CN112939193A

CN112939193A - Method for efficiently utilizing ozone gas to treat water

Info

Publication number: CN112939193A
Application number: CN202110182755.8A
Authority: CN
Inventors: 邹志平; 邹一
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-02-10
Filing date: 2021-02-10
Publication date: 2021-06-11
Anticipated expiration: 2041-02-10
Also published as: CN112939193B

Abstract

A method for efficiently utilizing ozone gas to treat water uses a set of gas-liquid mixing reaction device, adopts a process of sucking materials and ozone gas under negative pressure and discharging the materials under positive pressure, greatly improves the probability of contact between ozone in the ozone gas and treatment objects (bacteria in drinking water, organic matters in sewage and the like) in the materials, and utilizes the characteristic that oxidation reaction can be generated when the ozone is in contact with the treatment objects, thereby realizing efficient utilization of the ozone and basically realizing zero emission of the ozone.

Description

Method for efficiently utilizing ozone gas to treat water

Technical Field

The invention belongs to the field of water treatment, and particularly relates to a method for efficiently utilizing ozone gas to treat water.

Background

Ozone is an allotrope of oxygen (CAS: 10028-15-6) and has the chemical formula O₃Molecular weight 47.998, its name is fishy and it is a light blue gas at room temperature. The "ozone gas" herein may be pure ozone or a mixture of ozone and other gases (oxygen, nitrogen, etc.). Industrially, ozone gas is produced by an ozone generating apparatus, wherein the volume percentage of ozone is generally below 21%.

Ozone gas is mainly used in water treatment, food processing, medical and health, chemical reaction and other industries, and can treat water treatment materials, wherein the water treatment materials include drinking water, beverages, sewage, unsaturated compounds and the like, for example: the method is applied to disinfection and sterilization of drinking water and beverage, and purification treatment of domestic sewage and industrial wastewater; the air purifying and food storage and fresh keeping device is used for air purification, food storage and fresh keeping in food processing places; the air purifier is used for air purification and disease treatment in medical places; it is used in chemical and pharmaceutical industry to oxidize organic unsaturated compounds (double bond cleavage to generate aldehyde and ketone), etc.

In the process of drinking water treatment, ozone can be quickly fused into cell walls to destroy the internal structure of microorganisms, so that the ozone has a very strong killing effect on various pathogenic microorganisms, can kill various bacteria propagules, spores, viruses, fungi, protozoan cysts and other microorganisms in water, can destroy botulinum and toxins, rickettsia and the like, and has a very strong function of removing peculiar smells such as mildew, awakening, odor and the like.

The ozone gas can rapidly perform selective oxidation and quantitative oxidation reaction with organic matters in the wastewater at room temperature (even below zero degree) by mainly utilizing the extremely strong oxidation capacity of the ozone in the treatment process of domestic sewage and industrial wastewater, so that the organic matters are gradually decomposed into carbon dioxide and water.

At present, in the process of treating materials by using ozone gas, a bubbling method, a spraying method, a mixing pump method and the like are mainly adopted to ensure that the materials to be treated contain ozone with certain concentration and maintain certain reaction time (the CT value recommended by the industry is 1.6, C is the water-soluble concentration (mg/L) of the ozone, T is the reaction time (min), and the most economical operation scheme in practice is that the water-soluble concentration of the ozone is 0.4mg/L and the reaction time is 4 min).

The bubbling method is that ozone gas generated by an ozone generator is introduced into the bottom of an oxidation tower or an oxidation tank through a pipeline, micro bubbles are emitted by a micro-air bubbler, and the bubbles dissolve the ozone in water in the rising process. The bubbling in the oxidation tower for treating drinking water (including beverage) features large apparatus, complex structure, high requirement on bubbling apparatus (titanium or corundum), small pore size for generating micro bubbles, and low utilization rate of ozone (generally 20-30%).

The jet method is that under the action of high-speed water flow, negative pressure is formed in the air cavity of the jet device to suck in ozone gas, and the high-speed water flow pulverizes the ozone gas to form micro-bubbles which are fully contacted and mixed with water. The main characteristics of the injection method are large investment scale, high operation cost (needing a high-power booster pump), complex structure (the air inlet section is provided with a double or triple backflow prevention protection device), and low ozone utilization rate (generally 25-35%). The method is adopted to treat the drinking water, the outlet water can not be directly filled, although the ozone dissolution concentration reaches the specified value, the reaction time is too short, the sterilization effect is influenced, and multiple times of circulating treatment are needed.

The mixing pump method is generally a vortex type, in which negative pressure is formed in the pump, gas (or liquid) is sucked into a suction port, and gas-liquid or liquid-liquid mixing is performed by stirring with a plurality of impellers. When the mixing pump is adopted for gas-liquid mixing, the gas proportion is generally required to be about 10 percent, and the mixing efficiency of the mixing pump is optimal. The mixing pump is not suitable to be connected in the main path, and can not simultaneously undertake two functions of water supply and mixing, and the two effects are difficult to be simultaneously ensured. The ozone utilization rate by the mixed pump process is generally 30-40%.

At present, the literature and experience generally believe that when ozone gas reacts with the water treatment material, firstly ozone in the ozone gas is dissolved in liquid, secondly the ozone is contacted with a treatment object in the material to be treated in the liquid, and finally a certain contact time is ensured, so that the purpose of treating the material by the ozone can be achieved. Therefore, there is a consensus in the industry that ozone utilization must be improved by increasing CT values. However, in practice, ozone gas is hardly soluble in water, and even if dissolved in a trace amount (dissolved ozone reaches 2mg/L and is already at a high concentration), ozone is rapidly decomposed in a short time, and most of ozone is not effectively utilized.

For example, in the sewage treatment process using ozone gas, ozone gas is generally produced from an air source at a concentration of about 50mg/L, and ozone which does not meet organic matters in the sewage flows out of the sewage along with air in bubbling (commonly referred to as aeration). Within a larger range near the ozone gas treatment tank, the wet KI test paper is used for detecting air, but the detected sewage does not develop color, which shows that the dissolution rate of ozone in the sewage is very low (the ozone in contact with organic matters is consumed by oxidation reaction instantly, and the ozone not in contact with the organic matters overflows from the sewage along with the air quickly, so the wet KI test paper is used for detecting the sewage, the color is not developed, the loss is more, and the utilization rate is lower.

For example, when the reasonable ozone adding amount in bottled purified water is 2.0mg/L, the sterilization and quality guarantee requirements can be met, but in practice, the concentration requirement can be met only when the ozone amount is higher than 8.0mg/L, nearly 3/4 ozone is lost, and the utilization rate is low. Tap water is purified by ozone, the international conventional standard is only that the solubility value is 0.4mg/L, namely the actual effective utilization is only 5%, and most of tap water is wasted.

The prior process of utilizing ozone gas to treat water treatment materials mainly has the following problems: the ozone gas has low utilization rate when reacting with the water treatment material: mixing ozone gas with the water treatment material mainly by bubbling, spraying or other means; however, because ozone gas is poorly soluble in water, ozone gas has poor mixing effect with the material to be treated, resulting in O₃The utilization rate is usually less than 25% in practical use; ② the ozone gas is discharged into the environment to cause environmental pollution.

In view of the above problems, the present invention is generally improved from the following three aspects:

firstly, the mass transfer effect is enhanced to promote the reaction, for example, a small-aperture gas distributor and a high-pressure fine nozzle ejector are adopted to strengthen the gas-liquid reverse flow, prolong the retention time of gas in liquid, use a multi-stage U-shaped pipe and add a stirring coordination, and Chinese patent (CN201910626505.1) adopts a multi-port and multi-valve connection and an ozone module; chinese patent (CN201520139291.2) adopts ozone gas flow to gradually reduce to a nozzle at the back end, and the pipe diameter of the steam-water mixed liquid outlet pipe gradually increases along the water flow direction. These continuous improvement means are based on the intensive contact of ozone gas and liquid in the form of bubbles, and generally have the technical problems of complicated structure, huge equipment, unobvious improvement of mass transfer effect and low ozone utilization rate.

Secondly, other synergistic means are added to promote the oxidation reaction: the domestic patent (CN201420538487.4) utilizes the synergy of ultraviolet rays and activated carbon; the domestic patent (CN200810122388.7) adopts the integrated synergy of ozone and electrochemistry(ii) a The domestic patent (CN201510101137.0) adopts the synergy of ultraviolet light coupling catalyst ozone; domestic patent (CN201310355422.6) adopts the synergy of ozone oxidation and ionizing radiation; domestic patent (CN201810809079.0) is based on hydrodynamic cavitation in conjunction with ultraviolet intensified ozonation. Multiple technical means are used cooperatively for improving O₃Reaction rate with water treatment material, but actually only O₃Can quickly react when contacting with a treatment object of the water treatment material, has no obvious effect on improving the reaction rate by using other synergistic means, and does not substantially solve the problem of O₃The utilization rate is low.

Thirdly, increase O₃Tail gas recovery and treatment level: chinese patent (CN2019108277161) adopts catalysts such as activated carbon and manganese dioxide to treat industrial ozone-containing waste gas, but the equipment structure is complex and huge, and the activated carbon and the manganese dioxide become pollutants after being used. The Chinese patent (CN2017114804011) adopts a holaragat catalyst to decompose ozone, and the catalyst has a complex preparation process and higher cost. In order to realize the adsorption of ozone, a patent (CN2012800586623) applied by Americans in China basically adopts a huge tower structure by controlling or regulating an ozone exhaust gas flow and a recovery system, and adopts the synergistic action of various catalysts, so that the investment and the operation cost are high. These are used for recovering and treating O₃All means of (2) are because O cannot be increased₃The utilization rate is high, the adopted remedial measures are unavailable, and the cost is high.

In the conventional ozone gas-liquid mixing methods such as the bubbling method, the spraying method, the mixing pump method and the like, the average diameters of bubbles formed when ozone gas is mixed with the material are about 400 μm, 250 μm and 150 μm, respectively. Along with the reduction of the diameter of the bubbles, the contact area is enlarged, and the ozone utilization rate is improved. In order to reduce the diameter of ozone bubbles and improve the mixing efficiency of ozone bubbles and liquid, a great deal of research and development work is carried out by industry workers, and the intensive research on the traditional bubbling method, the injection method and the mixing pump method is mainly focused on the micronization treatment of gas holes of a gas distributor of the bubbling method, the optimization treatment of a fluid movement cavity of the injection method, the optimization treatment of a rotor structure in the mixing pump and the like. In the course of these improvements, the diameter of the ozone bubbles can be reduced to some extent, but always not beyond the lower limit of 100 um; the mixing efficiency of ozone and liquid can also be improved to a certain degree, but the utilization rate of ozone can not reach more than 50% all the time.

Thus, O is increased₃Utilization in Water treatment Process, to O used₃Residue O in the site₃Carrying out recovery and even innocent treatment to gradually realize O₃Zero emission is the effort direction of researchers in the industry, deep research is carried out on the zero emission, and the zero emission has wide application prospect and huge social value and economic value. If the gas-liquid mixing can reach 10 mu m level (emulsion diameter size), the O content is necessarily greatly increased₃The invention provides the following technical scheme according to the thinking of reducing the volume of ozone bubbles, increasing the surface area of gas and liquid and improving the gas-liquid contact probability.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings in the prior art, and provides a method for efficiently utilizing ozone gas to treat water, which improves the contact area of ozone and materials, shortens the time required by the ozone to meet treatment objects in the materials, and realizes the sufficient contact of the ozone and the treatment objects, thereby improving the utilization rate of the ozone and basically realizing zero emission of the ozone.

The invention is realized by the following technical scheme:

a method for efficiently utilizing ozone gas for water treatment comprises the following steps:

s1: providing a set of gas-liquid mixing reaction device, wherein the gas-liquid mixing reaction device comprises: the device comprises a liquid inlet pipe, an air inlet pipe, a dispersion pump set, a pump rear pipe, a pressure stabilizing tank, a discharge pipe and a material pool; the inlet end of the dispersion pump group is connected with the liquid inlet pipe, and the outlet end of the dispersion pump group is connected with the pump rear pipe; the liquid inlet pipe is provided with a liquid inlet regulating valve; the air inlet pipe is provided with an air inlet regulating valve; the air inlet pipe is communicated with the liquid inlet pipe, and the communicated position is positioned between the liquid inlet regulating valve and the dispersion pump set; one end of the pressure stabilizing tank is connected with the rear pump pipe, and the other end of the pressure stabilizing tank is connected with one end of the discharge pipe; the other end of the discharge pipe is communicated with the material pool; a discharge regulating valve is arranged on the discharge pipe; the material pool is connected with the liquid inlet pipe and is used for containing materials; s2: the dispersion pump group comprises at least one dispersion pump, the liquid inlet regulating valve and the material outlet regulating valve are fully opened, the gas inlet regulating valve is fully closed, the dispersion pump group is opened, and the material circularly flows in a loop of the gas-liquid mixing reaction device; s3: adjusting the liquid inlet adjusting valve to reach negative pressure before the liquid inlet adjusting valve reaches the dispersion pump group; adjusting the discharge adjusting valve until the pressure stabilizing tank reaches positive pressure; s4: opening the air inlet regulating valve to input the ozone gas into the dispersion pump group, wherein the ozone in the ozone gas is mixed with the materials in the dispersion pump group and reacts; s5: the reacted materials enter the material pool through a material outlet pipe, and S4 is repeated; s6: and ending the circulation when the reaction end point is reached.

The dispersion pump group comprises at least one dispersion pump, for which dispersion pumps it is currently common in industry to disperse one liquid into another, or to disperse a solid powder into a liquid. The dispersion pump continuously feeds the indissolvable liquid or solid powder into a pipeline in front of the pump by utilizing potential energy generated when the liquid is continuously conveyed in the pump, and the liquid or the solid powder is continuously dispersed in the liquid due to the high tangential velocity generated by the high-speed rotation of the rotor and the strong kinetic energy brought by the high-frequency mechanical effect in the pump body.

The invention relates to a method for efficiently utilizing ozone gas to treat water, which utilizes the capability of a dispersion pump to disperse solid powder in liquid, disperses the ozone gas which is difficult to dissolve in water in a water treatment material to achieve the aim of 'gas in liquid', but also utilizes the innovative use of the dispersion pump to form a dispersion pump group by a plurality of dispersion pumps, enables the dispersion pump group to feed in negative pressure and discharge in positive pressure, enables the dispersion pump group to be in a stable 'pressure-holding' state (namely the pressure is maintained near a certain stable value) in the continuous high-speed rotation process by reasonably adjusting a liquid inlet adjusting valve and a discharge adjusting valve, fills the space between the dispersion pump group and the discharge adjusting valve with the material to form a closed pressure container, the ozone gas is continuously sucked into a liquid inlet pipe by negative pressure through an air inlet pipe, and is firstly stretched into a sheet-shaped gas film under the high-speed rotation of a rotor of the dispersion pump group, then the flaky air film is cut into large bubbles, the large bubbles are broken into small bubbles again until the small bubbles are broken into bubbles with the diameter of mm level and micron level, finally the ozone gas wraps the organic matter and the water solution in the material to form an air film-liquid bubble 'air-in-liquid' composite structure from outside to inside, so that the 'liquid-in-gas' is converted into 'air-in-liquid', for the organic matter which is easy to dissolve in water, 'air-in-liquid' is the 'air-in-water', and for the organic matter which is insoluble or insoluble in water, in the liquid phase of the 'air-in-liquid', the organic phase which is insoluble or insoluble in water is covered on the surface of the water phase. The efficient mass transfer of ozone gas and water treatment materials is continuously realized in the dispersion pump group, the contact area of ozone and the materials is increased by hundreds of times, the moving time required by the meeting of the ozone and treatment objects in the materials is shortened by about 90 percent, the contact probability of the ozone and the treatment objects is greatly improved, and the utilization rate of the ozone is greatly improved by utilizing the characteristic that the ozone and the treatment objects are in contact to generate oxidation reaction immediately; in addition, due to the arrangement of the pressure stabilizing tank, the space of the 'pressure-building' state is multiplied, the holding time of the 'gas-in-liquid' state is prolonged, the chance that the ozone meets the treatment object in the material is increased again, the utilization rate of the ozone is further multiplied, and zero emission of the ozone is basically realized before the treated object reaches the reaction end point.

Further, in S3, slowly closing the liquid inlet regulating valve until the pressure in front of the dispersion pump group is (-0.07 +/-0.03) MPa; and after the pressure in front of the dispersion pump set is stable, slowly closing the discharge regulating valve until the pressure of the pressure stabilizing tank is (0.50 +/-0.30) MPa, and regulating to a proper pressure value to enable ozone to be sucked in at a negative pressure to be mixed and reacted with the material.

Further, in S4, after the pressure in front of the dispersion pump group and the pressure in the pressure stabilizing tank are stabilized, the air inlet adjusting valve is slowly opened, the ozone gas is input, the volume of the input ozone gas is not more than one third of the volume of the material, and the pressure in front of the dispersion pump group is-0.03 to-0.1 MPa. The ozone gas and the materials are effectively mixed under the high-speed rotation of the dispersion pump group, but the volume of the ozone gas is not suitable to be excessive, otherwise, the stable control of the front negative pressure of the dispersion pump group and the back positive pressure of the dispersion pump group is difficult to realize.

Further, in S6, ozone is detected in the air near the liquid level of the material tank, and the circulation is terminated. And detecting air near the liquid level of the material pool, detecting color development regularly through moist KI test paper or detecting ozone by using an online ozone detector, namely indicating that the ozone escapes, and finishing the circulation when the reaction reaches the end point.

Further, in S1, a liquid flow meter and a vacuum meter are disposed on the liquid inlet pipe; a gas flowmeter is arranged on the gas inlet pipe; and a pressure gauge is arranged on the pressure stabilizing tank. Through liquid flowmeter, vacuum gauge, gas flowmeter and manometer, can more accurate control pump back pipe pressure, disperse pressure before the pump package and gas flow and liquid flow to realize the control to production.

Further, the diameter of the surge tank is not less than 2 times the diameter of the post-pump pipe; the volume of the pressure stabilizing tank is more than or equal to half of the total volume of a closed space formed between the liquid inlet regulating valve, the gas inlet regulating valve and the discharge regulating valve, so that the reading on the pressure gauge is controlled to slow down the violent swing of a pointer of the pressure gauge, and the adjustment of the discharge regulating valve is guided; if the diameter of the pressure stabilizing tank is too thin, the pointer on the pressure gauge is unstable; and the display reading on the pressure gauge is stable after the diameter is increased, so that the system is efficiently adjusted and operated. Meanwhile, the ozone gas and the materials can continuously react in the pressure stabilizing tank, so that the time for gas-liquid mixing contact and reaction is prolonged.

Further, when the material comprises organic matters and aqueous solution, when the material is placed statically and layered to form an organic layer and a water layer, the inlet of the liquid inlet pipe is arranged at the position of the organic layer, and the outlet of the liquid outlet pipe is arranged at the position of the organic layer. The organic matter can exist in a solution form or a sludge form, and the inlet of the liquid inlet pipe is arranged in the organic layer, so that the organic matter can conveniently enter the dispersion pump group together with water; the outlet of the discharge pipe is arranged in the organic layer, so that the organic layer and the water layer can be mixed conveniently by utilizing the impact force of positive pressure discharge.

Further, the ozone gas is ozone or a gas mixture with ozone accounting for less than 21% of the volume. The "ozone gas" herein may be pure ozone or a mixture of ozone and other gases (oxygen, nitrogen, etc.). Industrially, ozone gas is produced by an ozone generating apparatus, wherein the volume percentage of ozone is generally below 21%.

Further, the dispersion pump unit includes a pump chamber; a disc type rotor is arranged in the pump cavity; and expanding the volume of the dispersion pump group, and increasing the number of the laminated rotors to ensure that the plurality of disc type rotors are sequentially arranged along the pump shaft. In a specific implementation mode, the capacity of the pump cavity of the dispersion pump group is expanded, the capacity expansion can be increased by 4-5 times by increasing the number of the rotors or the discs from 1 to 4-5, the dispersion pump group can realize higher negative pressure feeding and higher positive pressure discharging, the mixing time of ozone and the materials is prolonged, and the gas-liquid mixing effect is improved.

Further, the dispersion pump group comprises a plurality of dispersion pumps used in series and/or a plurality of dispersion pumps used in parallel, or a plurality of dispersion pumps used in series are connected in parallel for reuse. The dispersion pumps are combined to form the dispersion pump set according to the capacity requirement, so that the production efficiency is greatly improved.

For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.

Drawings

FIG. 1 is a schematic view of a mixing reactor for efficiently treating water with ozone gas.

Detailed Description

The embodiments of the present invention will be described in further detail with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad invention. It should be further noted that, for convenience of description, only some structures, not all structures, relating to the embodiments of the present invention are shown in the drawings.

Furthermore, the terms first, second, third and the like in the description and in the claims, are used for descriptive purposes only to distinguish one element from another, and are not to be construed as indicating or implying relative importance or implying any order or order to the indicated elements. The terms are interchangeable where appropriate. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.

Similarly, the terms "fixed" and "connected," as used in the description and claims, are not to be construed as limited to direct connection. Thus, the expression "device a is connected to device B" should not be limited to devices or systems in which device a is directly connected to device B, meaning that there is a path between device a and device B, which may be a path including other devices or tools.

Example 1

The invention provides a method for efficiently utilizing ozone gas to treat water, which comprises the following steps:

s1: providing a set of the gas-liquid mixing reaction device, as shown in fig. 1, the gas-liquid mixing reaction device comprises:

the device comprises a liquid inlet pipe 1, an air inlet pipe 2, a dispersion pump group 3, a pump rear pipe 4, a pressure stabilizing tank 5, a discharge pipe 6 and a material pool 7;

the dispersion pump group 3 comprises at least one dispersion pump, the inlet end of the dispersion pump group 3 is connected with the liquid inlet pipe 1, and the outlet end of the dispersion pump group is connected with the pump rear pipe 4;

the liquid inlet pipe 1 is provided with a liquid inlet regulating valve 11; the air inlet pipe 2 is provided with an air inlet regulating valve 21; the air inlet pipe 2 is communicated with the liquid inlet pipe 1, and the communicated position is positioned between the liquid inlet regulating valve 11 and the dispersion pump group 3;

one end of the surge tank 5 is connected with the pump rear pipe 4, and the other end is connected with one end of the discharge pipe 6;

the other end of the discharge pipe 6 is communicated with the material pool 7, and a discharge regulating valve 61 is arranged on the discharge pipe 6;

the material pool 7 is connected with the liquid inlet pipe 1 and used for containing materials;

s2: fully opening the liquid inlet regulating valve 11 and the material outlet regulating valve 61, fully closing the gas inlet regulating valve 21, and opening the dispersion pump group 3, wherein the materials circularly flow in the loop of the gas-liquid mixing reaction device;

s3: the liquid inlet regulating valve 11 is regulated to reach the negative pressure before reaching the dispersion pump group 3; adjusting the discharging adjusting valve 61 to the pressure stabilizing tank 5 to reach positive pressure;

s4: opening an air inlet adjusting valve 21 to input ozone gas into a dispersion pump group 3, wherein the ozone in the ozone gas is mixed with the materials in the dispersion pump group 3 to react;

s5: the reacted materials enter a material pool 7 through a material outlet pipe 6, and S4 is repeated;

s6: and ending the circulation when the reaction end point is reached.

The dispenser group 3 comprises at least one dispenser pump, for which the current common usage in industry is to dispense one liquid into another liquid, or to dispense a solid powder into a liquid. The dispersion pump continuously feeds the indissolvable liquid or solid powder into a pipeline in front of the pump by utilizing potential energy generated when the liquid is continuously conveyed in the pump, and the liquid or the solid powder is continuously dispersed in the liquid due to the high tangential velocity generated by the high-speed rotation of the rotor and the strong kinetic energy brought by the high-frequency mechanical effect in the pump body.

The invention relates to a method for efficiently utilizing ozone gas to treat water, which utilizes the capability of a dispersion pump to disperse solid powder in liquid, disperses the ozone gas which is difficult to dissolve in water in a water treatment material to achieve the aim of 'gas in liquid', but also utilizes the innovative use of the dispersion pump to form a dispersion pump group 3 by a plurality of dispersion pumps, enables the dispersion pump group 3 to be in a stable 'pressure-building' state (namely the pressure is maintained near a certain stable value) in the continuous high-speed rotation process by reasonably adjusting a liquid inlet adjusting valve 11 and a discharge adjusting valve 61, fills the space between the dispersion pump group 3 and the discharge adjusting valve 61 with the material and forms a closed pressure container, the ozone gas is continuously sucked into a liquid inlet pipe 1 by negative pressure through an air inlet pipe 2, and the ozone gas is firstly extended into a sheet-shaped gas film under the high-speed rotation of a rotor of the dispersion pump group 3, then the flaky air film is cut into large bubbles, the large bubbles are broken into small bubbles again until the small bubbles are broken into bubbles with the diameter of mm level and micron level, finally the ozone gas wraps the organic matter and the water in the material to form an air film-liquid bubble 'air-in-liquid' composite structure from outside to inside, so that the 'liquid-in-liquid' is converted into 'air-in-liquid', for the organic matter which is easy to dissolve in water, 'air-in-liquid' is the 'air-in-water', and for the organic matter which is insoluble or insoluble in water, in the liquid phase of the 'air-in-liquid', the organic phase which is insoluble or insoluble in water is covered on the surface of the water phase. The high-efficiency mass transfer of ozone gas and water treatment materials is continuously realized in the dispersion pump group 3, the contact area of the ozone and the materials is increased by hundreds times, the moving time required by the meeting of the ozone and treatment objects in the materials is shortened by about 90 percent, the contact probability of the ozone and the treatment objects is greatly improved, and the utilization rate of the ozone is greatly improved by utilizing the characteristic that the ozone and the treatment objects are in contact to generate oxidation reaction immediately; in addition, due to the arrangement of the pressure stabilizing tank 5, the space of the 'pressure-building' state is multiplied, the holding time of the 'gas-in-liquid' state is prolonged, the chance that the ozone meets the treatment object in the material is increased again, the utilization rate of the ozone is further multiplied, and zero emission of the ozone is basically realized before the treated object reaches the reaction end point.

The ozone gas is ozone or a gas mixture with ozone accounting for less than 21% of the volume. The "ozone gas" herein may be pure ozone or a mixture of ozone and other gases (oxygen, nitrogen, etc.). Industrially, ozone gas is produced by an ozone generating apparatus, wherein the volume percentage of ozone is generally below 21%.

The dispersion pump unit 3 comprises a pump cavity, and a disc type rotor is arranged in the pump cavity; the capacity of the dispersion pump group 3 is expanded, and the number of the laminated rotors is increased, so that the plurality of disc type rotors are sequentially arranged along the pump shaft. The pump cavity is a place where gas and liquid are mixed and react. In one embodiment, the pump cavity of the dispersion pump unit 3 is expanded, the number of the rotors or the discs is increased from 1 to 4 to 5, and the expansion can be increased by 4 to 5 times, so that the dispersion pump unit 3 can realize higher negative pressure feeding and higher positive pressure discharging, and simultaneously, the mixing time of ozone and materials is prolonged, and the gas-liquid mixing effect is improved. The dispersion pump group 3 includes a plurality of dispersion pumps used in series and/or a plurality of dispersion pumps used in parallel, or a plurality of dispersion pumps connected in series are reused in parallel. The dispersion pumps are combined to form the dispersion pump set according to the capacity requirement, so that the production efficiency is greatly improved.

The method for efficiently utilizing ozone gas to treat water can connect a plurality of dispersion pump groups 3 in series or in parallel, or connect a plurality of groups in series and then connect a plurality of groups in parallel, thereby improving the production efficiency and the productivity as required.

In S1, the liquid inlet pipe 1 is provided with a liquid flow meter 12 and a vacuum gauge 13; the gas inlet pipe 2 is provided with a gas flowmeter 22; the surge tank 5 is provided with a pressure gauge 51. Through the liquid flowmeter 12, the vacuum gauge 13, the gas flowmeter 22 and the pressure gauge 51, the pressure of the pump rear pipe 4, the pressure before the dispersion pump group 3, the gas flow and the liquid flow can be more accurately controlled, so that the production control is realized.

The side wall of the lower part of the pressure stabilizing tank 5 is communicated with the pump rear pipe 4, and the diameter of the communicated part of the pressure stabilizing tank 5 and the pump rear pipe 4 is the same as the diameter of the outlet of the dispersion pump group 3 and the diameter of the pump rear pipe 4. The surge tank 5 may be a vertical tank. The diameter of the surge tank 5 is not less than 2 times of the diameter of the pump rear pipe 4; the volume of the pressure stabilizing tank 5 is more than or equal to half of the total volume of a closed space formed between the liquid inlet regulating valve 11, the air inlet regulating valve 21 and the discharging regulating valve 61, so that the reading on the pressure gauge 51 is controlled to slow down the violent swing of the pointer of the pressure gauge 51, and the regulation of the discharging regulating valve 61 is guided; if the diameter of the surge tank 5 is too thin, the pointer on the pressure gauge 51 is unstable; the reading on the pressure gauge 51 is stable after the diameter is increased, so that the system is efficiently adjusted and operated. Meanwhile, the ozone gas and the materials can continue to react in the pressure stabilizing tank 5, so that the time for gas-liquid mixing contact and reaction is prolonged. The upper part and the lower part of the pressure stabilizing tank 5 are respectively provided with a sight glass for observing the gas-liquid mixing state in the pressure stabilizing tank 5.

In one embodiment, when the material comprises organic matter and aqueous solution, when the material is placed still to be layered to form an organic layer and an aqueous layer, the inlet of the liquid inlet pipe 1 is arranged at the position of the organic layer, and the outlet of the liquid outlet pipe 6 is arranged at the position of the organic layer. The material tank 7 is a sewage tank, and when the material comprises organic matters and aqueous solution, the material is easy to form an organic layer and a water layer in a layered manner, which is not beneficial to sewage treatment. The organic matter can exist in a solution form or a sludge form, and the inlet of the liquid inlet pipe 1 is arranged in the organic layer, so that the organic matter can conveniently enter the dispersion pump group 3 along with the water solution; the outlet of the discharge pipe 6 is arranged in the organic layer, so that the organic layer and the water layer can be conveniently mixed by utilizing the impact force of positive pressure discharge. If the organic matter is difficult to dissolve in water, or the sewage bottom contains silt, the impact force of malleation ejection of compact is not enough to mix the organic matter to the aqueous solution, can adopt agitating unit in coordination, can introduce the organic matter with the aqueous solution and circulate in dispersion pump group 3 and purify.

In another embodiment, the material tank 7 is a reaction kettle, and the same as the sewage tank treatment, the liquid inlet pipe 1 and the liquid outlet pipe 6 are properly connected according to the material properties, and for organic matters which are not easy to dissolve in water, if the impact force of positive pressure discharging is not enough to mix the organic matters into the aqueous solution, a stirring device can be matched to cooperate with the material tank to react in the dispersion pump group 3. When the materials comprise sludge, a filter screen can be additionally arranged before the materials enter the liquid inlet pipe 1, and a dispersion pump group 3 capable of bearing the sludge is selected, so that the sludge is input into the liquid inlet pipe 1 along with the water solution.

In another embodiment, the method for water treatment with high efficiency by using ozone gas of the present invention can be applied to a chemical reaction for ozone oxidation of organic matters, wherein the double bonds of unsaturated organic matters are broken by ozone and aldehydes and ketones are generated, the supply of ozone is limited and continuous supply of ozone is performed in the reaction, and the excess organic matters are generally required to be continuously circulated in the gas-liquid mixing reaction device for complete reaction. Because of the heat release of the oxidation reaction and the heat generated by the high-speed rotation friction of the dispersion pump group 3, the temperature of the materials in the reaction system rises, the temperature of the materials needs to be controlled, and the materials are properly cooled when exceeding a certain temperature, so that the reaction is prevented from being too violent. Preferably, water is selected as a solvent, air is firstly introduced to mix the organic matters with the aqueous solution after the dispersion pump group 3 is started, and safety accidents caused by local heat release due to direct contact reaction of a large amount of organic matters and ozone are avoided; preferably, the temperature is controlled below 80 ℃ in the reaction, and when the temperature exceeds 80 ℃, water vapor may be formed, which may cause difficulty in stabilizing the negative pressure in front of the dispersion pump group 3. If the organic matter is difficult to dissolve in the water solution, a stirring device can be added, so that the organic matter enters the dispersion pump group 3 along with the water solution, and the ozone oxidation reaction is realized. In another embodiment, the method of the present invention for water treatment with high efficiency using ozone gas can react with bacteria to kill the bacteria.

In another embodiment, the method for water treatment with high efficiency using ozone gas of the present invention can be applied to harmless treatment of indoor space ozone. After sterilization using ozone in a closed space (for example, a food production plant, a medical facility, etc.), it is necessary to discharge residual ozone gas in the closed space to the outside of the room through ventilation. The gas-liquid mixing reaction device can be added with an air guide pipeline, waste gas is sucked into the dispersion pump unit 3 under negative pressure, the pressure of the vacuum meter 13 in front of the dispersion pump unit 3 is preferably more than-0.05 MPa, and harmless treatment of ozone gas in a closed space can be realized.

In S3, slowly closing the liquid inlet regulating valve 11 until the pressure in front of the dispersion pump group 3 is (-0.07 +/-0.03) MPa; after the pressure in front of the dispersion pump unit 3 is stable, the discharge regulating valve 61 is slowly closed until the pressure of the pressure stabilizing tank 5 is (0.50 +/-0.30) MPa. Wherein the pressure in front of the dispersion pump group 3 can be represented by the reading of the vacuum gauge 13 on the liquid inlet pipe 1, and the pressure of the pressure stabilizing tank 5 can be represented by the reading of the pressure gauge 51 on the pressure stabilizing tank 5.

In S4, after the pressure in front of the dispersion pump group 3 and the pressure in the pressure stabilizing tank 5 are stabilized, the air inlet adjusting valve 21 is slowly opened, ozone gas is input, but the volume of the input ozone gas is not more than one third of the volume of the material, and the pressure in front of the dispersion pump group 3 is-0.03 to-0.1 MPa. Ozone gas and materials are effectively mixed under the high-speed rotation of the dispersion pump group 3, the pressure in front of the dispersion pump group 3 is kept to be not less than-0.03 MPa, but the volume of the ozone gas is not excessive, otherwise, the stable control of the negative pressure in front of the dispersion pump group 3 and the positive pressure behind the dispersion pump group 3 is difficult to realize.

In S6, ozone is detected in the air near the liquid level of the material tank 7, and the cycle is terminated. And detecting air near the liquid level of the material pool 7, detecting color development regularly through moist KI test paper or detecting ozone by using an online ozone detector, namely indicating that the ozone escapes, and finishing the circulation when the reaction reaches the end point.

According to the method for efficiently utilizing ozone gas to treat water, the negative pressure suction type is adopted to suck the ozone into the dispersion pump 3 to be continuously mixed with the materials, so that the defect of insufficient subsequent mixing when ozone is blown into the traditional positive pressure bubbling type is overcome, the gas-liquid mixing degree of the ozone and the materials almost reaches an 'emulsifying' state, the utilization rate of the ozone gas is greatly improved, and zero emission is basically realized; meanwhile, the negative pressure is used for sucking the ozone, so that the phenomenon of serious leakage of ozone in workplaces is avoided, the loss of ozone gas is reduced, and the pollution to the environment is reduced; the application range is wide, and the ozone generator can be applied to disinfection and sterilization of drinking water and the like, sewage treatment, chemical production of organic matter double-bond oxidation and the like only by properly adjusting the concentration of ozone and selecting a proper dispersion pump 3.

Example 2

An oxygen source ozone machine is adopted to produce ozone gas, the flow rate of the ozone gas is set to be 20L/min, the ozone content is adjusted to be 80mg/L, and about 2mol of ozone is generated per hour.

Adding 98.7% anise camphor (CAS:104-46-1, chemical formula C) into distilled water₁₀H₁₂O, molecular weight of 148.21, density of 0.99)3000.6g to obtain water treatment material containing anethole as the object of treatment and anisic aldehyde (CAS:123-11-5, chemical formula from C) as the ozonization product₈H₈O₂Molecular weight 136.15, density 1.12). The ozonization reaction mechanism is shown as follows:

the gas-liquid mixing reaction apparatus described in example 1 was used. The material tank 7 is a white plastic bucket (inner diameter 560mm, height 850mm) with the capacity of 210L, and is filled with water treatment material and the height reaches about 750 mm. The water inlet of the liquid inlet pipe 1 is positioned 150mm below the liquid level, and the outlet of the discharge pipe 6 is positioned 650mm below the liquid level.

The liquid inlet regulating valve 11 and the discharge regulating valve 61 are set in a fully open state, the air inlet regulating valve 21 is set in a fully closed state, the dispersion pump unit 3 is opened, and materials circularly flow between the material tank 7 and a loop of the dispersion pump unit 3.

The front pressure of the dispersion pump group 3 is adjusted to be-0.09 MPa, and the pressure of the pressure stabilizing tank 5 is adjusted to be 0.20 MPa. The air inlet adjusting valve 21 is opened to introduce ozone gas, and the front pressure of the dispersion pump group 3 is about-0.04 MPa at the moment.

The gas-liquid mixing reaction device is set to operate for 10 hours, the molar ratio of the supply amount of the ozone to the anise camphor is just 1:1, and the ozone and the anise camphor theoretically completely react. In 10 hours, in the air above the liquid level of the material pool 7 and the material pool 7, the color is not changed by detecting the reaction by using moist KI test paper every hour, namely no ozone escapes before the reaction reaches the end point; and (3) taking a sample of the material to be treated, detecting once per hour by using moist KI test paper, wherein the color is not changed, namely the ozone and the material are completely reacted before the reaction reaches the end point. The reaction is finished after the circulation in the gas-liquid mixed reaction device for 10 hours, the materials are kept stand and layered to obtain 2771.4g of crude product, the chromatographic detection analysis is carried out on the crude product, the content of the anisic acid is 6.8 percent (namely, the rest 188.4g of anisic acid is used up, namely 2772.6g of anisic acid is used up), the content of the anisic acid is 90.8 percent (namely, at least 2739.3g of anisic acid is oxidized to generate anisic acid, in addition, 33.3g of anisic acid can be lost along with air flow, the generated anisic acid can be continuously subjected to ozonization reaction to generate other substances), only 18.4mol of ozone consumed for generating the anisic acid is used up, 20.0mol of ozone is supplied in total, and the ozone utilization rate is at least 92.4 percent (a small amount of ozone can be continuously subjected to ozonization reaction with the anisic acid to generate other substances, and can not be decomposed before the contact with the anisic acid).

From example 2, it can be seen that the key to the full use of ozone (no overflow of ozone detected on the material surface) is that the ozone has enough time to contact with the object to be treated, and the ozone can instantaneously undergo an ozonization reaction once it contacts with anise camphor (in the absence of water, ozone burns almost immediately with anise oil, turpentine oil, etc.). When ozone is used as a limited substance for supply, as long as the ozone can be fully contacted with a treatment object, the ozone utilization rate is very high, zero emission can be basically realized, and moist KI test paper is adopted to detect that air near the liquid level does not develop color.

Example 3

3000.1g of anethole with the content of 98.7 percent is added into distilled water to obtain a material.

The gas-liquid mixing reaction apparatus described in example 1 was used. The material tank 7 is a plastic barrel (inner diameter 560mm, height 850mm) with a capacity of 210L, and is filled with material and has a height of about 750 mm. The water inlet of the liquid inlet pipe 1 is positioned 150mm below the liquid level, and the outlet of the discharge pipe 6 is positioned 650mm below the liquid level.

The front pressure of the dispersion pump group 3 is adjusted to be-0.09 MPa, and the pressure of the pressure stabilizing tank 5 is adjusted to be 0.5 MPa. The air inlet adjusting valve 21 is opened to introduce ozone gas, and the front pressure of the dispersion pump group 3 is about-0.07 MPa at the moment.

The gas-liquid mixing reaction device is set to operate for 10 hours, the molar ratio of the supply amount of the ozone to the anise camphor is just 1:1, and the ozone and the anise camphor theoretically completely react. In 10 hours, in the air above the liquid level of the material pool 7, the color is not developed once every hour by using moist KI test paper, namely no ozone escapes before the reaction reaches the end point; standing the sample of the material treated in the material taking pool 7 for several minutes, detecting the water layer once per hour by using KI test paper after bubbles of the sample are broken and layered to form an oil layer and a water layer, wherein the color is not developed, namely, the ozone completely reacts with the anise camphor in the water treatment material before the reaction reaches the end point. The reaction is finished after the circulation in the gas-liquid mixed reaction device is carried out for 10 hours, the materials are kept stand for layering to obtain 2762.3g of crude product, the chromatographic detection analysis is carried out on the crude product, the content of the anisic acid is 3.4 percent (namely, the rest 93.9g of anisic acid is used up, namely, 2867.7g of anisic acid is used up), the content of the anisic aldehyde is 94.9 percent, the content of the anisic aldehyde (namely, 2853.7g of anisic acid is oxidized to generate the anisic aldehyde, and in addition, 14.0g of the anisic acid is lost) is 19.2mol of ozone, 20.0mol of ozone is supplied in total, and the ozone utilization rate is 96.2 percent.

Example 4

3000.3g of anethole with the content of 98.7 percent is added into distilled water to obtain a material.

The front pressure of the dispersion pump group 3 is adjusted to be-0.09 MPa, and the pressure of the pressure stabilizing tank 5 is adjusted to be 0.80 MPa. The air inlet adjusting valve 21 is opened to introduce ozone gas, and the front pressure of the dispersion pump group 3 is about-0.07 MPa at the moment.

The gas-liquid mixing reaction device is set to operate for 10 hours. In 10 hours, in the air above the liquid level of the material pool 7 and the material pool 7, the color is not changed by detecting the reaction by using moist KI test paper every hour, namely no ozone escapes before the reaction reaches the end point; and (3) taking a sample of the material to be treated, detecting once per hour by using moist KI test paper, wherein the color is not changed, namely the ozone and the material are completely reacted before the reaction reaches the end point. And then the reaction is finished after the gas-liquid mixing reaction device is arranged for circulating for 5 hours, and the molar ratio of the ozone supply to the anise camphor is just 1.5:1, namely the ozone is excessive by 50% theoretically. The materials are kept stand for layering to obtain 1655.6g of crude product, and the crude product is subjected to chromatographic detection analysis, wherein the content of the anethole is 0.1% (namely the rest 1.65g of the anethole), the content of the anisic aldehyde is 65.9% (namely 1187.7g of the anethole is oxidized to generate anisic aldehyde), and other impurities are increased from 1.3% to 34.0%, which indicates that the anisic aldehyde generated by 1771.9g of the anethole is continuously oxidized by ozone to generate other small molecular substances.

Example 5

3kg of sludge in a sewage pool of a local printing and dyeing mill is added into distilled water to obtain a water treatment material, wherein the bottom layer of the material is dark green sludge, the distilled water is dark green solution, and treatment objects in the water treatment material are dark green organic pigments and the like.

The gas-liquid mixing reaction apparatus described in example 1 was used. The material pool is a white plastic barrel (with an inner diameter of 560mm and a height of 850mm) with the capacity of 210L, and the material is filled in the material pool and the height of the material pool reaches about 550 mm. The water inlet of the liquid inlet pipe is positioned at 650mm below the liquid level to facilitate the introduction of the substrate sludge into the liquid inlet pipe, and the outlet of the discharge pipe is positioned at 200mm above the liquid level (namely, about 100mm from the top of the barrel), so that a large amount of bubbles are crushed by the impact force of the material at the discharge port and then become liquid again, and the phenomenon that the bubbles overflow from the barrel due to the slow rupture speed is avoided.

The liquid inlet regulating valve 11 and the discharge regulating valve 61 are set in a fully open state, the air inlet regulating valve 21 is set in a fully closed state, the dispersion pump unit 3 is opened, and the materials circularly flow between the material tank 7 and a loop of the dispersion pump unit 3.

The front pressure of the dispersion pump group 3 is adjusted to be-0.09 MPa, and the pressure of the pressure stabilizing tank 5 is adjusted to be 0.8 MPa. The air inlet adjusting valve 21 is opened to introduce ozone gas, and the front pressure of the dispersion pump group 3 is about-0.07 MPa at the moment.

Within 4 minutes of the operation of the gas-liquid mixing reaction device, detecting air above the liquid level of the material pool 7 by using moist KI test paper, and not developing color; in the 5 th minute, KI test paper color development, stop the gas-liquid mixture reaction unit, the material is colorless, and the soil grey flocculus is gathered fast to liquid upper strata, and dark green pigment is handled by ozone completely.

In this example 5, by using the method of the present invention for efficiently utilizing ozone, the pigment in the sludge can be continuously dissolved in water, the sludge dissolved in water is not available, the pigment can be well dispersed in the dispersion pump group 3, the pigment in the sludge is rapidly and completely treated by ozone, and the substances not participating in the ozonization reaction in the sludge are also in the form of grayish soil floc suspended on the liquid surface. Ozone in the ozone gas can be completely utilized as a limited supply substance, and zero emission is basically realized.

Example 6

The food and medical industry adopts ozone gas disinfection and sterilization places, usually an ozone generator is started for air supply after leaving work on the same day, and the machine is stopped before working on the next day, so that the ozone amount in the environment is large, the smell is bad, and the throat and eyes are uncomfortable. Ventilation is often used at various locations to achieve rapid ozone removal. However, the ventilation fan is usually installed in the upper half of a place, and ozone is slightly heavier than air and exists near the ground, so that the ventilation effect is not good. By adopting the method, a certain number of air suction pipelines are distributed on the places close to the ground, ozone gas is introduced into the air inlet pipe of the method, and domestic sewage (containing organic components) is introduced into the liquid inlet pipe nearby, so that harmless treatment of the ozone gas can be realized, and meanwhile, the sewage is treated, thereby achieving two purposes. In order to facilitate the collection of the exhaust gas, it is preferable that the vacuum gauge pressure before the pump reaches-0.05 MPa or more.

Example 7

For the current place where ozone gas is adopted for sewage treatment, if the existing equipment is not convenient to reform or needs a certain time to complete the reformation, an air suction coil pipe can be connected around an ozone gas aeration point, ozone gas overflowing from the sewage is introduced into the air inlet pipe of the invention, and the sewage is introduced into the water inlet pipe, so that the overflowing ozone gas can be recycled. In order to facilitate the collection of the exhaust gas, it is preferable that the vacuum gauge pressure before the pump reaches-0.05 MPa or more. By appropriate modification, the method of the invention can fully utilize ozone gas, basically realize zero emission, greatly reduce sewage treatment cost and improve sewage treatment effect and efficiency.

Comparative example 1

The gas-liquid mixing reaction apparatus described in example 1 was used. The material pool is a plastic barrel (with an inner diameter of 560mm and a height of 850mm) with the capacity of 210L, and is filled with distilled water, and the height of the distilled water reaches about 750 mm. The water inlet of the liquid inlet pipe is positioned at the position 150mm below the liquid level, and the outlet of the discharge pipe is positioned at the position 650mm below the liquid level.

Will the feed liquor governing valve with ejection of compact governing valve 61 sets up at full on-state, the air inlet governing valve sets up at the state of closing entirely, opens the dispersion pump, the material is in the material pond with circulation flow between the return circuit of dispersion pump.

The front pressure of the dispersion pump is adjusted to be-0.08 MPa, and the pressure of the pressure stabilizing tank is 0.4 MPa. And opening the air inlet regulating valve to introduce ozone gas, wherein the front pressure of the dispersion pump group 3 is about-0.05 MPa.

And (3) detecting in the air above the liquid level of the material pool by using a wet KI test paper, wherein about 0.8g of ozone enters 180kg of the material within 0.5 minute, but the KI test paper is developed, so that the ozone overflow is detected. And (3) taking the sample in the material pool for detection, wherein the KI test paper is not developed, the reaction time is prolonged for 30min, and the KI test paper is not developed.

From comparative example 1, it can be seen that distilled water was used as a comparative example, and the aqueous solution had no material to be treated, and ozone was supplied in excess, and ozone did not undergo oxidation reaction in the aqueous solution and still easily overflowed from the aqueous solution. By adopting the gas-liquid mixing reaction device, even if the gas-liquid mixing reaches the emulsified state of 10 mu m grade, the dissolution rate of ozone in water is not improved, and the solubility of ozone in water is very low. Therefore, when drinking water and the like are treated by using ozone gas at present, only the effect of improving the ozone utilization rate by improving the adding amount of ozone is not obvious, but the drinking water and the ozone gas are in full contact, and the ozone and harmful substances such as various bacteria can be in contact for carrying out instant oxidation reaction, so that the disinfection and sterilization functions can be realized. The method of the invention can achieve the effect of disinfection and sterilization of the drinking water only by using ozone with the quantity less than 10% in the current practical production.

Comparative example 2

A bubbling process is selected to introduce ozone gas into the material to be treated.

Using a bubbling tube apparatus with an inner diameter of 235mm and a height of 4500mm, distilled water was charged into the bubbling tube apparatus and reached a height of about 4200mm and a mass of about 180 kg. Ozone gas was bubbled through the bottom of the distillation water (inner gas bubbling circular sparger diameter 60mm, 1/4 about the inner diameter of the material pipe, evenly distributed 27 groups of pores, each group consisting of 6 pores, each pore diameter about 0.2mm, ozone gas flow per pore 2ml/S), ozone gas outlet pressure was about 0.4 MPa.

And (3) detecting in the air above the liquid level by using a wet KI test paper, wherein about 0.8g of ozone enters 180kg of the material within 0.5 minute, but the KI test paper is developed, namely, the ozone overflow is detected. And (3) taking a water sample in the treatment process for detection, wherein the KI test paper does not develop color, the bubbling time is prolonged for 30min, and the KI test paper does not develop color. The dissolution rate of ozone in water is low, and it is difficult to improve the utilization rate of ozone gas by bubbling.

Comparative example 3

Using a bubble tube apparatus (the same apparatus as used in comparative example 2), the apparatus was charged with a material having a height of about 4200mm and a mass of about 180 kg. Ozone gas was bubbled in from the bottom of the batch at a pressure of about 0.4 MPa.

Detecting in the air above the liquid level by using moist KI test paper, and developing the color by using the KI test paper in the 1 st minute; the bubbling tube apparatus was set to run for 10 hours. Detecting air above the liquid level once per hour in 10 hours by using a wet KI test paper, and developing color every time; taking the material water sample in the treatment as a control, and detecting once per hour by using moist KI test paper without developing color. Sampling the material after reacting for 10 hours in the bubbling tubular equipment, and performing chromatographic detection analysis on an oil layer in the material, wherein the content of the anise camphor is 45.5%, the content of anisic aldehyde obtained by oxidizing the anise camphor is 53.2%, 1661g of the anise camphor is oxidized, the conversion rate is 56.1%, the ozone consumption is 11.2mol, and the ozone utilization rate is 56.1%.

Comparative example 4

3kg of sludge in a sewage pool of a local printing and dyeing mill is added into distilled water to obtain a material, and the material is dark green.

A bubbling tube apparatus (the same apparatus as used in comparative example 2) was selected and charged with material up to a height of about 4200mm and a mass of about 180 kg. Ozone gas was bubbled in from the bottom of the batch at a pressure of about 0.4 MPa.

And (3) detecting in the air above the liquid level by using a wet KI test paper, wherein 0.8g of ozone enters 180kg of the material within 0.5 minute, but the KI test paper is developed, namely, the ozone overflow is detected. And then bubbling for 5 minutes, 15 minutes, 30 minutes, 60 minutes and 90 minutes respectively, taking out 100ml of the material, standing and layering to obtain an upper layer, a middle layer and a lower layer, wherein the upper layer has grey-soil floccules, the middle layer is colorless liquid, and the lower layer still has sludge sediment. With the increase of the bubbling time, the layering speed is gradually increased, the sludge precipitation is reduced in proportion, but the sludge precipitation is not obviously reduced after 60 minutes and still presents dark green.

Therefore, among CT empirical values recommended by the ozone industry, the C value (ozone water concentration mg/L) has a very limited effect on improving the ozone utilization rate, and the T value has no practical significance, and the key to really improving the ozone utilization rate is to increase the contact amount of ozone with a target object (a processing object), wherein the higher the contact amount is, the higher the utilization rate is, and the ozonization reaction cannot occur without contact.

The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.

Claims

1. A method for water treatment by using ozone gas with high efficiency is characterized in that:

the method comprises the following steps:

s1, providing a set of gas-liquid mixing reaction device, wherein the gas-liquid mixing reaction device comprises:

the device comprises a liquid inlet pipe, an air inlet pipe, a dispersion pump set, a pump rear pipe, a pressure stabilizing tank, a discharge pipe and a material pool;

the dispersion pump group comprises at least one dispersion pump, the inlet end of the dispersion pump group is connected with the liquid inlet pipe, and the outlet end of the dispersion pump group is connected with the pump rear pipe;

the liquid inlet pipe is provided with a liquid inlet regulating valve; the air inlet pipe is provided with an air inlet regulating valve; the air inlet pipe is communicated with the liquid inlet pipe, and the communicated position is positioned between the liquid inlet regulating valve and the dispersion pump set;

one end of the pressure stabilizing tank is connected with the rear pump pipe, and the other end of the pressure stabilizing tank is connected with one end of the discharge pipe;

the other end of the discharge pipe is communicated with the material pool; a discharge regulating valve is arranged on the discharge pipe;

the material pool is connected with the liquid inlet pipe and is used for containing materials;

s2: fully opening the liquid inlet regulating valve and the discharge regulating valve, fully closing the gas inlet regulating valve, opening the dispersion pump set, and enabling the materials to circularly flow in a loop of the gas-liquid mixing reaction device;

s3: adjusting the liquid inlet adjusting valve to reach negative pressure before the liquid inlet adjusting valve reaches the dispersion pump group; adjusting the discharge adjusting valve until the pressure stabilizing tank reaches positive pressure;

s4: opening the air inlet regulating valve to input the ozone gas into the dispersion pump group, wherein the ozone in the ozone gas is mixed with the materials in the dispersion pump group and reacts;

s5: the reacted materials enter the material pool through a material outlet pipe, and S4 is repeated;

s6: and ending the circulation when the reaction end point is reached.

2. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

in S3, slowly closing the liquid inlet regulating valve until the pressure before the dispersion pump set is (-0.07 +/-0.03) MPa; and after the pressure in front of the dispersion pump set is stable, slowly closing the discharge regulating valve until the pressure of the pressure stabilizing tank is (0.50 +/-0.30) MPa.

3. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

in S4, after the pressure in front of the dispersion pump group and the pressure in the pressure stabilizing tank are stabilized, slowly opening the air inlet adjusting valve, inputting the ozone gas, wherein the volume of the input ozone gas is not more than one third of the volume of the material, and the pressure in front of the dispersion pump group is-0.03 to-0.1 MPa.

4. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

in S6, ozone is detected in the air near the liquid level of the material pool, and the circulation is finished.

5. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

in S1, a liquid flowmeter and a vacuum meter are arranged on the liquid inlet pipe; a gas flowmeter is arranged on the gas inlet pipe; and a pressure gauge is arranged on the pressure stabilizing tank.

6. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

the diameter of the pressure stabilizing tank is not less than 2 times of the diameter of the pump rear pipe; the volume of the pressure stabilizing tank is more than or equal to half of the total volume of the closed space formed between the liquid inlet regulating valve and the gas inlet regulating valve and between the liquid inlet regulating valve and the discharge regulating valve.

7. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

when the material comprises organic matters and water solution, when the material is placed statically and layered to form an organic layer and a water layer, the inlet of the liquid inlet pipe is arranged at the position of the organic layer, and the outlet of the liquid outlet pipe is arranged at the position of the organic layer.

8. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

the ozone gas is ozone or a gas mixture with ozone accounting for less than 21% of the volume.

9. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

the dispersion pump unit comprises a pump cavity, and a disc type rotor is arranged in the pump cavity; and expanding the volume of the dispersion pump group, and increasing the number of the disc type rotors to ensure that the disc type rotors are sequentially arranged along the pump shaft.

10. The method for water treatment with high efficiency using ozone gas as claimed in claim 1, wherein:

the dispersion pump group comprises a plurality of dispersion pumps used in series and/or a plurality of dispersion pumps used in parallel, or a plurality of dispersion pumps used in series are connected in parallel for reuse.