WO2018103461A1

WO2018103461A1 - Method and device for separating and recovering o2 and o3

Info

Publication number: WO2018103461A1
Application number: PCT/CN2017/107281
Authority: WO
Inventors: 小福特·斯科特·韦恩; 郎建峰
Original assignee: 山西北极熊环境科技有限公司
Priority date: 2016-12-05
Filing date: 2017-10-23
Publication date: 2018-06-14
Also published as: CN106731526A

Abstract

Provided are a method and a device for separating and recovering O2 and O3, falling within the technical field of oxygen recovery. O2 and O3 are separated and recovered from atmospheric air. Specifically, atmospheric air is collected with a fan and same passes through a plurality of gas separation filters step by step to separate and recover O2 and O3, and the remaining ingredients are released into the atmosphere. O2 and O3 can also be separated from industrial ozone generation. O2 is supplied to an ozone generator (3) through an O2 supply system (1), and the ozone generator (3) converts a portion of O2 into O3. A mixed gas of O2 and O3 passes through a polymer membrane filtration system (4) to separate O2 and O3, the separated O2 is introduced into the O2 supply system (1), and the separated O3 enters an industrial application. The separation and recovery of O2 and O3 from atmospheric air or an ozone generation system are realized, which can be widely extended to an industrial application and has a certain environmental and economic value.

Description

Method and device for separating and recovering O ₂ and 0 ₃

[0001] The present invention belongs to the technical field of oxygen recovery, and particularly relates to a method and device for separating and recovering 0 ₂ and 0 ₃

[0002] Oxygen has a wide distribution in nature, and oxygen is required in many industrial fields.

[0003] Currently, ozone has been widely used in many fields such as water treatment, medicine, food industry, and the like. It is well known that the typical ozone generating process in the prior art uses 0 _{2 to} produce 0 ₃ and has a relatively short half-life, so ozone is always produced on-site through an ozone generator. The main principle of the ozone generator is corona discharge. In the ozone generator, the presence of the corona discharge element provides a capacitive load, and 0 _{3 is} generated by 0 ₂ under the direct action of discharge. This corona discharge ruptures stable oxygen molecules and forms two oxygen radicals that can combine with oxygen molecules to form 0 ₃ . In most cases, only 10% of supply 0 ₂ is converted to 0 ₃ , unconverted 0 ₂ and required 0 ₃

They are imported into the application and are wasted. Separation and recycling of 0 ₂ will reduce the total consumption of 0 ₂ by about 80%.

[0004] Contaminant gases produced by human activities mainly include primary pollutants and stimulating pollutants. The primary pollutants mainly include: sulfur oxides (SOx), especially sulfur dioxide, compounds of the chemical formula SO ₂ , coal and petroleum usually contain sulfur compounds, which produce sulfur dioxide after combustion; nitrogen oxides (NOx), nitrogen oxides, In particular, nitrogen dioxide, produced under high temperature combustion; carbon monoxide (CO), CO colorless, odorless, toxic, but non-irritating, produced by incomplete combustion of fuels (such as natural gas, coal or wood); volatile organic compounds ( VOC), VOC is a well-known outdoor air pollutant, divided into methane (CH 4) and non-methane (NMVOCs); particulate matter, also known as particulate matter (PM), atmospheric particulate matter, or fine particulate matter, is suspended Solid or liquid microparticles in a gas; ammonia (NH ₃ ), produced in an agricultural production process, ammonia refers to a compound of the chemical formula NH ₃ , usually in the form of a gas, having a pungent odor. Secondary contaminants include: particulate matter produced by gaseous primary pollutants and compounds in photochemical smog, which is an air pollution, typical of smoke from a large number of coal-fired areas and The mixture of sulphur dioxide causes that modern smog usually does not come from coal, but emissions from vehicles and industry, which form secondary pollutants in the atmosphere under the action of the sun's ultraviolet rays, and combine with primary pollutants to form photochemical smog; Formed by NOx and VOC, ozone (0 ₃ ) is the main component of the troposphere and is also an important component of the stratosphere (often called the ozone layer) in a specific area. Many of the photochemical and chemical reactions involve ozone-driven night and night in the atmosphere. The chemical process that occurs, but in the case of abnormally high ozone concentrations caused by human activities (mostly fossil fuel combustion), ozone is also a pollutant, and is one of the components of smoke; peroxyacetyl nitrate (PAN).

Due to its small footprint, high energy efficiency and convenient modular design, membrane technology is a potential alternative to existing processes. The main gas separations that may be used in membrane technology include: 1) Separation of H ₂

/CO ₂ to prepare hydrogen for fuel cells; 2) CO ₂ /N ₂ separation for flue gas or lime furnace exhaust

To isolate CO _{2 ;} 3) CO ₂ /CH ₄ separation for natural gas processing or biogas purification; 4) Separation of 0 2 /N ₂ to prepare oxygen-enriched air or pure nitrogen. The recovery of organic vapors from membranes in gas stations or oil fields can reduce emissions of pollutants in the atmosphere and improve process efficiency and economic benefits. Selective separation of gases and/or vapors requires the membrane to be separated according to molecular properties. The film may be an inorganic porous film such as zeolite or mesoporous silica, which is separated according to the condensability of molecular size or permeation type. The material of the membrane can also be metal, which is mostly used for the separation of hydrogen, and is realized according to the possibility of performing chemical splitting and recombination reaction. The most common and most widely used film on the market is a polymer film, the separation of which is based on the principle commonly referred to as the solution diffusion mechanism. Despite some inherent limitations, one of the main objectives of gas separation studies using polymeric membranes is in material research to overcome such limitations. Molecular design and modeling techniques are used today to support and interpret test results on the one hand and to predict membrane performance on the other hand.

technical problem

Therefore, the separation and recovery of oxygen from atmospheric air and ozone generators has practical significance and certain economic value. The object of the present invention is to provide a method for separating and recovering 0 ₂ and 0 ₃ by using a polymer membrane system. And equipment.

Problem solution

Technical solution

An object of the present invention is to provide a method for separating and recovering 0 ₂ and 0 3 .

The present invention is achieved by the following technical solutions: [0009] A method for separating and recovering 0 ₂ and 0 _{3 is} a method for separating and recovering 0 ₂ and 0 ₃ from atmospheric air, the steps are: collecting air by using a fan, and filtering it through a plurality of gases step by step. Separate and recycle 0 2 and 0 ₃ and release the remaining components of atmospheric air into the atmosphere.

[0010] Further, the gas separation filter is a polymer membrane filter.

[0011] The above method for separating and recovering 0 ₂ and 0 ₃ , the specific steps are:

[0012] (1) Using a fan to collect atmospheric air, and entering the first-stage polymer membrane filter to separate and remove N ₂ and CO, N ^ nCO is re-released into the atmospheric air after passing through the pipeline and the damping device, and remaining The gas enters the second-stage polymer membrane filter through the pipeline;

[0013] (2) The gas is separated and removed in the second-stage polymer membrane filter, and the NO is re-released into the atmospheric air through the pipeline and the buffer device, and the remaining gas enters the third-stage polymer membrane filter through the pipeline; [0014] (3) the gas is separated in the third-stage polymer membrane filter 0 ₂ , 0 ₂ is introduced into the 0 ₂ treatment system through the pipeline for recycling, and the remaining gas enters the fourth-stage polymer membrane filter through the pipeline;

[0015] (4) in a fourth stage gas filter separator polymer film removing NO _2, and CO _2, and CO ₂ through duct and after re-released into the buffer means NO ₂ in the atmospheric air, through a pipe into the residual gas of Five-stage polymer membrane filter;

[0016] (5) The gas is separated in the fifth-stage polymer membrane filter by 0 ₃ , 0 ₃ is introduced into the ozone process through a pipeline, and the remaining gas is re-released into the atmospheric air through the pipeline and the buffer device.

[0017] The apparatus for performing the above method for separating and recovering 0 ₂ and 0 ₃ includes a fan sequentially connected through a pipeline, a first-stage polymer membrane filter, a second-stage polymer membrane filter 14, and a third stage a polymer membrane filter, a fourth-stage polymer membrane filter, and a fifth-stage polymer membrane filtration; wherein the first-stage polymer membrane filter is connected to the first-stage damping device through the first-stage pipeline; The second-stage polymer membrane filter is connected to the second-stage damping device through the second-stage pipeline; the third-stage polymer membrane filter is connected to the 0 ₂ processing system through the third-stage pipeline; the fourth The polymer membrane filter is connected to the fourth-stage damping device through the fourth-stage pipeline; the fifth-stage polymer membrane filtration is respectively connected to the ozone process through the ozone pipeline, and the fifth-stage damping device is connected through the fifth-stage pipeline. .

[0018] Further, a method for separating and recovering 0 ₂ and 0 ₃ is to separate 0 ₂ and 0 ₃ from industrial ozone generation, and then recover the method using 0 ₂ , the steps are: supplying ozone to the system through 0 ₂ The generator supplies 0 ₂ , the ozone generator converts the 0 ₂ portion to 0 ₃ , and passes the mixed gas of 0 ₂ and 0 ₃ discharged from the ozone generator through the high The molecular membrane filter separates 0 ₃ and 0 ₂ , and the separated 0 _{2 is} introduced into the 0 ₂ supply system, and the separated 0 ₃ enters the industrial application.

[0019] means for performing the above method for separating and recovering 0 ₂ and 0 ₃ , comprising a 0 ₂ supply system, a 0 ₂ storage container, an ozone generator, a polymer membrane filtration system, the 0 ₂ supply system, 0 _{2 The} storage container and the ozone generator are sequentially connected by a pipeline, the exhaust port of the ozone generator is connected to the polymer membrane filtration system, and the mixed gas of 0 ₂ and 0 ₃ is separated in the polymer membrane filtration system, The 0 ₂ is recycled through the pipeline to the 0 ₂ storage vessel, and 0 ₃ enters the industrial application.

[0020] The polymer film is a polyamide film made of a ceramic material.

[0021] In a typical polymer film application, the gas mixture can be effectively separated by a film made of a high molecular polymer such as a polyamide made of a ceramic material. The membrane can act as a permeable barrier to separate the gas mixture, with different compounds passing through the permeable barrier layer, or passing at different rates, or failing to pass. The membrane may be a polymer or the like, and the permeation of the gas molecules may vary depending on its size, diffusivity, or solubility. Further, it is known that a polymer film can separate the smallest molecules such as o ₂ , co ₂ , 0 ₃ and the like. Each type of membrane is designed according to its application to separate target molecules at specific pressures and flows.

[0022] Furthermore, those skilled in the art will appreciate that there are mainly three kinds of diffusion mechanisms: (a) Molecular sieve refers to a situation in which the pores of the membrane are too small to pass the component, and since the gas molecules are too small, the mechanism is not applicable to the gas. In application; (b) Knudsen diffusion occurs at very low pressures, where lighter molecules move faster in stabilizing larger pores. In such cases, the best description of molecular motion is the excessive tube convection driven by differential pressure, which can be quantified using Darcy's Law; (c) However, the more common model used in gas applications is solution diffusion. The particles dissolve first on the surface of the membrane and then diffuse through the membrane at different rates. In one or more embodiments of the invention, Figure 2 shows that the technique is applicable in the case where the appearance and disappearance of voids in the polymer film is relatively faster than the movement of the particles.

Advantageous effects of the invention

Beneficial effect

Compared with the prior art, the invention can realize the purpose of separating and recovering 0 ₂ and 0 3 from atmospheric air or ozone generating system, and can be widely popularized in industrial applications, and has certain environmental protection and economic value.

Brief description of the drawing DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention and the technical solutions in the prior art, the drawings used in the embodiments or the prior art description will be briefly described below, and obviously, in the following description The drawings are only some of the embodiments of the present invention, and other drawings may be obtained from those skilled in the art without departing from the drawings.

1 is a schematic structural view of a separation device of 0 ₂ and 0 ₃ in ozone generation;

2 is a schematic diagram of molecular diffusion;

3 is a schematic view of a typical polymer film;

4 is a schematic diagram of a system for separating 0 ₂ and 0 ₃ from the atmosphere.

Embodiments of the invention

[0029] In the following detailed description of the embodiments of the invention, reference to the claims However, it will be apparent to those skilled in the art that the present invention may be practiced without these details. In addition, the present invention does not introduce common knowledge in detail to avoid lengthy descriptions due to unnecessary description.

Embodiment 1

[0031] The separation device of 0 ₂ and 0 ₃ in ozone generation as shown in FIG. 1 includes 0 ₂ supply system 1, 0 ₂

2 storage container, an ozone generator 3, a polymer membrane filtration system 4, the supply system ₀₂ 1, ₀₂ 2 and the storage container are sequentially connected to the ozone generator 3 through a line, said discharge ozone generator 3 The gas port is connected with the polymer membrane filtration system 4, and the mixed gas of 0 ₂ and 0 ₃ is separated in the polymer membrane filtration system 4, and the 0 ₂ is recovered through the pipeline and input to the 0 ₂ storage container 2, ₀₃ into the industrial application. .

[0032] After the operation, the supply gas 0 _{2 is introduced} from the 0 ₂ supply system 1 into the storage container 2 of 0 ₂ through a series of typical pipe arrangements, and the raw material gas 0 ₂ is introduced into the ozone from the 0 ₂ storage container 2 through the pump. In the generator 3, where 0 ₂ is converted to 0 ₃ , 0 ₃ and (unconverted) 0 ₂ produced in the ozone generator 3 are introduced into the polymer membrane filtration system 4, where they are separated, pure 0 ₃ is introduced into the control panel through the network of pipes and auxiliary fittings, through a typical pipe arrangement through the control valve and flow meter, and then exported to the control panel into a specific application, where 0 ₃ can be delivered to the exhaust stream of the boiler, For converting NO to N0 _2; 0 ₂ by polymer The membrane filtration system 4 is separated from the 0 ₃ and introduced into the circulation pump through a network of pipes and auxiliary fittings, and is guided back to the 0 ₂ storage container 2 through a series of typical piping arrangements through the circulating pump 0 ₂ .

[0033] In one or more embodiments of the invention, Figure 2 shows molecular diffusion in different applications, where 5 is the flow through the pores, 6 is the diffusion through the pores, and 7 shows the molecular sieve process, 8 The solution is shown to diffuse through the dense membrane.

[0034] FIG. 3 shows a typical polymer membrane system in which the feed material of the feed tube 9 is separated into two components, including a permeate and a retentate, wherein the permeate passes through the membrane and passes through the conduit 10. The discharged gas, the retentate, is the remaining gas that is discharged through the line 11. The ease with which each substance passes through the membrane can be quantified by the permeability P i . Assuming ideal mixing on both sides of the membrane, using the ideal gas theorem, constant diffusion coefficient, and Henry's law

According to Fick's Law, the flux of matter is related to the pressure difference.

[0035] Example 2

[0036] The apparatus for separating 0 ₂ and 0 ₃ from the atmosphere as shown in FIG. 4 includes a fan 12 sequentially connected through a pipeline, a first-stage polymer membrane filter (PMF-01) 13, and a second-stage high Molecular Membrane Filter (PMF-02) 14. Third Stage Polymer Membrane Filter (PMF-03) 15. Fourth Stage Polymer Membrane Filter (PMF-04) 16. Fifth Stage Polymer Membrane Filtration (PMF) -05) 17, the first-stage polymer membrane filter (PMF-01) 13 is connected to the first-stage damper device 19 through the first-stage pipe 18, and the second-stage polymer membrane filter (P) MF-02) 14 is connected to the second stage damping device 21 through the second stage pipe 20, and the third stage polymer membrane filter (PMF-03) 15 is connected to the 0 ₂ processing system through the third stage pipe 22, The fourth-stage polymer membrane filter (PMF-04) 16 is connected to the fourth-stage damper device 24 through the fourth-stage pipeline 23, and the fifth-stage polymer membrane filtration (PMF-05) 17 is passed respectively. The ozone line 24 is connected to the ozone process, and the fifth stage damper 26 is connected through the fifth stage pipe 25.

[0037] After operation, atmospheric air is drawn into the device through a fan mounted on the side of the device, and the mixed atmospheric gas is guided by the fan 12 through the first-stage polymer membrane filter (PMF-01) 13, and separated from the mixed atmospheric gas. N ^ nCO , N ^ nCO is re-released into the atmospheric air after passing through the series first stage pipe 18 and the first stage damping device 19; the remaining atmospheric gas is sent to the second stage polymer membrane filter (PMF) -02 ) 14, where NO is separated from the mixed gas, and NO is re-released to the second-stage polymer membrane filter (PMF-02) 14 through the second-stage pipe 20 and the second-stage buffer device 21 to In the atmospheric air, the remaining atmospheric gas in the second-stage polymer membrane filter (PMF-02) 14 is introduced into the third-stage polymer membrane filter (P MF-03) 15, where 0 _{2 is} separated from other atmospheric gases and introduced into the industrial plant 0 ₂ treatment system through the series of third stage pipes 22; the remaining mixed atmospheric gas is made up of the third stage polymer membrane filter (PMF) -03 ) 15 was introduced into a fourth-stage polymer membrane filter (PMF-04) 16 where NO ₂ and CO ₂ were separated from the atmosphere mixture and passed through a series of fourth-stage tubes 23 and a fourth-stage buffer. The device 24 is re-released into the atmospheric air, and the remaining mixed atmospheric gas is introduced into the final fifth-stage polymer membrane filter (PMF-05) by the fourth-stage polymer membrane filter (PMF-04) 16. This 0 ₃ is separated and introduced into the ozone process of the industrial plant through the series ozone pipeline 24; the remaining mixed atmospheric gas passes through the series fifth-stage pipeline 25 after the fifth-stage polymer membrane filtration (PMF-05) 17 The fifth stage cushioning device 26 is re-released into the atmospheric air.

In one or more embodiments of the present invention, the apparatus of the present invention draws in atmospheric air, where the mixed gas is treated to include N ₂ , 0 ₂ and other mixed gases included in the atmosphere, and 0 ₂ and 0 are extracted from the mixed gas. ₃ , the order of extraction and the number of processing stages are not limited to the arrangement shown in FIG. 4, and those skilled in the art should understand that any order of any number of stages does not deviate from the scope of the present invention.

Claims

A method for separating and recovering O 2 and 0 3 is a method for separating and recovering 0 2 and 0 3 from atmospheric air, wherein the steps are: collecting air by using a fan, and passing it step by step A gas separation filter separates and recovers 0 2 and 0 3 and releases the remaining components of atmospheric air to the atmosphere. The method for separating and recovering 0 2 and 0 3 according to claim 1, wherein the gas separation filter is a polymer membrane filter. A method for separating and recovering 0 2 and 0 3 according to claim 1 or 2, wherein the steps are:

(1) Use a fan to collect atmospheric air and enter the first-stage polymer membrane filter to separate and remove N ₂ mCO , N ₂ and . 0 is re-released into the atmospheric air after passing through the pipeline and the damping device, and the remaining gas enters the second-stage polymer membrane filter through the pipeline;

(2) The gas is separated and removed in the second-stage polymer membrane filter, and the NO is re-released into the atmospheric air through the pipeline and the buffer device, and the remaining gas enters the third-stage polymer membrane filter through the pipeline;

(3) The gas is separated in the third-stage polymer membrane filter. 0 ₂ , 0 ₂ is introduced into the 0 ₂ treatment system through the pipeline for recycling, and the remaining gas enters the fourth-stage polymer membrane filter through the pipeline;

(4) separating and removing the gas NO ^ nC0 _{_2,} N0 ₂ and CO ₂ through the conduit and the buffer means after re-released into the atmospheric air in a fourth stage polymer membrane filter, the residual gas conduit into the fifth-stage polymer by Membrane filter

(5) The gas is separated in the fifth-stage polymer membrane filter. 0 ₃ , 0 ₃ is recycled through the pipeline into the ozone process, and the remaining gas is re-released into the atmospheric air through the pipeline and the buffer device.

Apparatus for performing the method according to any one of claims 1 to 3, characterized by comprising a fan sequentially connected through a pipeline, a first-stage polymer membrane filter, a second-stage polymer membrane filter 14, a three-stage polymer membrane filter, a fourth-stage polymer membrane filter, and a fifth-stage polymer membrane filtration; wherein the first-stage polymer membrane filter is connected through a first-stage pipeline The first stage damping device; the second stage polymer membrane filter is connected to the second stage damping device through the second stage pipeline; the third stage polymer membrane filter passes through the third stage pipeline and 0

₂ processing system connection; the fourth-stage polymer membrane filter is connected to the fourth-stage damping device through the fourth-stage pipeline; the fifth-stage polymer membrane filtration is respectively connected to the ozone process through the ozone pipeline, and the The fifth-stage pipe is connected to the fifth-stage damping device.

[Claim 5] A method for separating and recovering 0 ₂ and 0 3 is to separate 0 ₂ and 0 ₃ from industrial ozone generation.

Then, the method of recycling 0 ₂ is used, wherein the steps are: supplying 0 ₂ to the ozone generator through the 0 ₂ supply system, converting the 0 ₂ portion into 0 ₃ by the ozone generator, and 0 ₂ and 0 discharging the ozone generator The mixed gas of ₃ is passed through a polymer membrane filter, and 0 ₃ and 0 _{2 are} separated, and the separated 0 _{2 is} introduced and recovered into the 0 ₂ supply system, and the separated 0 _{3 is} put into industrial application.

[Claim 6] The apparatus for performing the method as claimed in claim 5, characterized in that the supply system ₀₂ comprises, storage container _02, an ozone generator, a polymer membrane filtration system, the supply system ₀₂ The 0 ₂ storage container and the ozone generator are sequentially connected through a pipeline, and the exhaust port of the ozone generator is connected with the polymer membrane filtration system, and the mixed gas of 0 ₂ and 0 ₃ is separated in the polymer membrane filtration system. The 0 ₂ is recycled through the pipeline and input to the 0 ₂ storage container, and 0 ₃ enters the industrial application.

[Clave 7] The apparatus according to claim 6, wherein the polymer film is a polyamide film made of a ceramic material.