way analysis condenser 22.
Further, the reboiler 6 is connected with the first-effect evaporation recovery tower 2 through a first reboiler pipe 24 and a water return pipe 25 respectively, and the reboiler 6 is sequentially connected with the first-effect feeding secondary preheater 9, the second-effect feeding secondary preheater 10 and the third-effect feeding preheater 11 through a second reboiler pipe 26.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments. If experimental details are not specified in the examples, the conditions are generally conventional or recommended by the reagent company; reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified.
Examples
95% (V/v) of the raw alcohol is preheated by the raw preheater 1 and then divided into three parts:
(1) Raw alcohol accounting for 42 mass percent enters the first-effect feeding primary preheater 7 to be preheated to 115 ℃ through the first alcohol feeding pipe 30, enters the first-effect feeding secondary preheater 9 to be heated to 125 ℃, and finally enters the upper part of the first-effect evaporation recovery tower 2 to be distilled. The water at the bottom of the first-effect evaporation recovery tower 2 enters a reboiler 6 through a water return pipe 25, steam enters the reboiler 6 to heat the water to 160 ℃, the steam pressure is 0.6MPa, and heated hot water enters the first-effect evaporation recovery tower 2 through a first reboiler pipe 24, so that the temperature at the bottom of the first-effect evaporation recovery tower 2 is 153 ℃, heat is provided for distillation of raw alcohol, and the raw alcohol is changed into alcohol steam. Condensed water in the shell pass of the reboiler 6 sequentially enters the first-effect feed secondary preheater 9, the second-effect feed secondary preheater 10 and the third-effect feed preheater 11 through the second reboiler pipeline 26 to provide heat, hot water after the heat is provided returns to a boiler room and is changed into steam to be heated for the reboiler 6. The alcohol vapor enters into an effect superheater 14 for further heating, then enters into an effect membrane assembly 15 for dehydration and purification, the alcohol vapor enters into the shell side of the effect membrane assembly 15, the water vapor in the alcohol vapor permeates into the inner tube with the molecular sieve membrane through the Dalton partial pressure law under the pressure of 0.5MPa, and meanwhile, a small amount of alcohol vapor is permeated into the inner tube with the water vapor, and the liquid in the inner tube becomes light alcohol vapor. The light alcohol steam is cooled into light alcohol through a first-effect analysis condenser 16, the light alcohol sequentially enters a first-stage light alcohol preheater 12 and a second-stage light alcohol preheater 13 for preheating, finally enters the middle part of a first-effect evaporation recovery tower 2, the light alcohol is heated, and the separated alcohol steam moves to the top of the tower and is converged with raw material alcohol steam at the upper part of the tower to be continuously dehydrated and purified in the next step. The water separated from the light alcohol moves to the bottom of the first-effect evaporation recovery tower 2, enters the reboiler 6 through the water return pipe 25 to be heated, and returns to the bottom of the tower through the first reboiler pipe 24 to continue to provide heat. The wastewater at the bottom of the tower is discharged after passing through the light alcohol secondary preheater 13 and provides heat for the light alcohol secondary preheater 13. The first anhydrous alcohol vapor is obtained after the purification of the first-effect membrane assembly 15, enters the upper part of the second-effect evaporator 3, moves downwards to provide distillation heat for the second-effect evaporator 3 so that the temperature of the second-effect evaporator 3 is maintained at 118 ℃, flows out of the lower part of the second-effect evaporator 3 and enters the first-effect feeding primary preheater 7 through the first alcohol discharging pipe 33 so as to provide heat for the first-effect feeding primary preheater 7, and the temperature of the first-effect feeding primary preheater 7 is maintained at 115 ℃; then enters a primary preheater 12 of the weak alcohol to provide heat for the weak alcohol, finally enters a finished product cooler 5, and is cooled to obtain the finished product absolute ethyl alcohol.
(2) Raw alcohol accounting for 33% of the mass fraction enters the second alcohol feed pipe 31 into the first-stage preheater 8 for preheating to 108 ℃, then enters the second-stage preheater 10 for second-stage feeding, finally enters the second-stage evaporator 3 for distillation to form alcohol vapor, the alcohol vapor enters the second-stage superheater 17 for further heating, then enters the second-stage membrane assembly 18 for dehydration and purification, the alcohol vapor enters the shell side of the second-stage membrane assembly 18, and under the pressure of 0.5MPa, the water vapor in the alcohol vapor permeates into the inner tube with the molecular sieve membrane through the Dalton partial pressure law, meanwhile, a small amount of alcohol vapor is permeated into the inner tube with the water vapor, and the liquid in the inner tube becomes light alcohol vapor. The light alcohol steam is cooled into light alcohol through a two-effect resolving condenser 19, the light alcohol sequentially enters a light alcohol primary preheater 12 and a light alcohol secondary preheater 13 for preheating, finally enters the middle part of a one-effect evaporation recovery tower 2, the light alcohol is heated, and the separated alcohol steam moves to the top of the tower and is converged with raw material alcohol steam at the upper part of the tower to be continuously dehydrated and purified in the next step. The water separated from the light alcohol moves to the bottom of the first-effect evaporation recovery tower 2, enters the reboiler 6 through the water return pipe 25 to be heated, and returns to the bottom of the tower through the first reboiler pipe 24 to continue to provide heat. The wastewater at the bottom of the tower is discharged after passing through the secondary pre-heater 13 for the weak alcohol. The second absolute alcohol vapor is obtained after the purification of the second-effect membrane assembly 18, enters the upper part of the three-effect evaporator 4 to move downwards to provide distillation heat for the three-effect evaporator 4 so that the temperature of the three-effect evaporator 4 is maintained at 112 ℃, and then enters the second-effect feeding primary preheater 8 from the lower part of the three-effect evaporator 4 through the second alcohol discharging pipe 34 to provide heat for the second-effect feeding primary preheater 8 so that the temperature of the second-effect feeding primary preheater 8 is maintained at 108 ℃; and finally, the mixture enters a finished product cooler 5 to be cooled to obtain finished absolute ethyl alcohol.
(3) Raw material alcohol accounting for 25% of the mass fraction enters a three-effect feed preheater 11 through a third alcohol feed pipe 32 to be preheated to 100 ℃, then enters a three-effect evaporator 4 to be distilled into alcohol steam, the alcohol steam enters a three-effect superheater 20 to be further heated, then enters a three-effect membrane component 21 to be dehydrated and purified, the alcohol steam enters a shell side of the three-effect membrane component 21, under the pressure of 0.5MPa, water vapor in the alcohol steam permeates into an inner tube with a molecular sieve membrane through a Dalton partial pressure law, meanwhile, a small amount of alcohol steam is permeated into the inner tube with the water vapor, and liquid in the inner tube becomes light alcohol steam. The light alcohol steam is cooled into light alcohol through a three-effect resolving condenser 22, the light alcohol sequentially enters a light alcohol primary preheater 12 and a light alcohol secondary preheater 13 for preheating, finally enters the middle part of a first-effect evaporation recovery tower 2, the light alcohol is heated, and the separated alcohol steam moves to the top of the tower and is converged with raw material alcohol steam at the upper part of the tower to be continuously dehydrated and purified in the next step. The water separated from the light alcohol moves to the bottom of the first-effect evaporation recovery tower 2, enters the reboiler 6 through the water return pipe 25 to be heated, and returns to the bottom of the tower through the first reboiler pipe 24 to continue to provide heat. The wastewater at the bottom of the tower is discharged after passing through the secondary pre-heater 13 for the weak alcohol. The third absolute alcohol vapor is obtained after the purification of the three-way film component 21, enters the raw material preheater 1 through a third absolute alcohol vapor pipeline 29 to maintain the temperature of the raw material preheater 1 at 80 ℃, is condensed through the three-way condenser 23, finally enters the finished product cooler 5, and is cooled to obtain the finished absolute alcohol.
Table 1 shows the steam energy consumption of the four dehydration technologies mentioned in the background art and the steam energy consumption of the examples.
TABLE 1 steam energy consumption for producing Anhydrous alcohol per ton
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (5)
1. The three-effect membrane separation dehydration energy-saving device for preparing absolute alcohol is characterized by comprising a raw material preheater; the raw material preheater is connected with a first alcohol evaporation and dehydration system through a first alcohol feeding pipe, the raw material preheater is connected with a second alcohol evaporation and dehydration system through a second alcohol feeding pipe, and the raw material preheater is connected with a third alcohol evaporation and dehydration system through a third alcohol feeding pipe; the reboiler is connected with a first alcohol evaporation and dehydration system through a first reboiler pipe, and the first alcohol evaporation and dehydration system is connected with a second alcohol evaporation and dehydration system through a first anhydrous alcohol vapor pipe; the second alcohol evaporation and dehydration system is connected with a third alcohol evaporation and dehydration system through a second anhydrous alcohol steam pipe; the second alcohol evaporation and dehydration system is sequentially connected with the first alcohol evaporation and dehydration system and the finished product cooler through a first alcohol discharging pipe, the third alcohol evaporation and dehydration system is sequentially connected with the second alcohol evaporation and dehydration system and the finished product cooler through a second alcohol discharging pipe, and the third alcohol evaporation and dehydration system is connected with the finished product cooler through a third anhydrous alcohol steam pipe;
The first alcohol evaporation and dehydration system comprises an effective evaporation recovery tower and an effective membrane component; the upper part of the first-effect evaporation recovery tower is sequentially connected with a first-effect feeding second-stage preheater, a first-effect feeding first-stage preheater and a raw material preheater through a first alcohol feeding pipe, and the top of the first-effect evaporation recovery tower is connected with a first-effect membrane component; the bottom of the first-effect evaporation recovery tower is connected with a light alcohol secondary preheater;
The second alcohol evaporation dehydration system comprises a two-effect evaporator and a two-effect membrane assembly; the bottom of the second-effect evaporator is sequentially connected with the second-effect feeding second-stage preheater, the second-effect feeding first-stage preheater and the raw material preheater through a second alcohol feeding pipe, and the top of the second-effect evaporator is connected with the second-effect membrane component;
The third alcohol evaporation dehydration system comprises a triple-effect evaporator and a triple-effect membrane component; the bottom of the triple effect evaporator is sequentially connected with the triple effect feed preheater and the raw material preheater through a third alcohol feed pipe, and the top of the triple effect evaporator is connected with the triple effect membrane component;
The top of the first-effect evaporation recovery tower is connected with the first-effect membrane component through a first-effect superheater; the top of the second-effect evaporator is connected with the second-effect membrane component through a second-effect superheater; the top of the triple-effect evaporator is connected with the triple-effect membrane component through a triple-effect superheater;
The first-effect membrane component is connected with the upper part of the second-effect evaporator through a first anhydrous alcohol vapor pipe; the second-effect membrane component is connected with the upper part of the three-effect evaporator through a second absolute alcohol steam pipe; the three-effect membrane component is sequentially connected with a raw material preheater, a three-effect condenser and a finished product cooler through a third absolute alcohol pipe;
The lower part of the second-effect evaporator is sequentially connected with a first-effect feeding primary preheater, a weak alcohol primary preheater and a finished product cooler through a first alcohol discharging pipe; the lower part of the three-effect evaporator is sequentially connected with a two-effect feeding primary preheater and a finished product cooler through a second alcohol discharging pipe;
The first-effect membrane component is sequentially connected with a first-effect analysis condenser, a light alcohol primary preheater and a light alcohol secondary preheater through pipelines and then connected with the middle part of the first-effect evaporation recovery tower; the second-effect membrane component is connected with the first-stage light alcohol preheater through a second-effect analysis condenser; the three-effect membrane component is connected with the light alcohol primary preheater through a three-effect analysis condenser;
The reboiler and the first-effect evaporation recovery tower are respectively connected through a first reboiler pipe and a water return pipe, and the reboiler is sequentially connected with the first-effect feeding secondary preheater, the second-effect feeding secondary preheater and the third-effect feeding preheater through a second reboiler pipe.
2. An energy efficient process for preparing absolute alcohol using the device of claim 1, characterized in that it comprises the steps of:
(1) The steam enters a reboiler, water flowing back from the one-effect evaporation recovery tower is heated to 160 ℃ under the pressure of 0.6MPa, and then enters the one-effect evaporation recovery tower to become hot water at 153 ℃, so that heat is provided for the one-effect evaporation recovery tower to evaporate raw alcohol; condensed water in the shell pass of the reboiler enters a first-effect feeding secondary preheater, heat is provided for the first-effect feeding secondary preheater to enable the temperature to reach 125 ℃, hot water after heating the first-effect secondary preheater enters the second-effect feeding secondary preheater, heat is provided for the second-effect feeding secondary preheater to enable the temperature to reach 113 ℃, hot water after heating the second-effect feeding secondary preheater enters a third-effect feeding preheater, and heat is provided for the third-effect feeding preheater to enable the temperature to reach 100 ℃;
(2) The raw material alcohol enters a raw material preheater to be preheated to 80 ℃, and then is divided into three parts: a first raw material alcohol, a second raw material alcohol, and a third raw material alcohol;
(3) The method comprises the steps that first raw material alcohol enters an effective feeding primary preheater to be heated to 115 ℃, then enters an effective feeding secondary preheater to be heated to 125 ℃, finally enters an effective evaporation recovery tower to be evaporated to obtain alcohol vapor at 125 ℃, the alcohol vapor at 125 ℃ is changed into superheated alcohol vapor through an effective superheater, the superheated alcohol vapor enters an effective membrane assembly to be dehydrated to obtain first anhydrous alcohol vapor, the first anhydrous alcohol vapor enters a secondary evaporator to provide heat for the secondary evaporator, the temperature of the secondary evaporator is kept at 118 ℃, then enters the effective feeding primary preheater to maintain the temperature of the effective feeding primary preheater, then enters a light alcohol primary preheater to provide heat for the light alcohol primary preheater, and finally enters a finished product cooler to be cooled to obtain anhydrous alcohol;
The second raw material alcohol enters a second-effect feeding primary preheater to be heated to 108 ℃, then enters a second-effect feeding secondary preheater to be heated to 113 ℃, finally enters a second-effect evaporator to be evaporated to obtain alcohol steam at 118 ℃, the alcohol steam at 118 ℃ is changed into superheated alcohol steam through the second-effect superheater and enters a second-effect membrane module to be dehydrated to obtain second absolute alcohol steam, the second absolute alcohol steam enters a third-effect evaporator to provide heat for the third-effect evaporator, the temperature of the third-effect evaporator is kept at 112 ℃, then enters the second-effect feeding primary preheater to maintain the temperature of the second-effect feeding primary preheater, and finally enters a finished product cooler to be cooled to obtain absolute alcohol;
the third raw material alcohol enters a three-effect feed preheater to be heated to 100 ℃, then enters a three-effect evaporator to be evaporated to obtain alcohol steam at 112 ℃, the alcohol steam at 112 ℃ is changed into superheated alcohol steam through the three-effect superheater, enters a three-effect membrane module to be dehydrated to obtain third absolute alcohol steam, and the third absolute alcohol steam enters the raw material preheater to provide heat for the raw material preheater, is condensed by the three-effect condenser and enters a finished product cooler to be cooled to obtain absolute alcohol;
(4) The first-effect membrane component is used for dehydrating alcohol steam and then separating water vapor containing a small amount of absolute ethyl alcohol, the water vapor enters the first-effect analysis condenser to be changed into light alcohol, the light alcohol enters the first-stage light alcohol preheater and the second-stage light alcohol preheater and then is gradually heated, finally, the light alcohol enters the middle part of the first-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the first-effect evaporation recovery tower and enters the reboiler through a water return pipe to be heated to 160 ℃ for recycling;
The vapor containing a small amount of absolute ethyl alcohol, which is separated by the second-effect membrane component, enters the second-effect resolving condenser to be changed into the absolute ethyl alcohol, the absolute ethyl alcohol enters the first-stage absolute ethyl alcohol preheater and the second-stage absolute ethyl alcohol preheater and then is gradually heated, finally enters the middle part of the first-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the first-effect evaporation recovery tower and enters the reboiler through a water return pipe to be heated to 160 ℃ for recycling;
The vapor containing a small amount of absolute ethyl alcohol, which is separated by the three-effect membrane component, enters the three-effect analysis condenser to be changed into the absolute ethyl alcohol, the absolute ethyl alcohol enters the absolute ethyl alcohol primary preheater and the absolute ethyl alcohol secondary preheater and then is gradually heated, finally enters the middle part of the one-effect evaporation recovery tower, absolute ethyl alcohol and water are separated, the absolute ethyl alcohol is evaporated and recovered, and the water enters the bottom of the one-effect evaporation recovery tower and enters the reboiler through the water return pipe to be heated to 160 ℃ for recycling.
3. The method according to claim 2, wherein in step (1), the concentration of the raw material alcohol is 95% (v/v); the first raw material alcohol accounts for 42% of the raw material alcohol in mass percent, the second raw material alcohol accounts for 33% of the raw material alcohol in mass percent, and the third raw material alcohol accounts for 25% of the raw material alcohol in mass percent.
4. The method of claim 2, wherein in step (2), the first-effect membrane module, the second-effect membrane module, and the third-effect membrane module are each a plurality of shell-and-tube membrane structures connected in series, each shell-and-tube membrane structure comprising an outer shell and an inner tube located inside the outer shell, the inner tube comprising a ceramic tube and a molecular sieve membrane coated on an outer surface of the ceramic tube.
5. The method of claim 2, wherein the reboiler, the two-way evaporator, and the three-way evaporator are all shell-and-tube structures comprising a housing and an inner tube positioned inside the housing; the raw material preheater, the first-effect feeding primary preheater, the second-effect feeding secondary preheater, the third-effect feeding preheater, the light alcohol primary preheater and the light alcohol secondary preheater are all spiral plate type heat exchangers.
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