CN113713617A - Solar energy coupling MVR vacuum membrane distillation concentrated sulfuric acid solution system and method - Google Patents
Solar energy coupling MVR vacuum membrane distillation concentrated sulfuric acid solution system and method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 123
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000004821 distillation Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000008878 coupling Effects 0.000 title claims description 7
- 238000010168 coupling process Methods 0.000 title claims description 7
- 238000005859 coupling reaction Methods 0.000 title claims description 7
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 230000005855 radiation Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000004064 recycling Methods 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000009825 accumulation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 8
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- 239000002699 waste material Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000010612 desalination reaction Methods 0.000 description 1
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- 230000014509 gene expression Effects 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
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- 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
- B01D61/366—Apparatus therefor
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- 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
- B01D61/368—Accessories; Auxiliary operations
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Abstract
一种太阳能耦合MVR真空膜蒸馏浓缩硫酸溶液系统及方法，属于MVR技术领域。该装置包括原料罐、控制阀、循环泵、换热器、太阳能、太阳能集热器、真空泵、蒸汽蓄热器、排管、喷嘴、凝水罐、真空膜组件、蒸汽压缩机，本发明将太阳能、MVR技术和真空膜蒸馏技术结合起来，根据太阳辐射的强弱设置三种运行模式，充分利用了太阳能和二次蒸汽冷凝潜热作为热源加热原料液，采用真空膜蒸馏技术保证硫酸溶液高纯分离的同时，采用太阳能和MVR保证了其蒸发过程的高效节能特性，并节省了冷却水装置，有效减少了运行费用,适用于石油化工、钢铁、氯碱、有色金属等行业硫酸废液的高效回收利用。
A solar-coupled MVR vacuum membrane distillation concentrated sulfuric acid solution system and method belong to the technical field of MVR. The device includes a raw material tank, a control valve, a circulating pump, a heat exchanger, solar energy, a solar heat collector, a vacuum pump, a steam heat accumulator, an exhaust pipe, a nozzle, a condensate tank, a vacuum membrane assembly, and a steam compressor. Combining solar energy, MVR technology and vacuum membrane distillation technology, three operating modes are set according to the intensity of solar radiation, making full use of solar energy and the latent heat of condensation of secondary steam as heat sources to heat the raw material liquid, and adopting vacuum membrane distillation technology to ensure high purity of sulfuric acid solution At the same time of separation, the use of solar energy and MVR ensures the high-efficiency and energy-saving characteristics of its evaporation process, saves cooling water devices, and effectively reduces operating costs. use.
Description
Technical Field
The invention relates to the technical field of MVR, in particular to a solar energy coupling MVR vacuum membrane distillation concentration sulfuric acid solution system and a method.
Background
Sulfuric acid is used as a basic industrial raw material and is widely applied to industries such as steel, petrifaction, chlor-alkali, titanium dioxide and the like. However, because production equipment is simple and crude, technical conditions are poor, and environmental protection is less conscious, a large amount of sulfuric acid waste liquid is generated in the production and utilization process, and the direct discharge of the sulfuric acid waste liquid wastes resources and pollutes the environment. At present, the treatment of the sulfuric acid waste liquid mainly comprises neutralization, pyrolysis, chemical oxidation, extraction, single-effect evaporation, multi-effect evaporation and the like, and the problems of low separation efficiency, high energy consumption, poor operation stability and the like generally exist. Therefore, the reasonable and efficient treatment of the sulfuric acid waste liquid is an urgent need of numerous industries.
Membrane Distillation (MD) is a new heat-driven separation process, and aims to realize high-purity separation of a solution by using a hydrophobic microporous membrane as a barrier, wherein water molecules in the solution at a hot side are evaporated on the surface of the membrane and penetrate through membrane pores to reach a cold side under the drive of steam pressure difference at two sides of the membrane, while solute molecules cannot pass through the membrane pores. The membrane distillation can be classified into direct contact type, air gap type, air sweep type and vacuum type according to the condensing mode of the cold side water vapor. The membrane distillation technology has been widely applied to the fields of seawater desalination, wastewater treatment, traditional Chinese medicine concentration, food processing and the like because of the advantages of low operation temperature, high separation efficiency, strong corrosion resistance, simple process flow and the like. However, the existing membrane distillation technology generally uses boiler fresh steam or electric energy as a heating source, and has no steam latent heat recovery device, and the whole process has small membrane flux and high energy consumption. Mechanical Vapor Recompression (MVR) is a high-efficiency energy-saving technology, in which secondary vapor generated by an evaporator is compressed by a vapor compressor, the temperature and the pressure of the secondary vapor are increased, and the secondary vapor is used as a heat source to heat feed liquid, so that the latent heat of the secondary vapor is fully recycled. This technique has been widely used. Some researchers have tried to concentrate the sulfuric acid solution, however, the separation efficiency using the conventional wire mesh and cyclone is 90%, and the secondary steam contains a certain sulfuric acid component, which severely corrodes the compressor, thereby limiting further application of MVR.
The invention patent CN201610983912.4 discloses an MVR membrane distillation device and a method, the device comprises a support body, a hollow fiber microporous hydrophobic membrane component, a hollow fiber solid wall heat conduction pipe, a partition board, a steam channel, a compressor and other equipment, secondary steam produced by membrane distillation is compressed and heated by using a steam compressor, and then is used as a heat source to heat feed liquid, so that latent heat of the secondary steam is recovered, evaporation energy consumption is reduced, and operation cost is reduced. In fact, as the concentration of the sulfuric acid solution is increased continuously in the actual evaporation concentration process, the electric power consumption of the steam compressor is also increased rapidly, and when the concentration of the sulfuric acid solution is increased to a certain degree, the MVR can not save energy any more. Obviously, the MVR film distillation apparatus described above is not adapted to handle high concentration sulfuric acid solutions.
Solar energy is a renewable energy source which is rich and can be widely obtained, can be used as a heat source to efficiently meet the energy requirement of sulfuric acid solution membrane distillation at low cost, and has important value and significance. If solar energy is combined with an MVR membrane distillation technology to be applied to concentration and recovery of a high-concentration sulfuric acid solution, high-purity separation of the sulfuric acid solution can be guaranteed through the vacuum membrane distillation technology, and meanwhile, the high-efficiency and energy-saving characteristics of the evaporation process are guaranteed through the solar energy and the MVR. Therefore, how to couple solar energy with the MVR membrane distillation technology to concentrate and recover a high-concentration sulfuric acid solution is difficult to study.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a solar MVR vacuum membrane distillation concentrated sulfuric acid solution system and a solar MVR vacuum membrane distillation concentrated sulfuric acid solution method.
The technical scheme adopted by the invention is as follows: a solar energy coupling MVR vacuum membrane distillation concentration sulfuric acid solution system comprises a raw material tank, a first control valve, a second control valve, a third control valve, a fourth control valve, a fifth control valve, a sixth control valve, a first circulating pump, a second circulating pump, a first heat exchanger, a second heat exchanger, solar energy, a solar heat collector, a vacuum pump, a steam heat accumulator, a discharge pipe, a nozzle, a condensation tank, a vacuum membrane assembly and a steam compressor;
a solution outlet of the raw material tank is communicated with a sulfuric acid solution inlet of the vacuum membrane component through a second control valve and a first circulating pump in sequence, a steam outlet of the vacuum membrane component is communicated with a hot side inlet of a second heat exchanger through a steam compressor, a hot side outlet of the second heat exchanger is communicated with a steam inlet of a steam heat accumulator, a steam outlet of the steam heat accumulator is communicated with a third control valve and a vacuum pump in sequence, a solution outlet of the steam heat accumulator is communicated with a solution inlet of a solar heat collector through a fourth control valve and a second circulating pump in sequence, a solution outlet of the solar heat collector is communicated with a hot side inlet of the first heat exchanger, and a hot side outlet of the first heat exchanger is communicated with a condensate tank;
a sulfuric acid solution outlet of the vacuum membrane component is communicated with a cold side inlet of a second heat exchanger, a cold side outlet of the second heat exchanger is communicated with a cold side inlet of a first heat exchanger, and a cold side outlet of the first heat exchanger is communicated with a solution inlet of a raw material tank;
a drain outlet of the steam heat accumulator is communicated with a fifth control valve;
the liquid outlet of the raw material tank is communicated with a first control valve;
and the liquid outlet of the condensate tank is communicated with a sixth control valve.
The steam heat accumulator is internally provided with a plurality of distributed calandria, and the outlet of each calandria is provided with a nozzle.
And the outer surface of the steam heat accumulator is provided with a heat insulation material with a certain thickness.
The vacuum membrane component is internally provided with a plurality of hollow fiber membrane tubes, and the membrane tubes are prepared by polytetrafluoroethylene hydrophobic microporous membranes with the membrane aperture of 0.2-0.4 mu m.
The solar energy radiation intensity is divided into three intervals, when the solar radiation intensity is in a first interval, solar energy is adopted to provide a heat source for the system and a first operation mode is carried out, when the solar radiation intensity is in a second interval, solar energy coupling MVR is adopted to provide the heat source for the system and a second operation mode is carried out, and when the solar radiation intensity is in a third interval, MVR is adopted to provide the heat source for the system and a third operation mode is carried out.
The first mode of operation: firstly, a first circulating pump and a second control valve are started, a sulfuric acid solution preheated to a required temperature in a raw material tank is filled with a vacuum membrane component under the driving of the first circulating pump, then a vacuum pump and a third control valve are started to vacuumize the system, so that a tube pass of the vacuum membrane component is kept in a required negative pressure environment, water molecules of the sulfuric acid solution in the vacuum membrane component are evaporated on the surface of a shell pass membrane, pass through membrane holes to reach the tube pass under the driving of transmembrane steam pressure difference, then sequentially pass through a steam compressor and a second heat exchanger to enter a distribution exhaust pipe of a steam heat accumulator, and then are mixed and condensed with liquid water in the steam heat accumulator through a nozzle; and opening a second circulating pump and a fourth control valve, enabling the heated liquid water in the steam heat accumulator to enter a solar heat collector to absorb heat again, then entering a first heat exchanger to heat the concentrated solution from the vacuum membrane module, finally collecting the concentrated solution into a condensate tank to be recycled, returning the heated concentrated solution to the raw material tank to continue circulating concentration, and recycling the concentrated solution after the required concentration is reached.
The second operation mode: firstly, a first circulating pump and a second control valve are started, sulfuric acid solution preheated to a required temperature in a raw material tank is filled with a vacuum membrane component under the driving of the first circulating pump, then a vacuum pump and a third control valve are started to vacuumize the system, so that a tube pass of the vacuum membrane component is kept in a required negative pressure environment, a vapor compressor is started, water molecules of the sulfuric acid solution in the vacuum membrane component are evaporated on the surface of a shell pass membrane, pass through membrane holes under the driving of transmembrane vapor pressure difference to reach the tube pass, enter a second heat exchanger after being compressed by the vapor compressor, exchange heat with concentrated liquid from the vacuum membrane component, produced condensed water enters a distribution calandria of a vapor heat accumulator, then enters a liquid water mixing heat accumulator in the vapor heat accumulator through a nozzle, the second circulating pump and the fourth control valve are started, and heated liquid water in the vapor heat accumulator enters a solar heat collector to absorb heat again, and then the concentrated solution enters a first heat exchanger to continuously heat the concentrated solution from the vacuum membrane module, and finally the concentrated solution is collected into a condensate tank to be recycled, and the heated concentrated solution returns to the raw material tank to be continuously recycled and concentrated to achieve the required concentration and then be recycled.
The third operating mode: firstly, a first circulating pump and a second control valve are started, sulfuric acid solution preheated to the required temperature in a raw material tank is filled with a vacuum membrane component under the driving of the first circulating pump, then a vacuum pump and a third control valve are started to vacuumize the system, so that the tube pass of the vacuum membrane component keeps the required negative pressure environment, a vapor compressor is started, water molecules of sulfuric acid solution in the vacuum membrane component are evaporated on the surface of the shell pass membrane, driven by transmembrane vapor pressure difference, the water passes through the membrane hole to reach the tube pass, is compressed by a vapor compressor and then enters a second heat exchanger, exchanging heat with the concentrated solution from the vacuum membrane component, leading the produced condensed water to enter a distribution calandria of the steam heat accumulator, and then the concentrated solution in the second heat exchanger is heated and then returns to the raw material tank through the first heat exchanger for continuous circulating concentration, and the concentrated solution is recycled after reaching the required concentration.
The invention has the following beneficial effects: the invention combines the solar energy, MVR technology and vacuum membrane distillation technology, fully utilizes the solar energy and the latent heat of condensation of secondary steam as heat sources to heat the raw material liquid, adopts the vacuum membrane distillation technology to ensure the high-purity separation of the sulfuric acid solution, simultaneously adopts the solar energy and the MVR to ensure the high-efficiency energy-saving characteristic of the evaporation process, saves a cooling water device, effectively reduces the operating cost, and is suitable for the high-efficiency recycling of the sulfuric acid waste liquid in the industries of petrochemical industry, steel, chlor-alkali, nonferrous metal and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a diagram of a system for concentrating sulfuric acid solution by solar energy coupled MVR vacuum membrane distillation according to the present invention;
in the figure, 1 a raw material tank, 2-1 a first control valve, 2-2 a second control valve, 2-3 a third control valve, 2-4 a fourth control valve, 2-5 a fifth control valve, 2-6 a sixth control valve, 3-1 a first circulating pump, 3-2 a second circulating pump, 4-1 a first heat exchanger, 4-2 a second heat exchanger, 5 solar energy, 6 a solar heat collector, 7 a vacuum pump, 8 a steam heat accumulator, 9 a discharge pipe, 10 nozzles, 11 a condensed water tank, 12 a vacuum membrane component and 13 a steam compressor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are merely for convenience of description and should not be construed as limitations of the embodiments of the present invention, which are not described in any more detail in the following embodiments.
The terms of direction and position of the present invention, such as "up", "down", "front", "back", "left", "right", "inside", "outside", "top", "bottom", "side", etc., refer to the direction and position of the attached drawings. Accordingly, the use of directional and positional terms is intended to illustrate and understand the present invention and is not intended to limit the scope of the present invention.
As shown in fig. 1, in an embodiment of the present invention, a system and a method for concentrating a sulfuric acid solution by solar energy coupled MVR vacuum membrane distillation include a raw material tank 1, a first control valve 2-1, a second control valve 2-2, a third control valve 2-3, a fourth control valve 2-4, a fifth control valve 2-5, a sixth control valve 2-6, a first circulation pump 3-1, a second circulation pump 3-2, a first heat exchanger 4-1, a second heat exchanger 4-2, solar energy 5, a solar heat collector 6, a vacuum pump 7, a steam accumulator 8, a discharge pipe 9, a nozzle 10, a condensate tank 11, a vacuum membrane module 12, and a steam compressor 13;
a solution outlet of the raw material tank 1 is communicated with a sulfuric acid solution inlet of the vacuum membrane component 12 through a second control valve 2-2 and a first circulating pump 3-1 in sequence, the steam outlet of the vacuum membrane module 12 is communicated with the hot side inlet of the second heat exchanger 4-2 through a steam compressor 13, the hot side outlet of the second heat exchanger 4-2 is communicated with the steam inlet of the steam heat accumulator 8, a steam outlet of the steam heat accumulator 8 is communicated with third control valves 2-3 and a vacuum pump 7 in sequence, the solution outlet of the steam heat accumulator 8 is communicated with the solution inlet of the solar heat collector 6 through a fourth control valve 2-4 and a second circulating pump 3-2 in sequence, a solution outlet of the solar heat collector 6 is communicated with a hot side inlet of the first heat exchanger 4-1, and a hot side outlet of the first heat exchanger 4-1 is communicated with the water condensing tank 11;
a sulfuric acid solution outlet of the vacuum membrane module 12 is communicated with a cold side inlet of a second heat exchanger 4-2, a cold side outlet of the second heat exchanger 4-2 is communicated with a cold side inlet of a first heat exchanger 4-1, and a cold side outlet of the first heat exchanger 4-1 is communicated with a solution inlet of a raw material tank 1;
a drain outlet of the steam heat accumulator 8 is communicated with a fifth control valve 2-5;
a liquid outlet of the raw material tank 1 is communicated with a first control valve 2-1;
and a liquid outlet of the condensate tank 11 is communicated with the sixth control valve 2-6.
A plurality of distribution calandria 9 are arranged in the steam heat accumulator 8, and a nozzle 10 is arranged at the outlet of each calandria 9.
The outer surface of the steam heat accumulator 8 is provided with a heat insulation material with a certain thickness, so that the heat loss of steam condensate water is reduced.
The vacuum membrane component 12 is internally provided with a plurality of hollow fiber membrane tubes, the membrane tubes are prepared by polytetrafluoroethylene hydrophobic microporous membranes with the membrane aperture of 0.2-0.4 mu m, and the material has the excellent characteristics of acid resistance, alkali resistance, heat resistance and cold resistance.
The radiation intensity of the solar energy 5 is divided into three intervals, when the solar radiation intensity is in a first interval, namely the solar radiation intensity can provide energy meeting system requirements, the solar energy is adopted to provide a heat source for the system and a first operation mode is carried out, when the solar radiation intensity is in a second interval, namely the solar radiation intensity can provide energy meeting part of system requirements, the solar energy coupled MVR is adopted to provide the heat source for the system and carry out a second operation mode, when the solar radiation intensity is in a third interval, namely the solar radiation intensity only provides a little energy meeting the system requirements, the MVR is adopted to provide the heat source for the system and carry out a third operation mode, and according to the actual operation condition of the system, the actual numerical values of the three intervals are set by taking energy conservation and high efficiency as targets.
The first mode of operation: firstly, a first circulating pump 3-1 and a second control valve 2-2 are started, a sulfuric acid solution preheated to a required temperature in a raw material tank 1 is filled with a vacuum membrane component 12 under the driving of the first circulating pump 3-1, then a vacuum pump 7 and a third control valve 2-3 are started to vacuumize the system, so that a tube pass of the vacuum membrane component 12 is kept in a required negative pressure environment, water molecules of the sulfuric acid solution in the vacuum membrane component 12 are evaporated on the surface of a shell pass membrane, pass through membrane holes to reach the tube pass under the driving of transmembrane steam pressure difference, then sequentially pass through a steam compressor 13 and a second heat exchanger 4-2 to enter a distribution calandria 9 of a steam heat accumulator 8, and then are mixed and condensed with liquid water in the steam heat accumulator 8 through a nozzle 10; and (3) starting a second circulating pump 3-2 and a fourth control valve 2-4, enabling the heated liquid water in the steam heat accumulator 8 to enter a solar heat collector 6 to absorb heat again, then entering a first heat exchanger 4-1 to heat the concentrated solution from the vacuum membrane module 12, finally collecting the concentrated solution into a condensate tank 11 to be recycled, returning the heated concentrated solution to the raw material tank 1 to be continuously and circularly concentrated, and recycling the concentrated solution after the required concentration is achieved.
The second operation mode: firstly, a first circulating pump 3-1 and a second control valve 2-2 are started, a sulfuric acid solution preheated to a required temperature in a raw material tank 1 is filled with a vacuum membrane component 12 under the driving of the first circulating pump 3-1, then a vacuum pump 7 and a third control valve 2-3 are started to vacuumize the system, so that a tube pass of the vacuum membrane component 12 is kept in a required negative pressure environment, a vapor compressor 13 is started, water molecules of the sulfuric acid solution in the vacuum membrane component 12 are evaporated on the surface of a shell pass membrane, pass through membrane holes under the driving of transmembrane vapor pressure difference to reach the tube pass, enter a second heat exchanger 4-2 after being compressed by the vapor compressor 13 to exchange heat with a concentrated solution from the vacuum membrane component 12, produced condensed water enters a distribution calandria distribution pipe 9 of a vapor heat accumulator 8, then is mixed with liquid water in the vapor accumulator 8 through a nozzle 10 to accumulate heat, and the second circulating pump 3-2 and the fourth control valve 2-4 are started, the heated liquid water in the steam heat accumulator 8 enters the solar heat collector 6 to absorb heat again, then enters the first heat exchanger 4-1 to continue heating the concentrated solution from the vacuum membrane component 12, and finally is collected into the condensate tank 11 to be recycled, and the heated concentrated solution returns to the raw material tank 1 to continue circulating concentration, and is recycled after reaching the required concentration.
The third operating mode: firstly, a first circulating pump 3-1 and a second control valve 2-2 are started, a sulfuric acid solution preheated to a required temperature in a raw material tank 1 is driven by the first circulating pump 3-1 to fill a vacuum membrane assembly 12, then a vacuum pump 7 and a third control valve 2-3 are started to vacuumize the system, so that a tube pass of the vacuum membrane assembly 12 is kept in a required negative pressure environment, a vapor compressor 13 is started, water molecules of the sulfuric acid solution in the vacuum membrane assembly 12 are evaporated on the surface of a shell pass membrane, the water molecules pass through membrane holes under the drive of transmembrane vapor pressure difference to reach the tube pass, the water molecules are compressed by the vapor compressor 13 and then enter a second heat exchanger 4-2 to exchange heat with a concentrated solution from the vacuum membrane assembly 12, the produced condensed water enters a distribution calandria 9 of a vapor heat accumulator 8 and then is mixed with liquid water in the vapor accumulator 8 through a nozzle 10 to accumulate heat, and the concentrated solution in the second heat exchanger 4-2 returns to the raw material tank 1 through the first heat exchanger 4-1 after being heated Continuously circularly concentrating to achieve the required concentration and then recycling.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (8)
1. A solar energy coupling MVR vacuum membrane distillation concentration sulphuric acid solution system which is characterized in that: the device comprises a raw material tank (1), a first control valve (2-1), a second control valve (2-2), a third control valve (2-3), a fourth control valve (2-4), a fifth control valve (2-5), a sixth control valve (2-6), a first circulating pump (3-1), a second circulating pump (3-2), a first heat exchanger (4-1), a second heat exchanger (4-2), solar energy (5), a solar heat collector (6), a vacuum pump (7), a steam heat accumulator (8), a drain pipe (9), a nozzle (10), a condensate tank (11), a vacuum membrane component (12) and a steam compressor (13);
a solution outlet of the raw material tank (1) is communicated with a sulfuric acid solution inlet of the vacuum membrane component (12) sequentially through a second control valve (2-2) and a first circulating pump (3-1), a steam outlet of the vacuum membrane component (12) is communicated with a hot side inlet of a second heat exchanger (4-2) through a steam compressor (13), a hot side outlet of the second heat exchanger (4-2) is communicated with a steam inlet of a steam heat accumulator (8), a steam outlet of the steam heat accumulator (8) is communicated with a third control valve (2-3) and a vacuum pump (7) sequentially, a solution outlet of the steam heat accumulator (8) is communicated with a solution inlet of a solar heat collector (6) sequentially through a fourth control valve (2-4) and the second circulating pump (3-2), and a solution outlet of the solar heat collector (6) is communicated with a hot side inlet of the first heat exchanger (4-1), the hot side outlet of the first heat exchanger (4-1) is communicated with the condensed water tank (11);
a sulfuric acid solution outlet of the vacuum membrane assembly (12) is communicated with a cold side inlet of a second heat exchanger (4-2), a cold side outlet of the second heat exchanger (4-2) is communicated with a cold side inlet of a first heat exchanger (4-1), and a cold side outlet of the first heat exchanger (4-1) is communicated with a solution inlet of a raw material tank (1);
a drain outlet of the steam heat accumulator (8) is communicated with a fifth control valve (2-5);
the liquid outlet of the raw material tank (1) is communicated with a first control valve (2-1);
and a liquid outlet of the condensate tank (11) is communicated with a sixth control valve (2-6).
2. The system of claim 1 for concentrating sulfuric acid by solar-coupled MVR vacuum membrane distillation, further characterized by: the steam heat accumulator (8) is internally provided with a plurality of distribution calandria (9), and the outlet of each calandria (9) is provided with a nozzle (10).
3. The system of claim 2, wherein the concentrated sulfuric acid solution is obtained by solar energy coupled MVR vacuum membrane distillation, and further comprises: and the outer surface of the steam heat accumulator (8) is provided with a heat insulation material with a certain thickness.
4. The system of claim 1 for concentrating sulfuric acid by solar-coupled MVR vacuum membrane distillation, further characterized by: the vacuum membrane component (12) is internally provided with a plurality of hollow fiber membrane tubes, and the membrane tubes are prepared by polytetrafluoroethylene hydrophobic microporous membranes with the membrane aperture of 0.2-0.4 mu m.
5. A method of operating the solar coupled MVR vacuum membrane distillation concentrated sulfuric acid solution system of claim 1, further characterized by: the solar energy (5) is divided into three sections, when the solar radiation intensity is in a first section, solar energy is adopted to provide a heat source for the system and a first operation mode is carried out, when the solar radiation intensity is in a second section, solar energy coupling MVR is adopted to provide the heat source for the system and a second operation mode is carried out, and when the solar radiation intensity is in a third section, MVR is adopted to provide the heat source for the system and a third operation mode is carried out.
6. The method of claim 5, wherein the solar energy coupled MVR vacuum membrane distillation concentrated sulfuric acid solution system is further characterized in that: the first mode of operation: firstly, a first circulating pump (3-1) and a second control valve (2-2) are started, a sulfuric acid solution preheated to a required temperature in a raw material tank (1) is filled with a vacuum membrane component (12) under the driving of the first circulating pump (3-1), then a vacuum pump (7) and a third control valve (2-3) are started to vacuumize a system, so that a tube pass of the vacuum membrane component (12) is kept in a required negative pressure environment, water molecules of the sulfuric acid solution in the vacuum membrane component (12) are evaporated on the surface of a shell pass membrane, and pass through membrane holes to reach the tube pass under the driving of transmembrane steam pressure difference, then enter a distribution calandria (9) of a steam heat accumulator (8) through a steam compressor (13) and a second heat exchanger (4-2) in sequence, and then are mixed and condensed with liquid water in the steam heat accumulator (8) through a nozzle (10); and (3) starting a second circulating pump (3-2) and a fourth control valve (2-4), enabling the heated liquid water in the steam heat accumulator (8) to enter a solar heat collector (6) to absorb heat again, then entering a first heat exchanger (4-1) to heat the concentrated solution from the vacuum membrane module (12), finally collecting the concentrated solution into a condensate tank (11) for recycling, and returning the heated concentrated solution into the raw material tank (1) for continuous circulating concentration to achieve the required concentration and then recycling.
7. The method of claim 5, wherein the solar energy coupled MVR vacuum membrane distillation concentrated sulfuric acid solution system is further characterized in that: the second operation mode: firstly, a first circulating pump (3-1) and a second control valve (2-2) are started, sulfuric acid solution preheated to the required temperature in a raw material tank (1) is filled with a vacuum membrane component (12) under the driving of the first circulating pump (3-1), then a vacuum pump (7) and a third control valve (2-3) are started to vacuumize a system, so that a tube pass of the vacuum membrane component (12) is kept in a required negative pressure environment, a vapor compressor (13) is started, water molecules of the sulfuric acid solution in the vacuum membrane component (12) are evaporated on the surface of a shell pass membrane, the water molecules pass through membrane holes to reach the tube pass under the driving of transmembrane vapor pressure difference, the water molecules are compressed by the vapor compressor (13) and then enter a second heat exchanger (4-2) to exchange heat with concentrated solution from the vacuum membrane component (12), and produced condensate water enters a distribution exhaust pipe (9) of a vapor heat accumulator (8), and then the mixture is mixed with liquid water in a steam heat accumulator (8) through a nozzle (10) for heat accumulation, a second circulating pump (3-2) and a fourth control valve (2-4) are started, the heated liquid water in the steam heat accumulator (8) enters a solar heat collector (6) for heat absorption again, then enters a first heat exchanger (4-1) for continuous heating of concentrated solution from a vacuum membrane assembly (12), and finally is collected into a condensed water tank (11) for recycling, and the heated concentrated solution returns to a raw material tank (1) for continuous circulating concentration, and is recycled after reaching the required concentration.
8. The method of claim 5, wherein the solar energy coupled MVR vacuum membrane distillation concentrated sulfuric acid solution system is further characterized in that: the third operating mode: firstly, a first circulating pump (3-1) and a second control valve (2-2) are started, sulfuric acid solution preheated to the required temperature in a raw material tank (1) is filled with a vacuum membrane component (12) under the driving of the first circulating pump (3-1), then a vacuum pump (7) and a third control valve (2-3) are started to vacuumize a system, so that a tube pass of the vacuum membrane component (12) is kept in a required negative pressure environment, a vapor compressor (13) is started, water molecules of the sulfuric acid solution in the vacuum membrane component (12) are evaporated on the surface of a shell pass membrane, the water molecules pass through membrane holes to reach the tube pass under the driving of transmembrane vapor pressure difference, the water molecules are compressed by the vapor compressor (13) and then enter a second heat exchanger (4-2) to exchange heat with concentrated solution from the vacuum membrane component (12), and produced condensate water enters a distribution exhaust pipe (9) of a vapor heat accumulator (8), then the concentrated solution in the second heat exchanger (4-2) is heated and then returns to the raw material tank (1) through the first heat exchanger (4-1) for continuous circulating concentration, and the concentrated solution is recycled after reaching the required concentration.
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