Unpowered adsorption device and system and adsorption method

Abstract

The invention relates to the field of comprehensive treatment of unorganized waste gas emission, in particular to an unpowered adsorption device and system and an adsorption method. The gas inlet and the gas outlet are formed in the two ends of the tank body 101, the first adsorption area, the second adsorption area and the third adsorption area are sequentially arranged in the tank body in the material flowing direction, macroporous adsorption materials used for adsorbing liquid compounds in the oil-containing tail gas are contained in the first adsorption area and the third adsorption area, and the macroporous adsorption materials are used for adsorbing the liquid compounds in the oil-containing tail gas. The second adsorption area contains a microporous adsorption material, and the macroporous adsorption material comprises a super-hydrophobic melamine porous material. According to the device, the waste gas treatment effect can be improved through pre-adsorption and precise adsorption, meanwhile, the replacement period of an adsorption material is prolonged, and the later maintenance cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of comprehensive treatment of fugitive emissions, specifically to a non-powered adsorption device and system and an adsorption method. Background Technology

[0002] Comprehensive treatment of fugitive emissions from petrochemical production processes has always been a challenge and a major pain point in environmental governance. Fugitive emissions are characterized by small volumes and low calorific values, making them difficult to integrate into a unified waste gas treatment system. Currently, commonly used fugitive emission treatment methods include thermal treatment, solvent absorption, biological methods, plasma methods, and adsorption methods, each with its own advantages and disadvantages. Among these, adsorption is the most widely used due to its low initial investment cost and excellent treatment effect on small volumes and low concentrations of waste gas.

[0003] Non-powered adsorption equipment using activated carbon as the adsorbent is playing an increasingly important role in the treatment of fugitive emissions. CN211886116U discloses an activated carbon adsorption tank and a non-powered adsorption system for treating fugitive emissions, which demonstrates excellent adsorption performance for these gases. However, due to the poor selective adsorption capacity and low saturation adsorption capacity of activated carbon, the equipment containing activated carbon has a short adsorbent replacement cycle, and the adsorption process is accompanied by a large amount of exothermic radiation, undoubtedly increasing costs and risks in the production process. The value of reusing the adsorbed activated carbon is low, and it is generally disposed of by incineration or landfill, which easily causes secondary pollution. Therefore, there is an urgent need for a non-powered adsorption equipment and system with a long replacement cycle and good adsorption performance. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of existing non-powered adsorption equipment and technology, such as short adsorbent replacement cycles, high operating costs, and large amounts of solid waste to be processed, and to provide a non-powered adsorption device, system, and adsorption method. This device can significantly improve the replacement cycle of equipment and systems and reduce the amount of solid waste generated when processing adsorbed gases.

[0005] The first aspect of the present invention is a non-powered adsorption device, which includes a tank, an air inlet and an air outlet at both ends of the tank, and a first adsorption zone, a second adsorption zone and a third adsorption zone arranged sequentially in the tank along the material flow direction. The first adsorption zone and the third adsorption zone contain macroporous adsorption materials for adsorbing liquid compounds in oily exhaust gas, and the second adsorption zone contains microporous adsorption materials. The macroporous adsorption materials include superhydrophobic melamine porous materials.

[0006] A second aspect of the present invention provides a non-powered adsorption system, the system comprising: the non-powered adsorption device described in the first aspect of the present invention.

[0007] The third aspect of the present invention provides a non-powered adsorption method, which is carried out in the system described in the present invention. The method includes: the gas to be adsorbed enters the non-powered adsorption device from the inlet, passes through the first adsorption zone, and makes a first contact with the macroporous adsorption material in the first adsorption zone; then enters the second adsorption zone and makes a second contact with the microporous adsorption material; finally, it passes through the third adsorption zone and makes a third contact with the macroporous adsorption material, and the purified adsorbed gas is obtained at the outlet.

[0008] Through the above technical solution, in the device of the present invention, the macroporous adsorption material in the first adsorption zone has a large saturated adsorption capacity and high selective adsorption efficiency, which pre-adsorbs the adsorbed gas and can filter out liquid compounds therein. The gas passes through the microporous adsorption material in the second adsorption zone and is discharged in compliance with standards. The macroporous adsorption material in the third adsorption zone protects the microporous adsorption material in the second adsorption zone from external water vapor or oil vapor, thereby significantly improving the replacement cycle of the equipment and system and reducing the amount of solid waste generated. Compared with the prior art, the device of the present invention can improve the treatment effect of waste gas through pre-adsorption and precise adsorption, while extending the replacement cycle of the adsorption material and reducing the later maintenance cost. Attached Figure Description

[0009] Figure 1 This is an internal structural diagram of a non-powered adsorption device according to one embodiment of the present invention;

[0010] Figure 2 This is an external structural diagram of a non-powered adsorption device according to one embodiment of the present invention;

[0011] Figure 3 This is a flowchart of a non-powered adsorption system in one embodiment of the present invention;

[0012] Figure 4 These are physical images and SEM images of the superhydrophobic melamine porous material S1 in Example 1;

[0013] Figure 5 The images show the physical and SEM images of the melamine porous material matrix D1 in Comparative Example 1.

[0014] Figure 6 These are physical images and SEM images of the superhydrophobic melamine porous material S8 in Example 8;

[0015] Figure 7 These are thermogravimetric curves of the superhydrophobic melamine porous material S1 in Example 1, the superhydrophobic melamine porous material S2 in Example 2, and the melamine porous material matrix D1 in Comparative Example 1.

[0016] Figure 8 These are the infrared spectra of superhydrophobic melamine porous materials S1, S7, S8, and D1.

[0017] Explanation of reference numerals in the attached figures

[0018] 101—Tank body; 102—Air inlet; 103—Air outlet

[0019] 104—First adsorption zone; 105—Second adsorption zone; 106—Third adsorption zone

[0020] 107—Porous mesh material; 108—Gas adsorption layer; 201—Spare plate

[0021] 202—Bolt; 301—Flame Arrestor; 302—Shut-off Valve

[0022] 303 Non-powered adsorption device; 304 Pressure relief valve; 305 Exhaust tower Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] In this invention, unless otherwise stated, directional terms such as "up," "down," "left," and "right" generally refer to the up, down, left, and right as shown in the accompanying drawings; "inner" and "outer" refer to the inner and outer contours of each component itself; and "connection" includes both direct connection between two components and connection between two components through at least one intermediate component.

[0025] like Figure 1-2 As shown, the first aspect of the present invention provides a non-powered adsorption device, which includes a tank 101, an air inlet 102 and an air outlet 103 disposed at both ends of the tank 101, and a first adsorption zone 104, a second adsorption zone 105 and a third adsorption zone 106 sequentially disposed within the tank 101 along the material flow direction. The first adsorption zone 104 and the third adsorption zone 106 contain macroporous adsorption materials for adsorbing liquid compounds in oily exhaust gas, and the second adsorption zone 105 contains microporous adsorption materials. The macroporous adsorption materials include superhydrophobic melamine porous materials.

[0026] In practical use, the non-powered adsorption device of the present invention is placed vertically, that is, the air inlet (102) is located at the bottom of the cylinder and the air outlet (103) is located at the top.

[0027] The device of the present invention has three adsorption zones arranged in sequence. By pre-adsorption and precise adsorption, the treatment effect of waste gas is improved, while extending the replacement cycle of adsorption materials and reducing the later maintenance cost.

[0028] According to a preferred embodiment of the present invention, along the material flow direction, the second adsorption zone 105 is provided with at least one layer of gas adsorption layer 108 formed of microporous adsorption material, preferably 2-8 layers of gas adsorption layer 108, such as 2, 3, 4, 5, 6, 7, or 8 layers.

[0029] In this invention, there are no special restrictions on the distribution of each gas adsorption layer 108. It is preferred that they are uniformly arranged in the second adsorption zone 105. For example, in some specific processes, the width of the gas adsorption layer 108 along the flow direction is 20-30 cm.

[0030] According to the present invention, there is no special limitation on the distance between two adjacent gas adsorption layers, which is generally 1 / 3 to 1 / 2 of the height of the gas adsorption layer.

[0031] According to a preferred embodiment of the present invention, the tank 101 includes a porous mesh material 107 for fixing the macroporous adsorption material in the first adsorption zone 104 and the third adsorption zone 106, and fixing the microporous adsorption material in the second adsorption zone 105.

[0032] According to a preferred embodiment of the present invention, the first adsorption region 104, the second adsorption region 105 and the third adsorption region 106 are separated by the porous mesh material 107.

[0033] According to the present invention, in order to fix the microporous adsorption material to form a gas adsorption layer 108, the second adsorption region 105 includes a porous mesh material disposed on the upper and lower surfaces of the gas adsorption layer 108 for supporting the microporous adsorption material.

[0034] According to the present invention, the widths of the first adsorption zone 104, the second adsorption zone 105, and the third adsorption zone 106 are selected within a wide range, as long as sufficient adsorption capacity can be provided. In a preferred embodiment, along the material flow direction, the length ratio of the first adsorption zone 104, the second adsorption zone 105, and the third adsorption zone 106 is (0.1-0.4):1:(0.1-0.4), preferably (0.12-0.3):1:(0.12-0.3). For example, in some specific processes, the lengths of the first adsorption zone 104 and the third adsorption zone 106 are 10-30 cm, and the length of the second adsorption zone 105 is 0.8-1 m.

[0035] The porous mesh material in this invention has a wide range of material selection. As long as it can provide support, does not affect gas flow, and has a slow corrosion rate, it is acceptable. According to a preferred embodiment of this invention, the porous mesh material includes at least one of iron, aluminum, polyethylene, polypropylene, and nylon.

[0036] The size of the openings in the porous mesh material of this invention is not particularly limited, as long as it does not affect gas flow and prevents the corresponding adsorbent material from passing through. In one embodiment, the side length of the openings in the porous mesh material is 10-20 mm.

[0037] According to a preferred embodiment of the present invention, the first adsorption zone 104, the second adsorption zone 105 and the third adsorption zone 106 are each provided with an opening on their side for replacing the corresponding adsorption material, and a partition plate 201 is covered above the opening.

[0038] According to the present invention, there are no special restrictions on the material of the partition, which is generally metal.

[0039] According to a preferred embodiment of the present invention, the partition 201 is fixedly connected to the tank 101, and the fixed connection can be any method in the art, such as using bolts 202 for connection.

[0040] According to the present invention, in order to prevent gas leakage during use of the adsorption device, in one embodiment, a polymer sealing layer is provided at the bottom of the partition 201.

[0041] According to a preferred embodiment of the present invention, the superhydrophobic melamine porous material contains hydrophobic groups, and the structure of the hydrophobic groups contains carbonyl groups. The aforementioned embodiment enables the non-powered adsorption device to achieve a larger saturated adsorption capacity for oil and gas during use, and a higher long-cycle adsorption efficiency.

[0042] According to a preferred embodiment of the present invention, the hydrophobic group is obtained by hydrolysis of the hydrophilic group in the melamine porous material matrix.

[0043] The melamine porous material matrix in this invention refers to an existing matrix with a melamine backbone, wherein the melamine backbone contains free amino groups and the ether bonds connecting the melamine backbone are all hydrophilic groups. According to a preferred embodiment of this invention, the hydrolysis rate is 5%-85%, for example 5%, 10%, 14%, 18%, 20%, 35%, 42%, 50%, 56%, 58%, 60%, 70%, 80%, 85%, preferably 10%-60%, and more preferably 15%-50%. Using the aforementioned embodiments, the non-powered adsorption device of this invention achieves high saturation adsorption capacity and long-cycle adsorption efficiency for oil and gas during use.

[0044] According to a preferred embodiment of the present invention, the hydrophilic group is selected from ether bonds and / or amino groups.

[0045] In this invention, specifically, the carbonyl group is obtained by converting the free amino group in the melamine skeleton in the melamine porous material matrix. Specifically, the carbonyl group is located on the melamine skeleton, and the ether bond (~HN-COC-NH~) connecting the melamine skeleton is converted into the ~HN-CH2-NH~ structure.

[0046] According to the present invention, it is understood that the macroporous adsorbent material contains through pores. Preferably, the pore size of the superhydrophobic melamine porous material is 50-800 μm, more preferably 100-400 μm; preferably, the porosity of the superhydrophobic melamine porous material is greater than or equal to 80%, more preferably greater than or equal to 90%.

[0047] According to the present invention, it is understood that the superhydrophobic melamine porous material has superhydrophobic properties. In one embodiment, the superhydrophobic melamine porous material has a static planar contact angle with water in air of not less than 125°, for example, 125°, 128.5°, 138.7°, 139.2°, 139.7°, 141°, 138.3°, 141.3°, 145.3°, preferably not less than 135°, and more preferably 135°-150°.

[0048] According to a preferred embodiment of the present invention, the static contact angle of the superhydrophobic melamine porous material with white oil is not higher than 20°, for example, 0°.

[0049] According to a preferred embodiment of the present invention, the superhydrophobic melamine porous material has flame-retardant and temperature-resistant properties.

[0050] According to a preferred embodiment of the present invention, the superhydrophobic melamine porous material has a UL-94 vertical burning test rating of V-0.

[0051] According to a preferred embodiment of the present invention, the superhydrophobic melamine porous material has a long-term temperature tolerance range of -150 to 200°C.

[0052] According to a preferred embodiment of the present invention, the preparation method of the superhydrophobic melamine porous material includes: contacting a melamine porous material matrix with an acid solution followed by microwave irradiation, washing, and drying to obtain the superhydrophobic melamine porous material. The superhydrophobic melamine porous material preparation method used in the aforementioned embodiment is simple in process, has a short preparation cycle, uses inexpensive and readily available solutions, and is easy to operate continuously, facilitating large-scale industrial production. Furthermore, the prepared material exhibits excellent superhydrophobic properties and temperature resistance, enabling the device to be applied in oil and gas adsorption and separation scenarios, demonstrating a large saturated adsorption capacity for oil and gas and high long-cycle adsorption efficiency, exhibiting significant advantages.

[0053] In this invention, a melamine porous material matrix is ​​contacted with an acid solution and subjected to microwave irradiation. This causes some functional groups in the melamine porous material matrix to undergo rapid hydrolysis, partially transforming into hydrophobic groups. The surface energy of the melamine porous material rapidly increases, thus constructing a superhydrophobic surface. The asymmetric structure of the hydrophobic groups during the modification process allows for rapid absorption of microwave energy and hydrolysis. The resulting superhydrophobic melamine porous material makes the device in this invention more advantageous for achieving higher saturation adsorption capacity and longer-term adsorption efficiency for oil and gas in the non-powered adsorption device.

[0054] According to the present invention, the acid solution refers to a solution prepared by mixing acid and water. Preferably, when preparing the superhydrophobic melamine porous material, the concentration of the acid solution is 0.01-3 mol / L, for example, it can be 0.08 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, 1.2 mol / L, 1.5 mol / L, or 1.8 mol / L, preferably 0.05-2 mol / L, and more preferably 0.05-1.5 mol / L. The superhydrophobic melamine porous material prepared by the foregoing embodiments results in better saturation adsorption capacity and long-cycle adsorption efficiency for oil and gas in the non-powered adsorption device of the present invention.

[0055] According to a preferred embodiment of the present invention, the acid in the acid solution is selected from one or more inorganic acids and organic acids.

[0056] According to a preferred embodiment of the present invention, the inorganic acid is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, boric acid and phosphoric acid, preferably at least one of hydrochloric acid and sulfuric acid;

[0057] According to a preferred embodiment of the present invention, the organic acid is selected from at least one of acetic acid, citric acid, formic acid and oxalic acid, preferably citric acid and / or acetic acid.

[0058] According to the present invention, when preparing superhydrophobic melamine porous materials, the contact method is not particularly limited. It can be static contact or dynamic contact, with static contact being preferred. Specifically, static contact can be achieved by immersion. In particular, during immersion, it is sufficient for the melamine porous material matrix to be in full contact with the acid solution. Generally, it is completely immersed in the acid solution. The present invention will not elaborate on this point.

[0059] According to a preferred embodiment of the present invention, the contact time is 0.5s-100s, for example, it can be 0.5s, 0.8s, 1.0s, 2.0s, 3.0s, 4.0s, 5.0s, 6.0s, 7.0s, 8.0s, 9.0s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, or 100s, preferably 0.5-10s.

[0060] In this invention, the solid material after contact is subjected to microwave irradiation. The microwave irradiation can be carried out in various microwave reactors that are already in use in the prior art, and this invention does not have any particular limitations on this.

[0061] According to a preferred embodiment of the present invention, the conditions for microwave irradiation include: microwave irradiation power of 100-2000W, for example, 200W, 300W, 400W, 500W, 600W, 700W, 900W, 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, preferably 100-1800W; irradiation time of 20s-20min, for example, 20s, 1min, 2min, 5min, 10min, 15min, 20min, preferably 2min-10min.

[0062] According to the present invention, the surface of the material subjected to microwave irradiation after contact may contain some hydrolysis products and acidic components, which can be removed by washing. There is no particular limitation on the specific method, such as washing with deionized water until the washing solution is neutral, but the present invention is not limited to this.

[0063] According to the present invention, there is no particular limitation on the drying method, as long as the solvent after washing is removed without damaging the structure of the superhydrophobic melamine porous material. Conventional drying methods in the art can be used, such as at least one of vacuum drying, forced air drying and microwave drying. Microwave drying is preferred because it has higher evaporation efficiency and is more energy-saving. The drying time is generally controlled to be 5-120 min and the drying temperature is 60-100℃.

[0064] According to a preferred embodiment of the present invention, the microporous adsorption material includes at least one of activated carbon, zeolite molecular sieve and superhydrophobic melamine porous material, preferably activated carbon and / or zeolite molecular sieve. Activated carbon is used in this invention as an example to illustrate the advantages of the invention without limitation, but the invention is not limited thereto.

[0065] like Figure 1-3 As shown, the second aspect of the present invention provides a non-powered adsorption system, which includes: the non-powered adsorption device 303 described in the first aspect of the present invention.

[0066] In this invention, the non-powered adsorption system of this invention is used to treat waste gas, which can improve the treatment effect of waste gas, extend the replacement cycle of adsorption materials and reduce the later maintenance cost. In addition, the system has a small footprint, low risk of pressure buildup and low later maintenance cost.

[0067] According to the present invention, in order to make the system of the present invention safer to use, the system includes: a flame arrester 301, a shut-off valve 302, and a non-powered adsorption device 303 connected in sequence along the material flow direction.

[0068] According to the present invention, in order to better discharge the purified adsorbed gas, the system further includes an exhaust tower 305 connected to the non-powered adsorption device 303.

[0069] In this invention, the purified adsorbed gas is discharged into the atmosphere through the outlet (103) and the exhaust tower (305) in succession.

[0070] According to the present invention, in order to prevent the adsorbent material in the non-powered adsorption device 303 from becoming saturated and generating pressure buildup, in a preferred embodiment, the system further includes a pressure relief bypass disposed between the flame arrester 301 and the shut-off valve 302, the bypass being connected to the venting tower 305, and a pressure relief valve 304 disposed on the bypass.

[0071] The third aspect of the present invention provides a non-powered adsorption method, which is carried out in the system described in the present invention. The method includes: the gas to be adsorbed enters the non-powered adsorption device 303 from the inlet 102, passes through the first adsorption zone 104 and makes a first contact with the macroporous adsorption material in the first adsorption zone 104, then enters the second adsorption zone 105 and makes a second contact with the microporous adsorption material, and finally passes through the third adsorption zone 106 and makes a third contact with the macroporous adsorption material, and the purified adsorbed gas is obtained at the outlet 103.

[0072] In this invention, there are no special restrictions on the conditions of the first and second contacts, and they are generally carried out at room temperature (generally 20-30°C).

[0073] Unless otherwise specified, the first and second contacts in this invention are performed at room temperature and atmospheric pressure.

[0074] In this invention, based on the total volume of the macroporous adsorption material in the first adsorption zone 104, the gas hourly space velocity of the adsorbed gas is generally 1000-50000 h⁻¹. -1 .

[0075] In this invention, after the adsorbed gas enters the first adsorption zone 104 and makes a first contact with the macroporous adsorption material, the liquid compounds in the adsorbed gas are partially or completely absorbed by the macroporous adsorption material. Then, it enters the second adsorption zone 105. Due to the concentration difference, it migrates to the surface of the microporous adsorption material and is adsorbed. The remaining gas continues to be adsorbed in the third adsorption zone 106.

[0076] In this invention, the method of this invention exhibits excellent long-cycle adsorption effect when treating the adsorbed gas, which can significantly increase the material replacement cycle and reduce operating costs, showing obvious advantages in the field of fugitive emission control.

[0077] According to a preferred embodiment of the present invention, the adsorbed gas originates from the tail gas in the petrochemical production process.

[0078] According to a preferred embodiment of the present invention, the adsorbed gas contains non-methane hydrocarbon gases (e.g., benzene compounds and C2-C5 hydrocarbons), preferably the total concentration of non-methane hydrocarbon gases in the adsorbed gas is not higher than 10000 mg / m³. 3 Generally 3000-10000 mg / m² 3 In this invention, the content of non-methane hydrocarbon gases is 3000 mg / m³. 3 The adsorbed gas is used as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0079] According to the present invention, such as Figure 1-3As shown, in one embodiment, the non-powered adsorption system includes a flame arrester 301, a shut-off valve 302, a non-powered adsorption device 303, and a venting tower 305 connected in sequence; a pressure relief bypass is provided between the flame arrester 301 and the shut-off valve 302, and the bypass is connected to the venting tower 305. The non-powered adsorption device 303 includes a tank 101 and a first adsorption zone 104, a second adsorption zone 105, and a third adsorption zone 106 sequentially arranged within the tank 101 along the material flow direction. The first adsorption zone 104, the second adsorption zone 105, and the third adsorption zone 106... The first adsorption zone 104 and the third adsorption zone 106 are separated by a porous mesh material. The first adsorption zone 104 and the third adsorption zone 106 are filled with macroporous adsorption material. The second adsorption zone 105 is uniformly provided with a gas adsorption layer 108 formed by four layers of microporous adsorption material. The distance between two adjacent gas adsorption layers is 1 / 3 to 1 / 2 of the height of the gas adsorption layer. The upper and lower surfaces of the gas adsorption layer 108 are covered with porous mesh material. The material flow direction and the width ratio of the first adsorption zone 104, the second adsorption zone 105 and the third adsorption zone 106 are (0.12-0). .3):1:(0.12-0.3), the first adsorption zone 104, the second adsorption zone 105 and the third adsorption zone 106 are each provided with an opening on their side, and a metal partition 201 is covered above the opening. The metal partition 201 is connected to the tank 101 by bolts 202. A polymer sealing layer is provided at the bottom of the metal partition 201. In a preferred embodiment of the present invention, a method for non-powered adsorption in the system of the aforementioned embodiment is provided. The method includes passing the adsorbed gas sequentially through a flame arrester 301 and a cut-off Valve 302 allows the gas to enter the non-powered adsorption device 303 through the inlet 102. The adsorbed gas passes through the first adsorption zone 104 and makes a first contact with the macroporous adsorption material in the first adsorption zone 104. Then it enters the second adsorption zone 105 (the second adsorption zone 105 is provided with 4 layers of gas adsorption layers 108) and makes a second contact with the microporous adsorption material. Finally, it passes through the third adsorption zone 106 and makes a third contact with the macroporous adsorption material to obtain the purified adsorbed gas. The purified adsorbed gas is discharged into the atmosphere through the outlet 103 and the exhaust tower 305.

[0080] According to a preferred embodiment of the present invention, the adsorbed gas originates from the tail gas of a petrochemical production process. According to a preferred embodiment of the present invention, the adsorbed gas contains non-methane hydrocarbons (e.g., benzene compounds and C2-C5 hydrocarbons), preferably with a total concentration of non-methane hydrocarbons in the adsorbed gas not exceeding 1000 mg / m³. 3 .

[0081] The present invention will be described in detail below through embodiments.

[0082] In the context of this specification, including the following examples, the hydrolysis rate of the hydrophilic group was calculated by Agilent Micro-Infrared Spectroscopy using the ATR test mode. (Measured at 1625±5 cm⁻¹) -1 The fitted peak area at 1480 cm⁻¹ divided by 1480 cm⁻¹ -1 The ratio of the fitted peak area (S) is correlated with the hydrolysis rate (H). The hydrolysis rate of the unmodified melamine porous material is 0%, and the hydrolysis rate of the fully hydrolyzed sample, i.e., the infrared peak area ratio does not increase with the modification time, is 100%. The calculation yields H = 1.2S * 100%, and then the hydrolysis rate is obtained according to the formula and the test ratios of various embodiments.

[0083] In the context of this specification, including the following embodiments, the water contact angle parameter is measured using an EASY DROP contact angle tester from KRUSS GmbH, Germany, with a measurement range of 1-180° and a resolution of ±0.1°. The static contact angle measurement mode is used, with a fixed volume of 2μL of water or white oil droplets dropped onto the porous material each time. The calculated initial contact angle is taken as the contact angle measurement value of the porous material surface. Six parallel measurements are performed, and the average value is calculated.

[0084] In the following preparation examples, the melamine porous material matrix was purchased from Beiyou Building Materials and is a melamine porous material with through pores.

[0085] Example 1

[0086] like Figure 1-2 As shown, the non-powered adsorption device is as follows: Superhydrophobic melamine porous material S1 is filled into the first adsorption zone 104 and the third adsorption zone 106 respectively, along the material flow direction. The lengths of the first and third adsorption zones 104 and 106 are 25 cm, the length of the second adsorption zone 105 is 1 m, and the width of the gas adsorption band formed by the uniformly arranged microporous adsorption material in the second adsorption zone 105 is 25 cm. The distance between two adjacent gas adsorption layers 108 is 10 cm of the height of the gas adsorption layer. The first adsorption zone 104, the second adsorption zone 105, and the third adsorption zone 106 are separated by a porous mesh material made of stainless steel. The side length of the openings is 15 mm. Activated carbon is used as the microporous adsorption material. Each of the three adsorption zones 104, 105, and 106 has an opening on its side. A metal partition 201 covers the openings and is connected to the tank body 101 by bolts 202. A polymer sealing layer is provided at the bottom of the metal partition 201. Figure 3 The above-mentioned non-powered adsorption device is connected to the non-powered adsorption system for the adsorption of fugitive waste gas. The adsorption method is as follows:

[0087] The adsorbed gas passes sequentially through the flame arrester 301 and the shut-off valve 302, and enters the non-powered adsorption device 303 through the inlet 102. The adsorbed gas passes through the first adsorption zone 104 and comes into full contact with the macroporous adsorption material in the first adsorption zone. The liquid compounds are absorbed by the macroporous adsorption material. The remaining adsorbed gas enters the second adsorption zone 105 and migrates to the surface of the microporous adsorption material under the action of the concentration difference and is adsorbed. The remaining gas passes through the third adsorption zone 106. The purified adsorbed gas passes through the outlet 103 and the exhaust tower 305 and is discharged into the atmosphere.

[0088] The content of non-methane total hydrocarbons (benzene series and C2-C5 hydrocarbons) in the adsorbed gas is 3000 mg / m³. 3 The gas volume is 100 Nm³. 3 / h

[0089] The preparation method of the superhydrophobic melamine porous material S1 is as follows:

[0090] Prepare a 0.05 mol / L hydrochloric acid aqueous solution, immerse the melamine porous material matrix (porosity 95%, average pore size 100 μm) in the solution for 2 seconds, then remove it. After irradiation with 800 W microwave power for 4 minutes, remove it, wash with deionized water until the pH is neutral, and microwave dry it (control the drying temperature at 60℃ for 10 minutes) to obtain the superhydrophobic melamine porous material S1.

[0091] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix is ​​18%, and the resulting superhydrophobic melamine porous material S1 has an average pore size of 100 μm, a porosity of 95%, a contact angle of 0° to white oil, and a contact angle of 138.3° to water.

[0092] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0093] Example 2

[0094] The method is the same as in Example 1, except that superhydrophobic melamine porous material S2 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S2 is as follows: prepare a 0.5 mol / L hydrochloric acid aqueous solution, immerse the melamine porous material matrix (porosity of 93%, average pore size of 300 μm) in the solution for 5 seconds, then remove it, irradiate it with a microwave irradiation power of 1800 W for 2 minutes, wash it with deionized water until the pH is neutral, and then microwave dry it (controlling the drying temperature at 80°C for 80 minutes) to obtain superhydrophobic melamine porous material S2.

[0095] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix is ​​50%, and the resulting superhydrophobic melamine porous material S2 has an average pore size of 300 μm, a porosity of 93.2%, a white oil contact angle of 0°, and a water contact angle of 145.3°.

[0096] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0097] Example 3

[0098] The method of Example 1 is followed, except that superhydrophobic melamine porous material S3 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S3 is as follows: prepare a 0.25 mol / L citric acid aqueous solution, immerse the melamine porous material matrix (porosity of 96%, average pore size of 400 μm) in the solution for 10 seconds, then remove it, irradiate it with a microwave irradiation power of 200 W for 10 minutes, wash it with deionized water until the pH is neutral, and then microwave dry it (controlling the drying temperature at 60°C for 50 minutes) to obtain superhydrophobic melamine porous material S3.

[0099] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix was 35%, resulting in a superhydrophobic melamine porous material S3 with an average pore size of 400 μm, a porosity of 96.6%, a white oil contact angle of 0°, and a water contact angle of 141.3°.

[0100] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0101] Example 4

[0102] The method of Example 3 is the same, except that superhydrophobic melamine porous material S4 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S4 is as follows: prepare a 0.25 mol / L boric acid aqueous solution, immerse the melamine porous material matrix (porosity of 96%, average pore size of 400 μm) in it for 10 s and then take it out. After that, irradiate it with a microwave irradiation power of 200 W for 10 min and then take it out. Wash it with deionized water until the pH is neutral, and then microwave dry it (control the drying temperature at 60°C and dry for 50 min) to obtain superhydrophobic melamine porous material S4.

[0103] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix was 20%; the superhydrophobic melamine porous material S4 obtained had an average pore size of 400 μm, a porosity of 96.1%, a white oil contact angle of 0°, and a water contact angle of 128.5°.

[0104] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0105] Example 5

[0106] The method of Example 1 is followed, except that superhydrophobic melamine porous material S5 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S5 is as follows: prepare a 2 mol / L oxalic acid aqueous solution, immerse the melamine porous material matrix (porosity 95%, average pore size 100 μm) in the solution for 50 s and then remove it. After that, irradiate it with a microwave irradiation power of 1800 W for 2 min and then remove it. Wash it with deionized water until the pH is neutral, microwave dry it, control the drying temperature at 60°C, and dry it for 10 min to obtain superhydrophobic melamine porous material S5.

[0107] Among them, the hydrolysis rate of hydrophilic groups in the melamine porous material matrix is ​​58%, the average pore size of the superhydrophobic melamine porous material S5 is 90μm, the porosity is 86%, the contact angle with white oil is 0°, and the contact angle with water is 139.7°.

[0108] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0109] Example 6

[0110] The method of Example 1 is followed, except that superhydrophobic melamine porous material S6 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S6 is as follows: prepare a 0.05 mol / L hydrochloric acid aqueous solution, immerse the melamine porous material matrix (porosity of 95%, average pore size of 100 μm) in the solution for 2 seconds, then remove it, irradiate it with a microwave irradiation power of 800 W for 15 minutes, wash it with deionized water until the pH is neutral, and then microwave dry it (controlling the drying temperature at 60°C for 10 minutes) to obtain superhydrophobic melamine porous material S6.

[0111] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix was 56%, and the resulting superhydrophobic melamine porous material S6 had an average pore size of 100 μm, a porosity of 84%, a white oil contact angle of 0°, and a water contact angle of 141.0°.

[0112] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0113] Example 7

[0114] The method of Example 1 is the same, except that superhydrophobic melamine porous material S7 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S7 is as follows: prepare a 0.01 mol / L hydrochloric acid aqueous solution, immerse the melamine porous material matrix (porosity of 95%, average pore size of 100 μm) in it for 2 s and then take it out. After that, irradiate it with a microwave irradiation power of 200 W for 20 s and then take it out for microwave drying. Control the drying temperature at 60°C and dry for 60 min to obtain superhydrophobic melamine porous material S7.

[0115] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix is ​​5%, and the resulting superhydrophobic melamine porous material S7 has an average pore size of 100 μm, a porosity of 95%, a white oil contact angle of 0°, and a water contact angle of 82.5°.

[0116] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0117] Example 8

[0118] The method is the same as in Example 1, except that superhydrophobic melamine porous material S8 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S8 is as follows: prepare a 3 mol / L nitric acid aqueous solution, immerse the melamine porous material matrix in it for 60s and then take it out. After that, irradiate it with a microwave irradiation power of 2000W for 10min and then take it out for microwave drying. Control the drying temperature at 60℃ and dry it for 60min to obtain superhydrophobic melamine porous material S8.

[0119] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix was 82%, and the resulting superhydrophobic melamine porous material S8 had an average pore size of 67 μm, a porosity of 53%, a white oil contact angle of 0°, and a water contact angle of 147.8°.

[0120] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0121] Example 9

[0122] The method of Example 1 is followed, except that superhydrophobic melamine porous material S9 is used instead of superhydrophobic melamine porous material S1. The preparation method of superhydrophobic melamine porous material S9 is as follows: prepare a 0.05 mol / L nitric acid aqueous solution, immerse the melamine porous material matrix (porosity of 95%, average pore size of 100 μm) in the solution for 2 seconds, then remove it, irradiate it with a microwave irradiation power of 800 W for 4 minutes, wash it with deionized water until the pH is neutral, and then microwave dry it (controlling the drying temperature at 60°C for 10 minutes) to obtain superhydrophobic melamine porous material S9.

[0123] The hydrolysis rate of the hydrophilic groups in the melamine porous material matrix was 14%, and the resulting superhydrophobic melamine porous material S9 had an average pore size of 100 μm, a porosity of 93.3%, a white oil contact angle of 0°, and a water contact angle of 138.7°.

[0124] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0125] Example 10

[0126] The method of Example 1 is followed, except that superhydrophobic melamine porous material S1 is replaced with superhydrophobic melamine porous material S10. The preparation method of superhydrophobic melamine porous material S10 is as follows: prepare a 0.05 mol / L hydrochloric acid aqueous solution, immerse the melamine porous material matrix (porosity of 95%, average pore size of 100 μm) in the solution for 90 s, then remove it, irradiate it with a microwave irradiation power of 800 W for 4 min, wash it with deionized water until the pH is neutral, and then microwave dry it (controlling the drying temperature at 60°C for 10 min) to obtain superhydrophobic melamine porous material S10.

[0127] Among them, the hydrolysis rate of the hydrophilic groups in the melamine porous material matrix is ​​42%, and the resulting superhydrophobic melamine porous material S10 has an average pore size of 95 μm, a porosity of 88%, a white oil contact angle of 0°, and a water contact angle of 139.2°.

[0128] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0129] Comparative Example 1

[0130] The method is the same as in Example 1, except that an unmodified melamine porous material matrix D1 (porosity of 95% and average pore size of 100 μm) is used instead of the superhydrophobic melamine porous material S1.

[0131] Comparative Example 2

[0132] The method of Example 1 is different in that the first adsorption region 104 and the third adsorption region 106 are not filled with superhydrophobic melamine porous material S1.

[0133] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0134] Comparative Example 3

[0135] The method is the same as in Example 1, except that activated carbon is used instead of the superhydrophobic melamine porous material S1.

[0136] The non-methane total hydrocarbon content at the outlet of the venting tower was tested every 14 days, and the results are shown in Table 1.

[0137] Testing and characterization of superhydrophobic melamine porous materials:

[0138] The physical image and SEM image of the superhydrophobic melamine porous material S1 in Example 1 are shown below. Figure 4 As shown

[0139] The physical image and SEM image of the superhydrophobic melamine porous material S8 in Example 8 are shown below. Figure 6 As shown

[0140] The physical image and SEM image of the melamine porous material matrix D1 in Comparative Example 1 are shown below. Figure 5 As shown.

[0141] pass Figures 4-6 It can be seen that, compared with the melamine porous material matrix D1, the size of the porous material framework and the overall size of the porous material S1 did not change significantly. This indicates that the superhydrophobic porous material obtained by melamine porous material treatment has little effect on the pore size and porosity of the porous material matrix. The superhydrophobic melamine porous material S8, compared with the superhydrophobic melamine porous material S1, showed a certain degree of collapse, with reduced porosity and pore size. This indicates that under this condition, the high hydrolysis rate of the hydrophilic groups reduced the rigidity of the porous material framework.

[0142] Thermogravimetric curves of the superhydrophobic melamine porous material S1 in Example 1, the superhydrophobic melamine porous material S2 in Example 2, and the melamine porous material matrix D1 in Comparative Example 1 are shown below. Figure 7 As shown.

[0143] pass Figure 7 The superhydrophobic melamine porous materials S1 and S2 exhibit good temperature resistance, indicating that the modified materials retain their temperature resistance below 200℃ and can be recycled using a steam purging method.

[0144] The infrared spectra of superhydrophobic melamine porous materials S1, S7, S8, and melamine porous material matrix D1 are as follows: Figure 8 As shown, the infrared spectra of superhydrophobic melamine porous materials S2-S6 and S8-S10 are similar to those of superhydrophobic melamine porous material S1.

[0145] pass Figure 8 It can be seen that: 1628cm -1 The characteristic peak at 1480 cm⁻¹ is a new peak generated after modification, that is, the characteristic peak of the hydrophobic group. -1The peak at 1540 cm⁻¹ represents the stretching vibration peak of the melamine ring. Since the modification did not destroy the melamine ring, its intensity remains unchanged. The area of ​​this peak can be used to characterize the initial content of hydrophilic groups. -1 This is the CN stretching vibration. According to the peaks S7, S1, and S8, as the hydrolysis rate of the melamine porous material matrix increases and the degree of modification increases, this peak gradually weakens, while the peak at 1624 cm⁻¹... -1 This peak represents the stretching vibration of cyclic amides and gradually increases in intensity. It is speculated that the free amino groups on the melamine-formaldehyde resin gradually hydrolyze into hydroxyl groups under acidic conditions. The hydroxyl groups on the melamine ring are unstable and exist as isomers of lactams. (1141 cm⁻¹) -1 and 967cm - S1 represents the symmetric and antisymmetric absorption peaks in the COC bond. The intensity of these two absorption peaks gradually decreases with the increase of the hydrolysis rate of the melamine porous material matrix and the degree of modification, according to S7, S1, and S8, until they disappear. This indicates that after the melamine porous material matrix is ​​modified, the NCOCN structure in the melamine-formaldehyde sponge undergoes a deformaldehyde reaction, thereby generating the NCN structure.

[0146] Table 1

[0147]

[0148] The results in Table 1 show that the non-powered adsorption device, system, and adsorption method described in this invention exhibit excellent long-cycle adsorption effects when treating gases. This can significantly increase the material replacement cycle and reduce operating costs, demonstrating a clear advantage in the field of fugitive emissions control.

[0149] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A non-powered adsorption device, comprising a tank body (101), an air inlet (102) and an air outlet (103) arranged at both ends of the tank body (101), and a first adsorption zone (104), a second adsorption zone (105) and a third adsorption zone (106) arranged in the tank body (101) in sequence along the material flow direction, wherein, The first adsorption zone (104) and the third adsorption zone (106) contain macroporous adsorbent material, and the second adsorption zone (105) contains microporous adsorbent material, and the macroporous adsorbent material comprises super-hydrophobic melamine porous material.

2. The device of claim 1, wherein, In the direction of the material flow, the second adsorption zone (105) is provided with at least one gas adsorption layer (108) formed by microporous adsorbent material, preferably 2-8 gas adsorption layers (108), and preferably the second adsorption zone (105) comprises porous grid material arranged on the upper and lower surfaces of the gas adsorption layer (108) for supporting the microporous adsorbent material; and / or The tank (101) comprises porous grid material (107) for fixing the macroporous adsorbent material in the first adsorption zone (104) and the third adsorption zone (106) and for fixing the microporous adsorbent material in the second adsorption zone (105); Preferably, the first adsorption zone (104), the second adsorption zone (105) and the third adsorption zone (106) are separated by the porous grid material (107); Preferably, The material of the porous grid material comprises at least one of iron, aluminum, polyethylene, polypropylene and nylon; and / or The opening size of the porous grid material is 10-20 mm.

3. The device of claim 1 or 2, wherein, In the direction of the material flow, the length ratio of the first adsorption zone (104), the second adsorption zone (105) and the third adsorption zone (106) is (0.1-0.4):1:(0.1-0.4), preferably (0.12-0.3):1:(0.12-0.3); and / or The side of the first adsorption zone (104), the second adsorption zone (105) and the third adsorption zone (106) is respectively provided with an opening for replacing the corresponding adsorbent material, and preferably a partition plate (201) is arranged above the opening; Preferably, The partition plate (201) is fixedly connected with the tank (101); and / or The bottom of the partition plate (201) is provided with a high-molecular sealing layer.

4. The device of any one of claims 1-3, wherein, The microporous adsorbent material comprises at least one of activated carbon, zeolite molecular sieve and super-hydrophobic melamine porous material, preferably activated carbon and / or zeolite molecular sieve; and / or The super-hydrophobic melamine porous material contains hydrophobic groups, and the structure of the hydrophobic groups contains a carbonyl group; Preferably, the hydrophobic groups are obtained by hydrolysis of hydrophilic groups in the melamine porous material matrix; More preferably, The hydrolysis rate is 5%-85%, preferably 10%-60%, more preferably 15%-50%; and / or The hydrophilic groups are selected from ether bonds and / or amino groups.

5. The device of any one of claims 1-4, wherein, The pore size of the super-hydrophobic melamine porous material is 50-800 μm, preferably 100-400 μm; and / or The porosity of the super-hydrophobic melamine porous material is greater than or equal to 80%, preferably greater than or equal to 90%; and / or The porosity of the super-hydrophobic melamine porous material is greater than or equal to 80%, preferably greater than or equal to 90%; and / or The super-hydrophobic melamine porous material has a static flat contact angle of not less than 125°, preferably not less than 135°, to water in air; and / or The super-hydrophobic melamine porous material has a static contact angle of not more than 20° to white oil.

6. The device according to any one of claims 1-5, wherein, The preparation method of the super-hydrophobic melamine porous material comprises: contacting a melamine porous material substrate with an acid solution, followed by microwave irradiation, washing, and drying to obtain the super-hydrophobic melamine porous material; Preferably, The concentration of the acid solution is 0.01-3 mol / L, preferably 0.05-2 mol / L, and more preferably 0.05-1.5 mol / L; and / or The acid in the acid solution is selected from one or more of inorganic acids and organic acids; More preferably, The inorganic acid is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, boric acid, and phosphoric acid, and preferably at least one of hydrochloric acid and sulfuric acid; and / or The organic acid is selected from at least one of acetic acid, citric acid, formic acid, and oxalic acid, and preferably citric acid and / or acetic acid.

7. The device according to claim 6, wherein, The contact time is 0.5 s-100 s, preferably 0.5-10 s; and / or The microwave irradiation conditions include: a microwave irradiation power of 100-2000 W, preferably 100-1800 W; and / or an irradiation time of 20 s-20 min, preferably 2 min-10 min; and / or The drying mode is selected from at least one of vacuum drying, air blowing drying, and microwave drying, and preferably microwave drying.

8. A passive adsorption system, characterized in that The system comprises: The unpowered adsorption device (303) according to any one of claims 1-8; Preferably, The system comprises: a flame arrester (301), a shut-off valve (302), and the unpowered adsorption device (303) connected in sequence along the material flow direction; and / or The system further comprises an emptying tower (305) connected after the unpowered adsorption device (303); More preferably, The system further comprises a pressure relief bypass provided between the flame arrester (301) and the shut-off valve (302), the bypass being connected to the emptying tower (305), and a pressure relief valve (304) being provided on the bypass.

9. A non-powered adsorptive method, characterized by, The method is performed in the system according to claim 8, and the method comprises: The adsorbed gas enters the unpowered adsorption device (303) from the gas inlet (102), passes through the first adsorption zone (104), and is in first contact with the macroporous adsorbent material in the first adsorption zone (104), then enters the second adsorption zone (105) and is in second contact with the microporous adsorbent material, and finally passes through the third adsorption zone (106) and is in third contact with the macroporous adsorbent material to obtain the purified adsorbed gas at the gas outlet (103).

10. The method according to claim 9, wherein, The adsorbed gas is derived from tail gas in a petroleum chemical production process; and / or The adsorbed gas contains non-methane hydrocarbon gas, preferably the total concentration of non-methane hydrocarbon gas in the adsorbed gas is not higher than 10000 mg / m 3 , and is not 0 mg / m 3 .

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