CN109437112B - Gas dryer for ozone by using concentrated sulfuric acid as drying agent - Google Patents
Gas dryer for ozone by using concentrated sulfuric acid as drying agent Download PDFInfo
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- CN109437112B CN109437112B CN201811622064.XA CN201811622064A CN109437112B CN 109437112 B CN109437112 B CN 109437112B CN 201811622064 A CN201811622064 A CN 201811622064A CN 109437112 B CN109437112 B CN 109437112B
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
Abstract
The invention belongs to the technical field of high-concentration ozone production equipment, and particularly relates to a gas dryer for ozone, which uses concentrated sulfuric acid as a drying agent; the gas-liquid mixer comprises a cylinder body arranged in a pressure barrel, wherein a partition plate and a bottom plate are respectively arranged at the upper part and the lower part in the cylinder body, a plurality of porous plates are arranged in the cylinder body between the partition plate and the bottom plate at intervals up and down, through holes are formed in the partition plate and the porous plates, an air inlet pipe is inserted into the through holes, a concentrated sulfuric acid inlet pipe is inserted into the air inlet pipe, a concentrated sulfuric acid inlet and outlet, an air inlet and an air outlet are formed in a top cover, the air inlet pipe is communicated with the air inlet, the upper end of the concentrated sulfuric acid inlet pipe is connected with the concentrated sulfuric acid inlet and outlet in the top cover, an air outlet pipe is also arranged on the partition plate, and the air outlet pipe is connected with the air outlet in the top cover.
Description
The technical field is as follows:
the invention belongs to the technical field of high-concentration ozone production equipment, and particularly relates to a gas dryer for ozone, which uses concentrated sulfuric acid as a drying agent.
Background art:
it is well known that ozone has important applications as a strong oxidizing agent in many industries, especially after sterilization and oxidation of compounds, without leaving any undesirable by-products by itself, and is the oxidizing agent of choice for the industry. But the ozone has high production cost and influences the popularization and application of the ozone. When producing ozone, most enterprises select oxygen-rich sources for oxygen production by air and molecular sieves to produce ozone, and the concentration of ozone produced by an ozone machine is closely related to the dryness of air or oxygen besides being directly related to the concentration of oxygen. If the specific ozone machine has the ozone concentration of only 100g/m at the dew point temperature dryness of-40 DEG C3However, at a dew point temperature dryness of-60 ℃, oxygen passing through an ozone generator has the ability to have an ozone concentration of up to 200g/m in the oxygen3The dew point temperature from-40 ℃ to-60 ℃ can double the concentration of ozone, so that the power consumption can be reduced, the oxidation capacity is increased, the water vapor partial pressure is only reduced from 12.9Pa to 1.08Pa, the water vapor partial pressure is reduced by 11.8Pa, the quantity of condensed water is not large, the water vapor partial pressure reduction value from-30 ℃ to-40 ℃ is only half of that of 38.1-12.9 which is 25.2Pa, but the dehydration difficulty is increased, and the dew point temperature of-60 ℃ cannot be reached by conventional compression, cooling, silica gel drying agents and molecular sieve oxygenerator drying. This phenomenon has triggered many experts, and some solid desiccants can reach a dew point temperature of-60 ℃, but face the problem of high dehydration cost.
Common solid desiccants mainly comprise phosphorus pentoxide, magnesium perchlorate, potassium hydroxide, aluminum oxide, silica gel, calcium sulfate, magnesium oxide, magnesium bromide, sodium hydroxide, calcium oxide, calcium chloride, zinc bromide, copper sulfate and the like, according to the prior knowledge, desiccants such as silica gel, calcium sulfate, magnesium oxide, magnesium bromide, sodium hydroxide, calcium oxide, calcium chloride, zinc bromide, copper sulfate and the like are not easy to be used as drying agents at 60 ℃ below zero, potassium hydroxide and aluminum oxide can be used as drying agents at 60 ℃ below zero, but the drying agents are not suitable for frequent replacement with small capacity, the suitable solid drying agents are phosphorus pentoxide and magnesium perchlorate, the magnesium perchlorate is very toxic and troublesome to regenerate, the phosphorus pentoxide absorbs water to become phosphoric acid, and cannot be regenerated, and the cost problem exists because a large amount of water absorption.
The common liquid desiccant is concentrated sulfuric acid, and the concentrated sulfuric acid has the advantages of convenience in replacement, heating and regeneration and basically unchanged resistance after absorbing water, and has the defects of strong oxidizing property, strong acidity, strong corrosivity and weak volatile decomposability; concentrated sulfuric acid is used as a drying agent, and the dried gas component can only be neutral or acidic and can not chemically react with the concentrated sulfuric acid, so that the commonly used dried gas comprises oxygen, nitrogen, hydrogen, carbon dioxide, inert gas, partial hydrocarbon and the like; when the gas is used for producing ozone by an ozone machine, the effective component is oxygen, and the impurity gas components comprise nitrogen and carbon dioxide; the gas for the ozone machine is in a flowing state rather than a static state, so that the gas and the liquid are mainly considered to be fully and uniformly mixed when in aeration contact, the contact area is as large as possible, and the gas can instantaneously absorb the moisture in the gas; the dew point temperature of 100% concentrated sulfuric acid can reach-68 ℃, the problem of sulfur trioxide volatilization exists in an aeration state, the sulfuric acid concentration can only be concentrated to 98% after water absorption is failed and then heated, and the dew point temperature of-60 ℃ is difficult to reach under the condition of normal pressure and 25 ℃ of 98% concentrated sulfuric acid, so that whether the woolen cloth is replaced by 100% concentrated sulfuric acid every time? Obviously, under which conditions the 98% concentrated sulfuric acid can act as a water-absorbing desiccant at a dew point temperature of-60? The invention not only solves the difficult problem theoretically, but also solves the problem on the specific structure of the dryer.
The invention content is as follows:
the invention aims to provide a gas dryer for ozone, which can instantly absorb moisture in gas by using concentrated sulfuric acid as a drying agent so that the dew point temperature of the gas reaches-60 ℃ under pressure.
The invention is realized by the following steps:
a gas dryer for ozone using concentrated sulfuric acid as drying agent comprises a pressure vessel, a gas-liquid mixer, wherein the pressure vessel comprises a pressure barrel and a top cover, the gas-liquid mixer comprises a barrel body arranged in the pressure barrel, a partition plate and a bottom plate are respectively arranged at the upper middle part and the lower part in the barrel body, the barrel body is separated into a backflushing storage device and a perforated plate aeration mixer by the partition plate, the partition plate is provided with a communicating backflushing storage device and a gas outlet hole of the perforated plate aeration mixer, a plurality of perforated plates are arranged at intervals up and down in the perforated plate aeration mixer, a first exhaust hole communicated with the perforated plate aeration mixer is arranged at the lower part of a gas inlet pipe, a through hole is arranged on the partition plate and the perforated plate, the gas inlet pipe is inserted in the through hole, a concentrated sulfuric acid inlet pipe is inserted in the gas inlet pipe, a concentrated sulfuric acid inlet and outlet pipe and a gas outlet are arranged on the top cover, all be provided with the switch on air inlet, concentrated sulfuric acid import and export, the gas outlet, intake pipe and air inlet intercommunication, concentrated sulfuric acid import and export the upper end of exit tube and be connected with concentrated sulfuric acid import and export on the top cap, still be provided with the outlet duct on the division board, the outlet duct passes through the hose connection with the gas outlet on the top cap, barrel, perforated plate, division board, bottom plate are made by corrosion-resistant material.
In the gas dryer for ozone using concentrated sulfuric acid as a drying agent, separating pipes are arranged between adjacent porous plates, between the porous plates and the separating plates and between the porous plates and the bottom plate, the separating pipes are sleeved outside the air inlet pipe, and exhaust holes II communicating the inner cavity of the air inlet pipe and the porous plate aeration mixer are arranged on the separating pipes.
In the above-mentioned gas dryer for ozone using concentrated sulfuric acid as a drying agent, a three-way joint is arranged on the concentrated sulfuric acid inlet and outlet, one interface is a concentrated sulfuric acid inlet and outlet interface, and the other interface is a motorized interface. The other interface is a pressure measuring port, and a three-way joint is also arranged on the motor interface.
In the gas dryer for ozone using concentrated sulfuric acid as a drying agent, the aperture of the holes on the porous plates is 0.5-2mm, the holes are arranged in concentric circles, the circles are spaced at intervals of 5-20mm, the holes in each circle are spaced at intervals of 5-10mm, and the spacing distance between adjacent porous plates is 100-200 mm.
In the gas dryer for ozone using concentrated sulfuric acid as the drying agent, the isolation plate is fixedly connected with the cylinder body, the gas inlet pipe and the gas outlet pipe in a welding mode, and the porous plate is fixedly connected with the cylinder body and the gas inlet pipe in a welding or tight connection mode.
In the above-mentioned gas dryer for ozone using concentrated sulfuric acid as a drying agent, the corrosion-resistant material is glass or polytetrafluoroethylene or plastic.
In the above-mentioned gas dryer for ozone using concentrated sulfuric acid as a drying agent, a ventilation port is provided at the bottom of the pressure barrel, and a switch is provided on the ventilation port.
In the above-described gas dryer for ozone using concentrated sulfuric acid as a drying agent, the pressure vessel is made of carbon steel or stainless steel.
In the above gas dryer for ozone using concentrated sulfuric acid as a drying agent, the pressure vessel is externally wrapped with heat insulation cotton.
In the above-mentioned gas dryer for ozone using concentrated sulfuric acid as a drying agent, a cooling dryer is provided on a pipeline between the air inlet and the air compressor.
Compared with the prior art, the invention has the outstanding advantages that:
the gas dryer is an innovative gas dryer combining various container structures under theoretical guidance, and on the basis of analyzing the fact that concentrated sulfuric acid is pressurized by an external air compressor and cooled by a cold dryer, the condition of the concentrated sulfuric acid serving as a gas dryer for ozone is met.
Description of the drawings:
FIG. 1 is a schematic cross-sectional view of the present invention;
FIG. 2 is a cross-sectional view A-A of FIG. 1;
fig. 3 is a top view of the overcap of the present invention.
In the figure: 1. a pressure barrel; 2. a top cover; 3. a barrel; 4. a separator plate; 5. a base plate; 6. a perforated plate; 7. an air inlet pipe; 8. a concentrated sulfuric acid inlet and outlet pipe; 9. an air inlet; 10. an inlet and an outlet for concentrated sulfuric acid; 11. an air outlet; 12. a switch; 13. an air outlet pipe; 14. a hose; 15. a load-bearing ring; 16. heat insulation cotton; 17. a ventilation port; 18. a motorized interface; 19. a pressure measurement port; 20. a separation tube; 21. and (5) fastening the flange.
The specific implementation mode is as follows:
the invention will now be further described in the following by way of specific examples, with reference to figures 1 to 3:
the utility model provides an utilize concentrated sulfuric acid to be gas desicator for ozone of drier, including pressure vessel, gas-liquid mixer, pressure vessel includes pressure vessel 1 and top cap 2, gas-liquid mixer is including setting up barrel 3 in pressure vessel 1, well upper portion in barrel 3, the lower part is provided with division board 4 respectively, bottom plate 5, division board 4 separates barrel 3 for the recoil memory on upper portion and the perforated plate aeration mixer of lower part, be provided with the intercommunication recoil memory on division board 4, the venthole of perforated plate aeration mixer, the interval is provided with a plurality of perforated plates 6 from top to bottom in the perforated plate aeration mixer, at division board 4, be provided with the through-hole on perforated plate 6, intake pipe 7 is inserted and is established in the through-hole, exhaust hole one that is provided with perforated plate and aeration mixer intercommunication radially at the lower extreme of intake pipe 7, it advances exit tube 8 to be equipped with concentrated sulfuric acid in the interpolation of intake pipe 7, be provided with air inlet 9 on top cap 2, concentrated sulfuric acid import and export 10, gas outlet 11, air inlet 9, concentrated sulfuric acid import and export 10 and open and close by switch 12 control, intake pipe 7 and air inlet 9 intercommunication, the upper end of concentrated sulfuric acid inlet and outlet pipe 8 is connected with concentrated sulfuric acid import and export 10 on top cap 2, still be provided with outlet duct 13 on division board 4, outlet duct 13 passes through hose 14 and is connected with gas outlet 11 on top cap 2, barrel 3, perforated plate 6, division board 4, bottom plate 5 are made by corrosion-resistant material.
The recoil storage device is communicated with the porous plate aeration mixer through the air inlet pipe 7 to form a first U-shaped anti-recoil structure, so that possible leakage accidents of concentrated sulfuric acid are avoided, and the device is safe and reliable.
Specifically, the air inlet pipe 7 is arranged in the middle of the isolation plate 4, the air outlet pipe 13 is located on one side of the air inlet pipe 7, and the air outlet pipe 13 is fixedly connected with the isolation plate 4 in a welding mode. The division plate 4 is fixedly connected with the inner wall of the cylinder 3 in a welding mode. The porous plate 6 is connected with the inner wall of the cylinder 3 and the air inlet pipe 7 in a close contact or welding mode. The bottom of the bottom plate 5 is welded with a bearing ring 15 to adapt to the problem that the bottom of the pressure barrel 1 is uneven in circular arc shape. The welding deformation and fracture of the bottom plate 5 and the cylinder 3 caused by the weight can be prevented by thickening the bottom plate.
The invention takes 98% concentrated sulfuric acid as an initial drying agent, oxygen and the concentrated sulfuric acid are mixed in a gas dryer, the concentrated sulfuric acid absorbs moisture in the oxygen, and the oxygen is changed into dry gas for producing ozone. The concentrated sulfuric acid has strong corrosivity, only acid corrosion resistant materials such as polytetrafluoroethylene, plastics and glass can be used as a holding container, the concentrated sulfuric acid can reach the required dehydration capacity only under certain pressure, and the polytetrafluoroethylene, plastics and glass containers are not pressure-resistant, so that a pressure-resistant carbon steel or stainless steel shell is required to be matched with the pressure container for use. Carbon steel has a special corrosion resistance to concentrated sulfuric acid, and is cheaper than stainless steel, so the pressure vessel is preferably made of carbon steel.
Similarly, considering that the liquid medium of the present invention is concentrated sulfuric acid, the vapor in the gas is dissolved in the concentrated sulfuric acid, the concentrated sulfuric acid does not flow, but only the gas flows, and therefore, the cylinder 3 may be a corrosion-resistant material such as plastic, teflon, glass, or a titanium plate; considering the cost and the processing difficulty, the plastic material is processed most conveniently with the lowest cost; the processing difficulty of the glass porous plate is increased; the polytetrafluoroethylene porous plate is processed in a manner similar to that of plastic, but the cost is increased; titanium plates can take the form of punched holes but are costly. The materials of the cylinder 3 and the porous plate 6 can be corrosion-resistant materials such as glass, polytetrafluoroethylene, plastics and the like, and taking the cylinder 3 and the porous plate 6 as plastic PP materials as an example, for the problem of the aperture pitch of the porous plate 6, the aperture is 0.5-2mm, the aperture is 6 times of the aperture, the aperture is in an adaptive range, but the aperture is influenced by the specific gravity of concentrated sulfuric acid, the viscosity and the punching mode, and the aperture is preferably 1mm, so that the effect is better; the pitch is restricted by the punching mode, and if the stainless steel plate is subjected to modular heating and die casting, the pitch is 2 times of the hole diameter when the stainless steel plate is arranged in a mechanical punching mode; if manual punching is adopted, the holes are arranged in concentric rings at intervals of 5-20mm, and the holes are punched in the rings at intervals of 5-10 mm. If 0.5mm, 0.6mm, 0.7mm drill bit is adopted, the drill bit is easy to break off when actually perforating manually, so that the drill bit with 1mm is more suitable for perforating. The top of the cylinder 3 is sealed with only an air inlet pipe 7 and an air outlet pipe 13, after the gas and the acid are mixed and aerated to contact, the acid is left in the cylinder 3 as much as possible, and the gas is connected to a pressure container; a porous plate 6 is arranged in the cylinder 3; the spacing distance between the perforated plates 6 is preferably set to an empirical value of 100 and 200mm, which is more suitable for comparison in practical tests. According to the invention, the separation pipes 20 are arranged between the isolation plate 4 and the porous plate 6 positioned at the uppermost end, between the bottom plate 5 and the porous plate 6 positioned at the lowermost end, and between the porous plate 6 and the porous plate 6, so that the porous plates 6 which are in close contact with the inner wall of the cylinder 3 and the air inlet pipe 7 are prevented from being loosened and superposed, and the air inlet pipe 7 and the concentrated sulfuric acid inlet and outlet pipe 8 both pass through the separation pipes 20. From the above data, the length of the separation tube 20 is 100-200 mm. Similarly, a second exhaust hole communicating the intake pipe 7 and the perforated aeration mixer is provided in the radial direction in the partition pipe 20.
Further, sulfuric acid is generated by dissolving sulfur trioxide in water, is an inorganic acid which is not easy to volatilize and has strong stability under static and room temperature conditions, is different from hydrochloric acid and nitric acid which are easy to volatilize, but more sulfur trioxide gas sulfuric acid mist escapes in an aeration state at the temperature of more than or equal to 25 ℃ of concentrated sulfuric acid, the aeration gas has stink, and particularly, when the gas is compressed by an air compressor, the gas temperature can reach 54 ℃, so that the gas is not suitable for being used as drying gas for ozone. Therefore, concentrated sulfuric acid and gas must be cooled simultaneously. The partial pressure of water vapor in the gas is more and less, and is directly and positively correlated with the gas temperature. Therefore, the cooling measures are taken for the compressed gas and the concentrated sulfuric acid, the volatilization pollution of sulfur trioxide sulfuric acid mist can be reduced, the carrying amount of water vapor can be greatly reduced, the service cycle of the drying agent is prolonged, and the concentrated sulfuric acid is taken as the drying agent and becomes convenient and practical. Therefore, in order to realize synchronous cooling and temperature reduction of concentrated sulfuric acid and gas, a cooling and drying machine is further arranged on a pipeline between the air inlet 9 and the air compressor. The cold drying machine cools the pressure gas, and the cooled pressure gas can also realize the cooling of concentrated sulfuric acid. The regulation of pressure and temperature is controlled by an external air compressor and a freeze dryer.
Further, carbon steel or stainless steel is also a good thermal conductor, and when the ambient temperature is increased due to summer with high external temperature or other factors, the pressure gas cooled by the freeze dryer is easily heated to the ambient temperature, so that it is necessary to wrap the heat insulation cotton 16 on the outer surface of the pressure vessel to prevent the temperature of the acid and the gas from increasing, and to reduce the volatilization of the acid and the water vapor partial pressure of the gas. Such as: the pressure vessel of the embodiment requires a carbon steel material which can withstand pressure of 1.0MPa, is resistant to concentrated sulfuric acid corrosion and has a cylindrical middle part. After the pressure resistance is checked and the sealing effect is checked, the outer surface of the pressure container 1 is wrapped with heat insulation cotton 16 and then is sleeved with an outer package.
Of course, when the concentrated sulfuric acid is in an aerated state and in an environment of less than 25 ℃, a cold dryer and heat insulation cotton are not used.
Furthermore, the pressure barrel 1 is cylindrical, and the top cover 2 is fixedly connected with the pressure barrel 1 through a fastening flange 21. The bottom of the pressure barrel 1 of the invention is also provided with a ventilation port 17, and the ventilation port 17 is provided with a switch 12.
In addition, the air inlet 9, the concentrated sulfuric acid inlet and outlet 10 and the air outlet 11 on the top cover 2 are also fixedly connected with the top cover 2 through flanges, each flange comprises two flange pieces, one flange piece is directly fixed on the top cover 2, and the other flange piece is provided with different parts. The outer side of the flange of the air inlet 9 is connected with a corrosion-resistant switch, and the inner side of the flange is connected with a corrosion-resistant short pipe, so that the contact between a metal part and concentrated sulfuric acid is reduced or avoided; the outer side of a flange of the air outlet 11 is connected with a corrosion-resistant switch, the inner side of the flange is connected with a hose 14, and the hose 14 is connected with an air outlet pipe 13 in the backflushing storage device, so that the pressure barrel 1 and the top cover 2 can be conveniently detached; the inner side of a flange of the concentrated sulfuric acid inlet and outlet pipe 10 is connected with a concentrated sulfuric acid inlet and outlet pipe 8, the outer side of the flange is connected with a tee joint, one of the joints is a concentrated sulfuric acid inlet and outlet 10 joint which is connected with a corrosion-resistant switch, one joint is a pressure measuring port 19 which is provided with a switch 12, and the switch 12 is provided with a pressure gauge and a pressure safety valve. The other interface is connected with any switch on the three-way of the motorized interface 18. When the device normally operates, the switch 12 of the concentrated sulfuric acid inlet/outlet 10 is closed, and one of the switches 12 connected to the maneuvering measuring port 18 is opened, so that pressure balance is kept, and once the switch 12 of the concentrated sulfuric acid inlet/outlet 10 leaks air, back-flushing leakage can be prevented, and a second U-shaped anti-back-flushing structure is formed.
Furthermore, a three-way joint is arranged on the motorized interface 18, and two switches are arranged, wherein one switch is used for motorized measurement, negative-pressure extraction of concentrated sulfuric acid and motorized deflation; the other switch is connected with a three-way interface at the outer side of the flange of the concentrated sulfuric acid inlet and outlet, when the switch is opened, the upper end of the concentrated sulfuric acid inlet and outlet pipe 8 keeps pressure balance with the backflushing storage, a second U-shaped anti-backflushing structure is formed between the concentrated sulfuric acid inlet and outlet pipe 8 and the backflushing storage, and during the operation of the equipment, when the switch above the flange of the concentrated sulfuric acid inlet and outlet 10 is opened carelessly, the concentrated sulfuric acid cannot be sprayed out, so that the safety and the reliability are realized.
The working principle analysis of the invention is as follows:
the invention relates to an ozone dryer taking concentrated sulfuric acid as a drying agent, which is used for producing ozone after drying gas, and the working principle analysis is as follows:
analysis of water-absorbing and drying capacity of concentrated sulfuric acid
As is well known, concentrated sulfuric acid, phosphorus pentoxide and magnesium perchlorate all have very strong water absorption capacity, and specific data thereof prove that the dew point temperature of less than or equal to-60? According to known book data, the water weight remained in 1L of air at 25 ℃ under 1 atmosphere 101325Pa, and the 100% concentrated sulfuric acid is 3X 10-3mg, 95% concentrated sulfuric acid 0.3mg, phosphorus pentoxide 2X 10-5mg, magnesium perchlorate is 5X 10-4mg。
The calculation results of phosphorus pentoxide, magnesium perchlorate and 95% concentrated sulfuric acid are shown in Table 1:
according to the physical knowledge, 1mol to 18g to 22.4L of water vapor gas at 0 DEG CThen, 3X 10-3mg＝3×10- 6g＝3÷18×10-6mol＝3÷18×22.4×10-6L＝3.73×10-6L, 1L of air converted from 25 ℃ to 0 ℃ according to V1 XT 2 ═ V2 XT 1, V0＝V25×273÷298＝0.916V250.916L, the water content remained in 1L of air at 25 ℃, and the 100% concentrated sulfuric acid is 3X 10-3mg corresponds to a water vapor volume of 3.73X 0.916X 10 at 0 DEG C-6L＝3.42×10-6L, corresponding to 3.42X 101325X 10-6Water vapor partial pressure 0.346Pa, corresponding to a dew point temperature of-68 ℃.
As can be seen from Table 1, the water absorption capacity of the phosphorus pentoxide and anhydrous magnesium perchlorate powder is stronger than that of concentrated sulfuric acid, the dew point temperature is lower, and the phosphorus pentoxide and anhydrous magnesium perchlorate powder are theoretically more suitable for being used as a water absorption desiccant, but the magnesium perchlorate powder has oxidability and high toxicity, is dangerous and difficult to heat and regenerate and replace, and is changed into phosphoric acid after absorbing water, so that the phosphorus pentoxide and the anhydrous magnesium perchlorate powder are not renewable, so that the phosphorus pentoxide and the anhydrous magnesium perchlorate powder are more suitable for being used as a trace moisture absorption desiccant. The replacement and dehydration regeneration of the liquid sulfuric acid are convenient, so the water absorption is mainly concentrated sulfuric acid, the concentrated sulfuric acids with different concentrations have different water absorption capacities, and the required dryness can be achieved by multistage series connection. If the concentrated sulfuric acid needs drier gas after absorbing water, it is valuable to connect phosphorus pentoxide powder for further water absorption. However, 100% concentrated sulfuric acid cannot be obtained by heating regeneration, generally 98% concentrated sulfuric acid, and the dew point is not easy to reach-60 ℃ under normal pressure.
Secondly, increasing the pressure can reduce the dew point temperature and prevent the volatilization of acid gas
According to the data in Table 1, the dew point temperature of 100% concentrated sulfuric acid at normal pressure is-68 deg.C, but the mass fraction of the commonly used concentrated sulfuric acid is 98.3%, and the density is 1.84g/cm3The concentration is 18.4mol/L, the boiling point is 338 ℃, the dew point temperature of 95 percent sulfuric acid is only-31 ℃, the heating regeneration cannot reach 100 percent, the highest concentration is 98.3 percent, and concentrated sulfuric acid with the concentration less than or equal to 98.3 percent is adopted for absorbing water, so the dew point temperature of-60 ℃ is not easy to reach; in addition, at 98.3% concentration, sulfur trioxide is close to dynamic equilibrium and is concentratedDuring the aeration of the sulfuric acid, a small amount of sulfur trioxide gas escapes to form acid mist, and the acid mist or acid gas which is used as dry clean gas for an ozone machine cannot contain highly corrosive acid mist or acid gas.
Concentrated sulfuric acid is not suitable as a gas desiccant for ozone at a dew point temperature of-60 ℃ under normal pressure.
According to the existing relationship between pressure and dew point temperature, the dew point temperature under the pressure of 0.3-0.7MPa and the dew point temperature under normal atmospheric pressure are roughly related as shown in the following table 2:
according to the data in Table 2, with the increase of the air pressure, the difference between the pressure dew point temperature and the normal pressure dew point temperature is increased continuously, for example, when the dew point temperature of 0MPa is-60 ℃, the pressure is increased from 0.3MPa to 1.0MPa, the dew point temperature difference delta t is increased from 11 ℃ to 20 ℃, and the rest is analogized; under the same pressure, the dew point temperature is from low temperature to high temperature, the difference between the pressure dew point temperature and the normal pressure dew point temperature is increased continuously, for example, when the 0MPa dew point temperature is 0.7MPa and the 0MPa dew point temperature is increased from minus 70 ℃ to 10 ℃, the dew point temperature difference delta t is increased from 15 ℃ to 32 ℃, so that the gas dehydration effect of the higher pressure to temperature is better; at a pressure of 0.7MPa, the instrument measures a dew point temperature of about 98% sulfuric acid of-75 ℃. In addition, the gas pressure is increased, the amount of sulfur trioxide decomposed and escaped is continuously reduced, and when the pressure is 0.7MPa, the gas flowing out by aeration can be born by smelling through a nose.
The pressurization pressure can enable 98% concentrated sulfuric acid to reach the dew point temperature of-60 ℃, the problem of sulfur trioxide volatilization can be solved, and the condition of a gas drying agent for ozone is met.
Thirdly, cooling can reduce the dew point temperature and the volatilization of acid gas and prolong the service life
The sulfuric acid is prepared by dissolving sulfur trioxide in water, is an inorganic acid which is not easy to volatilize and has strong stability under the static and room temperature conditions, is different from hydrochloric acid and nitric acid which are easy to volatilize, but the dynamic balance is broken under the concentrated sulfuric acid in the aeration state of normal pressure and at the temperature of more than or equal to 25 ℃, so that more sulfur trioxide gas escapes to generate sulfuric acid mist, the aeration gas has stink, and particularly, when the gas is compressed by an air compressor, the gas temperature can reach 54 ℃, and more sulfur trioxide gas is released. Not only can reduce the volatilization of dew point temperature and sulfur trioxide through increasing pressure, through direct cooling, also can reduce the volatilization of dew point temperature and sulfur trioxide, more can directly reduce vapor partial pressure.
According to the data of the pressure, the temperature and the water vapor partial pressure Pa under 0MPa in the table 2, if only the pressure is provided with a cooling device, the temperature rises to 54 ℃ after the gas is compressed at 30 ℃ in summer and the dew point temperature is 20 ℃ and the water vapor partial pressure is 2339Pa under 0.7MPa, if the natural heat dissipation is reduced to 30 ℃ of the air temperature, the dew point temperature is 0 ℃ and the water vapor partial pressure is 610Pa, and when the air temperature is reduced to 18 ℃ after cooling measures are taken, the dew point temperature is-10 ℃, the water vapor partial pressure is 260Pa, the temperature is continuously cooled and reduced to 6 ℃, the dew point temperature is-20 ℃ and the water vapor partial pressure is 102 Pa. When the running time is the same, the difference of the carrying amount of the water vapor after compression at 54 ℃ and 6 ℃ is about 23 times; compared with the cooling temperature of 6 ℃, the difference of the carrying amount of the water vapor is about 6 times when the temperature is naturally cooled to 30 ℃. Therefore, the temperature is reduced or not reduced in summer at 30 ℃, the difference of the vapor carrying amount is about 6 times, if 1-time replacement in 1 month is intolerable, the desiccant can be accepted by enterprises after 1-time replacement in 6 months.
Therefore, cooling measures are taken for the compressed gas and the concentrated sulfuric acid, so that the volatilization pollution of sulfur trioxide sulfuric acid mist can be reduced, the dew point temperature can be greatly reduced, the carrying amount of water vapor can be reduced, the service cycle of the drying agent is prolonged, and the concentrated sulfuric acid is taken as the drying agent to be convenient and practical.
Application of anti-recoil principle of U-shaped tube
The single porous plate oxygen increasing device for dispersing bubbles in water can normally operate in the process of stable-pressure unidirectional gas flow, but in the operation and suspension processes, the gas often flows in the opposite direction due to pipeline gas leakage or other reasons, and when the liquid is water, the liquid has no harm to people and can possibly damage instruments and equipment; when the liquid is concentrated sulfuric acid, once the liquid flows in the reverse direction, damage is caused to people and instruments, so that accidents which should not happen are caused, and the problem that the concentrated sulfuric acid cannot leak from the gas in the forward and reverse flow directions must be considered. A plurality of accidents occur in the test until the anti-backflushing principle of the U-shaped pipe is thought, the anti-backflushing device is applied to a dryer, the problems of backflushing corrosion and leakage can be satisfactorily solved, but a backflushing storage device is connected with an aeration mixer through an air inlet pipe instead of two containers with the same diameter which are communicated in parallel at the bottoms, and the purpose of preventing the backflushing corrosion and the leakage of concentrated sulfuric acid is achieved.
The U-shaped pipe anti-recoil structure is formed by the concentrated sulfuric acid inlet and outlet, the concentrated sulfuric acid inlet and outlet pipe, the air inlet pipe, the recoil storage, the concentrated sulfuric acid inlet and outlet and the motor-driven outlet connecting switch.
When air is fed, concentrated sulfuric acid enters the aeration mixer, the concentrated sulfuric acid enters the backflushing storage device during backflushing, the volume of the backflushing storage device is slightly larger than that of the concentrated sulfuric acid after water absorption, once gas flows in the opposite direction, the gas cannot leak, and leakage accidents possibly caused by the porous plate oxygenation device are avoided.
Use of corrosion-resistant vessel and pressure-resistant vessel in combination
The concentrated sulfuric acid has strong corrosivity, a container in contact with the concentrated sulfuric acid can only be made of acid corrosion resistant materials such as polytetrafluoroethylene, plastic and glass to serve as a containing container, the concentrated sulfuric acid can reach the required water absorption capacity only under certain pressure, the polytetrafluoroethylene, plastic and glass containers are poor in compressive strength, a pressure-resistant carbon steel or stainless steel shell and the like are needed to be matched for use as a pressure-resistant container, and the carbon steel has special corrosion resistance to the concentrated sulfuric acid and is cheaper than the stainless steel, so that the shell is preferably made of the carbon steel.
Application of perforated plate oxygenation device technology
Although the measures of pressurizing and cooling are taken for concentrated sulfuric acid, a corrosion-resistant container and a pressure-resistant container are used, the purpose is to create conditions for the concentrated sulfuric acid to quickly absorb moisture in gas, the traditional aeration technology is not enough to quickly and efficiently absorb moisture, and the invention patent technology of a porous plate oxygenation device for dispersing bubbles in water can make up the defect of uneven gas-liquid mixing.
Analysis of water absorption regularity of heptaconcentrated sulfuric acid
According to the existing public data, the specific gravity and the mol concentration of concentrated sulfuric acid under different concentrations are respectively collected, the total weight after water absorption is calculated when the concentration of the concentrated sulfuric acid is reduced by 2%, the total water absorption amount and the water absorption increment of 2% concentration difference are obtained, the regularity of the water absorption amount and the calculation result are summarized in a table 3.
According to the data in table 3, in the concentration range of 100% -88%, it is found that when the concentrated sulfuric acid concentration is reduced by 2%, the water increase weight is slowly increased on the basis of 38.2 g, and the increase is between 1.6-2.1, but the difference between the water absorption increase of 88% and 86% is 9 g, the water absorption increase of 86% and 86% is reduced by 11.9 g, and 86% has a sudden inflection point, and the concentrated sulfuric acid concentration, the water absorption amount and the dew point temperature are linearly changed in a straight line manner on the whole. This rule is favorable to the dryer a plurality of series connection, and the gradient increases on average approximately, can descend to 88% concentration from 98% and reheat regeneration all the time, prolongs about 5 times than single live time, if extend to 84%, then the time extension is about 8 times, also is favorable to reducing the change frequency, reduces work load, practices thrift regeneration power consumption. And by combining the data in the table 2, after the compressed air is cooled to the room temperature at a proper environmental temperature, particularly when the gas flowing speed is high and the cooling effect is poor and the power consumption is increased, the cold dryer can be stopped and directly enter the concentrated sulfuric acid dryer for water absorption and drying.
Eighth, proportional relation between each element of the dryer
The invention is based on the specific gas flow, assuming that the gas flow through the ozone generator is 1m3The flow velocity of gas flowing through a perforated plate in the perforated plate aeration mixer is 0.5m/s as an example, the aperture of the perforated plate is 1mm, the hole number of the perforated plate is roughly calculated, the diameter of the perforated plate is determined according to the punching rule, the diameter and the length of a cylinder are determined, and a pressure capacity is selectedThe diameter range and height of the device, and the calculation results of each component are as follows:
1. the number of wells of the perforated plate 6 is required
The aperture of 0.5-2mm is in the adaptive range, taking manual punching as an example, the aperture of 1mm is selected here, and the area of 1 hole is 7.85 multiplied by 10-7m2The effective cross-sectional area of the aperture is required to be 1 ÷ 3600 ÷ 0.5 ÷ 5.555 × 10-4m2The number of wells required in a multi-well plate is 5.555X 10-4m2÷7.85×10-7m2707 pieces.
2. Perforated plate 6 and cylinder 1 size
The aeration holes are arranged in a linear and circular mode, when the aeration holes are arranged on a plastic plate in a circular mode, holes are punched according to the rule that the circumference length is 5mm and the circular ring interval is 10mm, the first circle of the aeration holes is 3.14 multiplied by 60/5 which is 37, the second circle of the aeration holes is 3.14 multiplied by 80/5 which is 50, the third circle of the aeration holes is 3.14 multiplied by 100/5 which is 62.8, 60 is obtained, and the like, the first circle of the aeration holes is punched on a circular ring with the diameter of 220mm, the third circle of the aeration holes is 3.14 multiplied by 220/5 which is 138, 136 is 9 circles, 782 holes are larger than 707, the requirement is met, the diameter of the porous plate is at least 240mm when the porous plate is 10mm, the diameter of the plastic pipe is 250mm, the wall thickness is 4.5mm, the inner diameter of the plastic pipe is 241mm, and the diameter of the plastic pipe is just matched with the porous plate with the diameter of 240mm, namely the plastic pipe with the diameter of 250mm and the wall thickness of 4.5 mm;
the perforation can also be continued until a circular ring with the diameter of 280mm is perforated, the holes are 3.14 multiplied by 280/5 which is 176 holes, 12 circles are formed, 1268 holes are formed, the edge is empty by 10mm, the diameter of the perforated plate is at least 300mm, the existing specification of the plastic pipe has the diameter of 315mm, the wall thickness is 4.5mm, the inner diameter is 306mm, and the diameter of the perforated plate can be matched with 305 mm. Namely the diameter of the porous plate is 305mm, and the cylinder adopts a plastic pipe with the diameter of 315mm and the wall thickness of 4.5 mm. See Table 4
3. Determination of the diameter of a pressure vessel
The inner wall of pressure vessel is not an ideal circle, when the cylinder was embedded in the inner wall of pressure vessel, the perforated plate could not in close contact with the cylinder, so the gas-liquid mixer must independently place in the pressure vessel, and left the space, and the internal diameter of general pressure vessel will be greater than the 20mm of plastics cylinder external diameter, and the plastics cylinder of being convenient for is placed in the pressure vessel. When the cylinder external diameter is 250mm, 300mm is taken to the pressure barrel external diameter, 315mm is taken to the cylinder external diameter, and 350mm phase-match is taken to the pressure barrel external diameter.
4. The volume proportion problem of the recoil storage and the porous plate aeration mixer
According to experimental experience, the adding amount of concentrated sulfuric acid is 1/3 which accounts for the effective height of the barrel of the aeration mixer, the gas-liquid mixing height accounts for 2/3 after aeration, the rest 1/3 height is a gas-liquid separation space, the height of the backflushing storage is 1.2 times of the height of the concentrated sulfuric acid in consideration of the 17.4% volume increase after water absorption of 98% to 86% concentrated sulfuric acid and the safe height of oscillation overflow during backflushing, so that if the effective height of the barrel is 42, the height of the backflushing storage is 12, the height of the aeration mixer is 30, and the heights of the isolation plate, the porous plate and the bottom plate are considered, namely the total length of the barrel, and the height of the pressure container is larger than the total length of the barrel.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, so: all equivalent changes made according to the shape, structure and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. The utility model provides an utilize concentrated sulfuric acid as ozone gas desicator of drier which characterized in that: including pressure vessel, gas-liquid mixer, pressure vessel includes pressure vessel (1) and top cap (2), gas-liquid mixer is including setting up barrel (3) in pressure vessel (1), well upper portion in barrel (3), the lower part is provided with division board (4) respectively, bottom plate (5), division board (4) are separated into recoil memory and perforated plate aeration blender with barrel (3), be provided with intercommunication recoil memory on division board (4), the venthole of perforated plate aeration blender, the interval is provided with a plurality of perforated plates (6) from top to bottom in perforated plate aeration blender, the lower part of intake pipe (7) is provided with the exhaust hole one of intercommunication perforated plate aeration blender, at division board (4), be provided with the through hole on perforated plate (6), intake pipe (7) are inserted and are established in the through hole, the interpolation is equipped with concentrated sulfuric acid business turn over pipe (8) in intake pipe (7), be provided with air inlet (9) on top cap (2), concentrated sulfuric acid imports and exports (10), gas outlet (11), air inlet (9), concentrated sulfuric acid imports and exports (10), all be provided with switch (12) on gas outlet (11), intake pipe (7) and air inlet (9) intercommunication, the upper end of concentrated sulfuric acid business turn over pipe (8) is connected with concentrated sulfuric acid import and exports (10) on top cap (2), still be provided with outlet duct (13) on division board (4), outlet duct (13) are passed through hose (14) with gas outlet (11) on top cap (2) and are connected, barrel (3), perforated plate (6), division board (4), bottom plate (5) are made by corrosion-resistant material.
2. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1, wherein: separating pipes (20) are arranged between the adjacent porous plates (6), between the porous plates (6) and the partition plates (4) and between the porous plates (6) and the bottom plate (5), the separating pipes (20) are sleeved outside the air inlet pipe (7), and exhaust holes II which are communicated with the inner cavity of the air inlet pipe (7) and the porous plate aeration mixer are arranged on the separating pipes (20).
3. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1, wherein: the aperture of the holes on the porous plates (6) is 0.5-2mm, the holes are arranged in concentric circles, the interval between the circles is 5-20mm, the holes in each circle are arranged at intervals of 5-10mm, and the interval between the adjacent porous plates (6) is 100-200 mm.
4. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to any one of claims 1 to 3, wherein: the partition plate (4) is fixedly connected with the cylinder body (3), the air inlet pipe (7) and the air outlet pipe (13) in a welding mode, and the porous plate (6) is fixedly connected with the cylinder body (3) and the air inlet pipe (7) in a welding or tight connection mode.
5. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to any one of claims 1 to 3, wherein: the corrosion-resistant material is glass or polytetrafluoroethylene or plastic.
6. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1, wherein: the bottom of the pressure barrel (1) is provided with a ventilation port (17), and the ventilation port (17) is provided with a switch (12).
7. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1, wherein: the pressure vessel is made of carbon steel or stainless steel.
8. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1 or 7, wherein: the pressure container is externally wrapped with heat insulation cotton (16).
9. The gas dryer for ozone using concentrated sulfuric acid as a drying agent according to claim 1, wherein: and a cooling dryer is arranged on a pipeline between the air inlet (9) and the air compressor.
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| PCT/CN2019/113984 WO2020134515A1 (en) | 2018-12-28 | 2019-10-29 | Ozone gas dryer using concentrated sulfuric acid as drying agent |
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| CN112851491A (en) * | 2021-01-20 | 2021-05-28 | 武威合才化工有限责任公司 | Method for producing high-purity formic acid by acidifying sodium formate with sulfuric acid |
| CN115198341B (en) * | 2022-07-07 | 2023-07-14 | 四川大学 | Dehydration sintering device for preparing magnesium oxide whisker from magnesium nitrate solution and preparation method |
| CN116889788B (en) * | 2023-09-04 | 2023-11-24 | 福建盈浩文化创意股份有限公司 | Spray tower is handled to coating cloud |
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