Tail gas adsorption device and method for adsorbing tail gas of oil-containing pool

Abstract

The invention relates to the field of oil-containing sewage tail gas treatment, in particular to a tail gas adsorption device and an oil-containing pool tail gas adsorption method. The adsorption device comprises a shell and a containing cavity formed by the shell in a surrounding mode. The supporting structure is arranged in the containing cavity, and a gas flowing cavity is formed by the bottom of the supporting structure and the shell; the top of the supporting structure and the shell form an adsorption cavity; the supporting structure is provided with an opening; the adsorption material, the pressing plate and the filler cavity are arranged in the adsorption cavity and are sequentially arranged above the supporting structure; the adsorption material is used for adsorbing condensable gas in the tail gas of the oil-containing pool; the pressing plate extrudes the adsorption material through lifting; and the filler cavity is used for filling adsorption filler and adsorbing uncondensed gas in the tail gas of the oil-containing pool. And the oil absorption sponge which adsorbs the condensed tail gas is extruded by the extrusion unit to have an adsorption function again.

Description

Technical Field

[0001] The invention relates to the field of tail gas treatment of oily sewage, and in particular to a tail gas adsorption device and a tail gas adsorption method for an oily sewage pool. Background Art

[0002] The country has introduced stricter and more standardized standards for the emission of volatile organic compounds (VOCs).

[0003] In the petrochemical industry, a large amount of oily wastewater is inevitably produced. The composition of oily wastewater is complex, and it generally contains VOCs such as hexane, benzene, and toluene that are harmful to the environment and human safety. Oily wastewater is temporarily stored in oily wastewater pools. Standard GB 37822-2019 requires that "open liquid surfaces with VOCs escaping must be equipped with floating top covers or fixed covers to collect and treat oil vapor."

[0004] At present, the two main methods for treating VOCs emissions from oily wastewater pools are the above two. Among them, the investment cost of the floating top cover is large, and as the service time increases, the sealing performance decreases, resulting in unqualified VOCs emissions. Most companies choose to open tail gas emission ports on the fixed cover and set up oil and gas collection facilities such as activated carbon. However, the activated carbon oil and gas collection facility requires regular replacement of a large amount of activated carbon, which generates a large amount of solid waste. Summary of the invention

[0005] The purpose of the present invention is to overcome the defect of the existing activated carbon oil and gas collection facilities that regularly produce a large amount of solid waste. The present invention provides an oily sewage pool tail gas adsorption device and adsorption method. The device can effectively reduce the VOCs emission of the oily sewage pool and significantly reduce the amount of activated carbon used.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a tail gas adsorption device, the adsorption device comprising:

[0007] A housing and a receiving cavity formed around the housing;

[0008] A support structure is arranged in the accommodating cavity, wherein the bottom of the support structure and the shell form a gas flow cavity; the top of the support structure and the shell form an adsorption cavity; the support structure is provided with an opening;

[0009] An adsorption material, a pressure plate, and a packing cavity are arranged in the adsorption cavity and sequentially arranged above the support structure;

[0010] The adsorbent material is used to adsorb condensable gases in the tail gas of the oily sewage pool;

[0011] The pressing plate squeezes the adsorbent material by lifting and lowering;

[0012] The packing cavity is filled with adsorption packing for adsorbing uncondensed gas in the tail gas of the oily sewage pool;

[0013] The adsorption material includes an oil-absorbing sponge, which includes a three-dimensional porous polymer matrix and a thermosetting resin coated on the three-dimensional porous polymer matrix; the saturated adsorption capacity of the oil-absorbing sponge for oil products is not less than 30g / g; the saturated adsorption capacity of the oil-absorbing sponge for oil products is still not less than 30g / g after 30 adsorption-desorption cycles.

[0014] A second aspect of the present invention provides a method for adsorbing tail gas from an oily sewage pool, the method comprising:

[0015] The tail gas from the oily sewage pool contacts the adsorption material above the support structure through the openings of the support structure; then contacts the adsorption filler filled in the filler cavity and is discharged;

[0016] After the oil-absorbing sponge is saturated with adsorption, pressure is applied through the connecting rod mechanism to make the pressure plate descend, and the oil droplets formed by the condensable gas absorbed by the oil-absorbing sponge are discharged, flowing into the gas flow cavity from the openings of the supporting structure and discharged; the pressure plate rises, and the oil-absorbing sponge regains its adsorption function.

[0017] Through the above technical scheme, the oil-containing sewage pool adsorption device described in the present invention adopts the adsorption material described in the present invention, and the oil-absorbing sponge has super-hydrophobic and super-oleophilic properties. The porous skeleton of the oil-absorbing sponge and the super-oleophilic properties of the porous skeleton make the condensable gas in the tail gas of the oil-containing sewage adsorbed and condensed on the skeleton surface, intercepting most of the tail gas emissions. The oil-absorbing sponge after adsorbing the condensed tail gas is squeezed by the extrusion unit to regain the adsorption function. The adsorption filler (such as activated carbon) can adsorb a small amount of uncondensed gas. Since the oil-absorbing sponge has already adsorbed a large amount of condensable gas, the replacement cycle of the adsorption filler (such as activated carbon) is greatly reduced.

[0018] In the present invention, the oil and gas adsorption rate of the oil-absorbing sponge is greater than 90%, and the passing rate of the oil-containing tail gas is 100%; at the same time, the flame retardant grade of the oil-absorbing sponge can reach V-0, and it has very excellent flame retardant properties, which provides a more stable safety guarantee for the normal use of the oil-containing sewage pool, has a wide range of application conditions, and has achieved unexpected technical effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic diagram of a tail gas adsorption device for an oily sewage pool provided in a preferred embodiment of the present invention;

[0020] Figure 2 is a scanning electron microscope (SEM) image of the oil-absorbing sponge prepared in Preparation Example 1;

[0021] Figure 3is a scanning electron microscope (SEM) image of the oil-absorbing sponge prepared in Preparation Example 1 after 30 cycles;

[0022] Figure 4 is a scanning electron microscope (SEM) image of the porous melamine-formaldehyde sponge matrix in Preparation Example 1;

[0023] Figure 5 is a scanning electron microscope (SEM) image of the oil-absorbing sponge prepared in Preparation Example 8;

[0024] Figure 6 This is a scanning electron microscope (SEM) image of the oil-absorbing sponge prepared in Preparation Example 8 after being cycled 30 times.

[0025] Description of Reference Numerals

[0026] 1—filling cavity 2—adsorption material

[0027] 3—Support structure 4—Gas inlet pipeline

[0028] 5—Top cover 6—Connecting rod mechanism

[0029] 7—Shell 8—Gas outlet pipeline

[0030] 9—Press plate DETAILED DESCRIPTION

[0031] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0032] In the present invention, unless otherwise specified, directional words such as "up, down, left, right" generally refer to up, down, left, right as shown in the reference drawings; "inside, outside" refer to inside and outside relative to the outline of each component itself.

[0033] In the present invention, condensable gas refers to the part of the tail gas of the oily sewage pool that exists in the form of small droplets or condenses into liquid after contacting the oil absorbent sponge, and uncondensed gas refers to the component in the tail gas of the oily sewage pool that has not condensed into gaseous state.

[0034] The present invention provides a tail gas adsorption device, which comprises:

[0035] A housing and a receiving cavity formed around the housing;

[0036] A support structure is arranged in the accommodating cavity, wherein the bottom of the support structure and the shell form a gas flow cavity; the top of the support structure and the shell form an adsorption cavity; the support structure is provided with an opening to provide a flow channel for the fluid, so that the fluid can flow from the support structure into the gas flow cavity;

[0037] An adsorption material, a pressure plate, and a packing cavity are arranged in the adsorption cavity and sequentially arranged above the support structure;

[0038] The adsorbent material is used to adsorb condensable gases in the tail gas of the oily sewage pool;

[0039] The pressing plate, by lifting and lowering, squeezes the adsorbent material, discharges the condensable gas absorbed by the adsorbent material, and flows the gas into the gas flow cavity through the openings of the supporting structure;

[0040] The packing cavity is filled with adsorption packing for adsorbing uncondensed gas in the tail gas of the oily sewage pool;

[0041] The adsorption material includes an oil-absorbing sponge, which includes a three-dimensional porous polymer matrix and a thermosetting resin coated on the three-dimensional porous polymer matrix; the saturated adsorption capacity of the oil-absorbing sponge for oil products is not less than 30g / g; the saturated adsorption capacity of the oil-absorbing sponge for oil products is still not less than 30g / g after 30 adsorption-desorption cycles.

[0042] The tail gas adsorption device of the present invention adopts the adsorption material of the present invention. The oil-absorbing sponge has super-hydrophobic and super-oleophilic properties. The porous skeleton of the oil-absorbing sponge and the super-oleophilic properties of the porous skeleton allow the condensable gas in the tail gas of the oily sewage to be adsorbed and condensed on the skeleton surface, intercepting most of the tail gas emissions. The oil-absorbing sponge after adsorbing the condensed tail gas is squeezed by the extrusion unit to regain the adsorption function. The adsorption filler (such as activated carbon) can adsorb a small amount of uncondensed gas. Since the oil-absorbing sponge has already adsorbed a large amount of condensable gas, the replacement cycle of the adsorption filler (such as activated carbon) is greatly reduced.

[0043] According to a preferred embodiment of the present invention, the adsorption device further comprises:

[0044] A connecting rod mechanism, connected to the pressing plate and passing through the housing, for driving the pressing plate to move up and down; and / or

[0045] A top cover disposed above the housing to prevent rainwater or air impurities from reducing the adsorption capacity of the adsorption filler and the adsorption material; and / or

[0046] A gas inlet pipeline is arranged below the supporting structure and on the shell, and is used for the tail gas of the oily sewage pool to enter from below the supporting structure;

[0047] A gas outlet pipeline is arranged above the supporting structure and on the shell.

[0048] In the present invention, the support structure only needs not to be deformed during the descending process of the pressure plate. According to a preferred embodiment of the present invention, the support structure is selected from a support plate, a support net or a welded structure.

[0049] In the present invention, the adsorption filler is used to adsorb a small amount of uncondensed gas in the exhaust gas. There is no special limitation on the type of the adsorption filler. According to a preferred embodiment of the present invention, the adsorption filler is selected from at least one of activated carbon, zeolite, activated carbon fiber and coal-based adsorbent.

[0050] In the present invention, there is no particular limitation on the type of material of the support structure. According to a preferred embodiment of the present invention, the material of the support structure is selected from at least one of metals, inorganic non-metals and polymer materials, and more preferably selected from at least one of stainless steel, aluminum, silicates, aluminates, phosphates, borates, ABS, polypropylene, polyethylene and nitrile rubber.

[0051] According to a preferred embodiment of the present invention, the diameter of the openings on the support structure is preferably 5-20 mm, which is conducive to sufficient contact between the exhaust gas and the adsorption material and prevents the sponge from clogging the exhaust gas channel after adsorption saturation.

[0052] The oil-absorbing sponge of the present invention has super-hydrophobic and super-oleophilic properties while maintaining the high resilience and high porosity of the original three-dimensional porous polymer matrix. The oil-absorbing sponge has good resilience and strong adsorption capacity for oil products.

[0053] According to a preferred embodiment of the present invention, the mass of the thermosetting resin accounts for 0.5-5%, preferably 2-3%, of the total mass of the sponge.

[0054] According to a preferred embodiment of the present invention, the saturated adsorption capacity of the oil-absorbing sponge for oil is 30-50 g / g.

[0055] The oil-absorbing sponge of the present invention has strong selectivity for oil products in oily wastewater, large adsorption capacity for oil products and can be recycled. The adsorption capacity is basically not attenuated after being recycled for 30 times. According to a preferred embodiment of the present invention, the saturated adsorption capacity of the oil-absorbing sponge for oil products is still 30-50g / g after 30 desorption-adsorption cycles.

[0056] In the present invention, the thermosetting resin can be selected from a wide range, and conventional thermosetting resins in the field can meet the requirements of the present invention. According to a preferred embodiment of the present invention, the thermosetting resin is selected from at least one of phenolic resin, epoxy resin, urea-formaldehyde resin, unsaturated polyester resin and silicone resin; preferably selected from at least one of phenolic resin, epoxy resin and silicone resin.

[0057] In the present invention, the three-dimensional porous polymer matrix only needs to have a through-hole structure inside and a porosity greater than 70%. According to a preferred embodiment of the present invention, the three-dimensional porous polymer matrix is ​​selected from at least one of melamine-formaldehyde sponge, polyurethane sponge and ethylene-vinyl acetate sponge, preferably melamine-formaldehyde sponge.

[0058] In the present invention, the pore size of the oil absorbing sponge can be selected in a wide range. According to a preferred embodiment of the present invention, the pore size of the oil absorbing sponge is 10-500 μm, preferably 100-400 μm.

[0059] In the present invention, the porosity of the oil-absorbing sponge can be selected in a wide range. According to a preferred embodiment of the present invention, the porosity of the oil-absorbing sponge is greater than or equal to 60%, preferably greater than or equal to 90%.

[0060] The oil-absorbing sponge of the present invention has super-hydrophobic and super-oleophilic properties. According to a preferred embodiment of the present invention, the static plane contact angle of the surface of the oil-absorbing sponge to water in air is greater than 135°; preferably greater than 145°.

[0061] The oil-absorbing sponge of the present invention has super-hydrophobic and super-oleophilic properties. According to a preferred embodiment of the present invention, the static contact angle of the surface of the oil-absorbing sponge to white oil is less than 30°; preferably 0-20°; more preferably 0°.

[0062] The oil-absorbing sponge of the present invention also has flame retardant properties; according to a preferred embodiment of the present invention, the UL94 vertical burning test grade of the oil-absorbing sponge is above V-2, preferably above V-1; more preferably V-0.

[0063] The oil-absorbing sponges having the above-mentioned characteristics of the present invention can achieve the purpose of the present invention, and there is no special requirement for the preparation method thereof. With respect to the present invention, according to a preferred embodiment of the present invention, the present invention provides a method for preparing the oil-absorbing sponge of the present invention, the method comprising:

[0064] The solution containing the thermosetting resin prepolymer and the curing agent is dispersed into the three-dimensional porous polymer matrix, and cured under vacuum conditions to obtain the oil-absorbing sponge. The preparation method of the present invention disperses (for example, extrusion absorption dispersion, spray absorption dispersion) the solution containing the thermosetting resin prepolymer and the curing agent into the three-dimensional porous polymer matrix and then heats and cures it in vacuum, which can cure the thermosetting resin on the three-dimensional porous polymer matrix while maintaining the high resilience and high porosity of the original three-dimensional porous polymer matrix.

[0065] In the present invention, there is no particular limitation on the dispersion method of dispersing the solution containing thermosetting resin prepolymer and curing agent into the three-dimensional porous polymer matrix, as long as it can be evenly dispersed. According to a preferred embodiment of the present invention, the dispersion method is extrusion absorption dispersion or spray absorption dispersion, preferably extrusion absorption dispersion.

[0066] In the present invention, extrusion absorption dispersion refers to extruding the three-dimensional porous polymer matrix, placing it in a solution containing a thermosetting resin prepolymer and a curing agent, absorbing and restoring it to its original shape, and then extruding it to a certain proportion to discharge the excess solution and disperse it evenly.

[0067] In the present invention, spray absorption dispersion refers to uniformly dispersing a certain amount of thermosetting resin prepolymer and curing agent solution onto the surface of the three-dimensional porous polymer matrix in a spraying manner, waiting for absorption and then heating and curing.

[0068] In the present invention, the curing pressure may be selected in a wide range. According to a preferred embodiment of the present invention, the pressure is 0 to 10 kPa, preferably 3 to 5 kPa.

[0069] In the present invention, the curing conditions have a wide range of optional ranges. According to a preferred embodiment of the present invention, the curing conditions include: a temperature of 80 to 200°C, preferably 100 to 180°C; the curing time can be reasonably adjusted according to actual needs, preferably, the time is 5 to 120 minutes, more preferably 20 to 100 minutes.

[0070] According to a preferred embodiment of the present invention, the method for preparing the oil-absorbing sponge comprises:

[0071] (1) dispersing a solution containing a thermosetting resin prepolymer and a curing agent into a three-dimensional porous polymer matrix, and pre-curing under a first vacuum condition;

[0072] (2) dispersing a solution containing a thermosetting resin prepolymer and a curing agent into the product obtained in step (1), and curing the product under a second vacuum condition;

[0073] The first vacuum condition and the second vacuum condition each include: a pressure of 0-10 kPa;

[0074] Pre-curing conditions include: temperature of 80-120°C;

[0075] Curing conditions include: temperature of 140-180°C.

[0076] In the present invention, the thermosetting resin prepolymer is pre-cured to make the overall temperature of the sponge uniform, the thermosetting resin inside reaches a gel state, and is attached to the three-dimensional porous polymer matrix skeleton. The vacuum condition is conducive to the gas discharge in the thermosetting resin in the gel state, and better combined with the sponge skeleton. Then, the solution containing the thermosetting resin prepolymer and the curing agent is dispersed on the three-dimensional porous polymer matrix containing the gel-state thermosetting resin, and cured to obtain the oil-absorbing sponge, which is conducive to the uniform distribution of the thermosetting resin on the sponge skeleton, thereby maintaining the elasticity of the three-dimensional porous polymer matrix, improving the recyclable performance of the oil-absorbing sponge, and the adsorption capacity is basically not attenuated when it is recycled for 30 times.

[0077] According to a preferred embodiment of the present invention, in step (1), the gel-state thermosetting resin accounts for 0.5-1% of the total mass of the sponge, which is beneficial to further maintain the elasticity of the three-dimensional porous polymer matrix and improve the recycling performance of the oil-absorbing sponge.

[0078] In the present invention, in step (1), there is no special requirement for the pre-curing time, which can be reasonably adjusted according to actual needs, as long as the thermosetting resin prepolymer forms a gel-state thermosetting resin in the three-dimensional porous polymer matrix. According to a preferred embodiment of the present invention, the pre-curing time is 40-90 minutes.

[0079] In the present invention, in step (2), the curing time is 20-100 minutes.

[0080] According to a preferred embodiment of the present invention, in the solution containing the thermosetting resin prepolymer and the curing agent, the mass concentration of the thermosetting resin prepolymer is 0.02 to 0.6 g / mL, preferably 0.03 to 0.5 g / mL, and more preferably 0.05 to 0.3 g / mL.

[0081] According to a preferred embodiment of the present invention, in the solution containing the thermosetting resin prepolymer and the curing agent, the mass of the curing agent accounts for 1 to 10% of the mass of the thermosetting resin prepolymer; preferably 5 to 10%.

[0082] In the present invention, in the solution containing thermosetting resin prepolymer and curing agent, the optional range of solvent is relatively wide, as long as it can dissolve the thermosetting resin prepolymer and the curing agent. According to a preferred embodiment of the present invention, in the solution containing thermosetting resin prepolymer and curing agent, the solvent is selected from at least one of water, C1-C4 alcohol and C1-C4 ketone; preferably ethanol and / or acetone.

[0083] In the present invention, in the solution containing the thermosetting resin prepolymer and the curing agent, the curing agent has a wide range of options, as long as it can form the thermosetting resin with the thermosetting resin prepolymer. According to a preferred embodiment of the present invention, the curing agent is selected from at least one of organic acids, acid anhydrides, boron trifluoride, aliphatic polyamines and aromatic polyamines; preferably at least one of benzenesulfonic acid, hexamethylenetetramine and meta-phenylenediamine.

[0084] According to a preferred embodiment of the present invention, the distance between the lower surface of the top cover and the outlet of the gas outlet pipeline is 10-20 cm; the diameter of the top cover is 1.5-3 times the diameter of the gas outlet pipeline; through the above-mentioned arrangement, the top cover can effectively protect the adsorption filler and prevent pressure build-up, so that the oil-containing exhaust gas can flow out of the adsorption device smoothly.

[0085] According to a preferred embodiment of the present invention, the present invention provides a Figure 1 The schematic diagram of the tail gas adsorption device of the oily sewage pool shown in the figure, the adsorption device comprises:

[0086] A housing 7 and a receiving cavity formed around the housing 7;

[0087] A support structure 3 is arranged in the accommodating cavity, wherein the bottom of the support structure 3 and the shell 7 form a gas flow cavity; the top of the support structure 3 and the shell 7 form an adsorption cavity; the support structure 3 is provided with an opening;

[0088] The adsorption material 2, the pressing plate 9 and the filling cavity 1 are arranged in the adsorption cavity and are arranged in sequence above the support structure 3;

[0089] The adsorbent material 2 is used to adsorb condensable gases in the tail gas of the oily sewage pool;

[0090] The pressing plate 9 squeezes the adsorption material 2 by lifting and lowering;

[0091] The packing cavity 1 is used to load adsorption packing to adsorb uncondensed gas in the tail gas of the oily sewage pool;

[0092] A connecting rod mechanism 6, connected to the pressing plate 9 and passing through the housing 7, for driving the pressing plate 9 to move up and down; and / or

[0093] A top cover 5 disposed above the housing 7 to prevent rainwater or air impurities from reducing the adsorption capacity of the adsorption filler and the adsorption material; and / or

[0094] A gas inlet pipeline 4 is arranged below the supporting structure 3 and on the shell 7, and is used for the tail gas of the oily sewage pool to enter from below the supporting structure 3;

[0095] A gas outlet pipeline 8 is arranged above the supporting structure 1 and on the housing 7 .

[0096] According to a preferred embodiment of the present invention, the tail gas from the oily sewage pool includes C5-C8 alkanes, olefins and aromatics.

[0097] A second aspect of the present invention provides a method for adsorbing tail gas from an oily sewage pool, the method comprising:

[0098] The tail gas from the oily sewage pool contacts the adsorption material above the support structure through the openings of the support structure; then contacts the adsorption filler filled in the filler cavity and is discharged;

[0099] After the oil-absorbing sponge is saturated with adsorption, pressure is applied through the connecting rod mechanism to make the pressure plate descend, and the oil droplets formed by the condensable gas absorbed by the oil-absorbing sponge are discharged, flowing into the gas flow cavity from the openings of the supporting structure and discharged; the pressure plate rises, and the oil-absorbing sponge regains its adsorption function.

[0100] In the present invention, the tail gas of the oily sewage pool enters the adsorption device through the gas outlet pipeline, the tail gas of the oily sewage pool contacts the adsorption material above the support structure through the opening of the support structure, the condensable gas in the tail gas of the oily sewage pool condenses and is adsorbed in the porous structure of the oil-absorbing sponge, thereby adsorbing the condensable gas in the tail gas of the oily sewage pool; the tail gas containing sewage after the condensable gas is removed passes through the adsorption filler filled in the filler cavity, adsorbs the uncondensed gas in the tail gas of the oily sewage pool, so that the tail gas meets the emission standard, and then is discharged through the gas outlet pipeline. Since the oil-absorbing sponge has already adsorbed a large amount of condensable gas, the replacement cycle of the adsorption filler is greatly reduced.

[0101] After the oil-absorbing sponge is saturated with adsorption, pressure is applied through the connecting rod mechanism to make the pressure plate descend, and the oil droplets formed by the condensable gas absorbed by the oil-absorbing sponge are discharged, flowing into the oil storage cavity from the openings of the supporting structure and discharged; the pressure plate rises, and the oil-absorbing sponge resumes its adsorption function.

[0102] According to a preferred embodiment of the present invention, the filling height of the oil absorbing sponge is 8-15 cm.

[0103] According to a preferred embodiment of the present invention, the filling height of the adsorption filler is 5-10 cm.

[0104] In the present invention, the tail gas from the oily sewage pool includes C5-C8 alkanes, C5-C8 olefins and aromatic hydrocarbons, the C5-C8 olefins include isopentene, and the aromatic hydrocarbons include at least one of benzene, xylene and toluene.

[0105] The present invention will be described in detail below through examples.

[0106] In the following examples, the vertical burning test grade is tested according to the UL94 flame retardant test method.

[0107] In the following test examples, the saturated oil phase adsorption and the saturated oil phase adsorption after 30 cycles were tested using the following steps: weigh the mass of the sponge to be tested m1, place it in a beaker filled with 200mL toluene, weigh the mass of the sponge after adsorption saturation m2, and the saturated oil phase adsorption (Ф): Ф = m2 / m1. The test of the saturated oil phase adsorption after 30 cycles was first performed by saturating the sponge with toluene, mechanically squeezing it until no oil phase dripped naturally, and repeating it 30 times. The subsequent test steps were consistent with the saturated oil phase adsorption.

[0108] In the following embodiments, the water contact angle parameters were measured using the EASY DROP contact angle tester from KRUSS, Germany, with a measurement range of 1-180° and a resolution of ±0.1°. A static contact angle measurement mode was used, and a water droplet or white oil droplet with a fixed volume of 2 μL was dropped on the sponge each time. The calculated initial contact angle was taken as the contact angle measurement value of the sponge surface. Six parallel measurements were performed to calculate the average value.

[0109] In the following examples, the VOCs components of the sewage pool are mainly a mixture of C5-C8 alkanes, olefins and aromatics.

[0110] In the following examples, the oil and gas adsorption effect was tested for the non-methane total hydrocarbon content according to GB 37822-2019, and each example was tested after being placed at the same oil and gas adsorption site for 10 days and 30 days.

[0111] In the following examples, the porous melamine-formaldehyde sponge matrix (Xuxian Industrial) had a porosity of 95% and an average pore size of 100 μm;

[0112] The porous melamine-formaldehyde sponge matrix (Beiyou Building Materials) has a porosity of 96% and an average pore size of 250 μm.

[0113] In the following examples, the following method is used to test the oil and gas adsorption rate of the purge gas: the test temperature (T) is set to 35°C, and the PX device closed sampler is used as an example. After the sampling is completed, the sampled gas fills the pipeline of the same length. Nitrogen is used as the purge gas for purging, and the cumulative purge is n times. The total mass of the condensable gas of the sampled gas is (0.05*n)g, and the weight increase m of the purge gas adsorption tank is recorded.

[0114] Oil and gas adsorption rate (η): η = m / (0.05*n).

[0115] In the following examples, the porous melamine-formaldehyde sponge matrix (Xuxian Industrial) had a porosity of 95% and an average pore size of 100 μm;

[0116] The porous melamine-formaldehyde sponge matrix (Beiyou Building Materials) has a porosity of 96% and an average pore size of 250 μm.

[0117] Preparation Example 1

[0118] (1) Weigh 10 g of phenolic resin prepolymer solution (plasticized by Meisheng Chemical) and 1 g of hexamethylenetetramine and dissolve them in 200 mL of ethanol. Stir thoroughly to make the solution clear and transparent.

[0119] (2) A 200*200*150 mm porous melamine-formaldehyde sponge matrix (Xuxian Industrial) was measured and the above solution was dispersed into the sponge by extrusion dispersion so that the curing agent solution evenly infiltrated the sponge. The extruded sponge was placed in a vacuum oven at 180°C and 3 kPa for curing for 20 min to obtain an oil-absorbing sponge S1.

[0120] In the oil-absorbing sponge S1, the mass of phenolic resin accounts for 2% of the total mass of the oil-absorbing sponge; the average pore size of the oil-absorbing sponge S1 is 100 μm, the porosity is 95%, the open porosity is 98%, the vertical combustion grade is V-0, the contact angle to white oil is 0°, the contact angle to water is 152.3°; the saturated oil phase adsorption amount is 40 g / g.

[0121] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0122] Among them, the SEM image of the oil absorbing sponge S1 is as follows Figure 2 As shown, compared with the melamine-formaldehyde sponge matrix (SEM image as Figure 4 ), the porous skeleton size of the oil-absorbing sponge is slightly larger than that before modification, indicating that the phenolic resin is uniformly solidified on the surface of the porous melamine-formaldehyde sponge matrix skeleton and has through holes, which makes the oil-absorbing sponge highly selective for oil products in oily wastewater and has a large adsorption capacity for oil products.

[0123] Figure 3 The SEM image of the oil-absorbing sponge S1 after 30 cycles. Figure 2 Compared with the above, there is basically no change, so the adsorption capacity of the oil-absorbing sponge has basically not declined when it is recycled 30 times.

[0124] Preparation Example 2

[0125] (1) Weigh 10 g of phenolic resin prepolymer solution (plasticized by Meisheng Chemical), 0.3 g of hexamethylenetetramine and 0.2 g of m-xylylenediamine and dissolve them in 200 mL of ethanol. Stir thoroughly to make the solution clear and transparent.

[0126] (2) Weigh a 200*200*150 mm porous melamine-formaldehyde sponge matrix (Xuxian Industrial), and disperse the above solution into the sponge by extrusion dispersion so that the curing agent solution evenly infiltrates the sponge. Place the sponge after extrusion in a 140° C. vacuum oven for curing for 100 min to obtain an oil-absorbing sponge S2.

[0127] In the oil-absorbing sponge S2, the mass of phenolic resin accounts for 3% of the total mass of the sponge; the average pore size of the oil-absorbing sponge S2 is 100 μm, the porosity is 95%, and the open porosity is 98%; the vertical combustion grade is V-1, the contact angle to white oil is 0°, and the contact angle to water is 153.2°; the saturated adsorption capacity is 38 g / g.

[0128] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0129] Preparation Example 3

[0130] (1) Weigh 10 g of epoxy resin prepolymer solution (Willigut) and 0.6 g of hexamethylenetetramine and dissolve them in 200 mL of acetone. Stir thoroughly to make the solution clear and transparent.

[0131] (2) Weigh a 200*200*150 mm porous melamine-formaldehyde sponge matrix (Beyou Building Materials), and disperse the above solution into the sponge by spraying so that the curing agent solution evenly infiltrates the sponge. Place the extruded sponge in a vacuum oven at 150°C and 5 kPa for curing for 20 min to obtain an oil-absorbing sponge S3.

[0132] In the oil-absorbing sponge S3, the mass of epoxy resin accounts for 3% of the total mass of the sponge; the average pore size of the oil-absorbing sponge S3 is 250 μm, the porosity is 96%, and the open porosity is 98%; the vertical combustion grade is V-0; the contact angle to white oil is 0°, and the contact angle to water is 151.1°; the saturated adsorption capacity is 40 g / g.

[0133] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0134] Preparation Example 4

[0135] The method of Preparation Example 3 was followed, except that the volume of the porous melamine-formaldehyde sponge matrix was 400*400*150 mm; the other conditions were the same as Preparation Example 3, to obtain oil-absorbing sponge S4.

[0136] In the oil-absorbing sponge S4, the mass of epoxy resin accounts for 0.5% of the total mass of the sponge; the average pore size of the oil-absorbing sponge S4 is 250 μm, the porosity is 92%, and the open porosity is 93%; the vertical combustion grade is V-0; the contact angle to white oil is 0°, and the contact angle to water is 146°; the saturated adsorption capacity is 37 g / g.

[0137] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0138] Preparation Example 5

[0139] The method of Preparation Example 3 was followed, except that 20 g of epoxy resin prepolymer solution (Willigut) and 1.2 g of hexamethylenetetramine were weighed and dissolved in 200 mL of acetone; the other conditions were the same as those of Preparation Example 3 to obtain oil-absorbing sponge S5.

[0140] In the oil-absorbing sponge S5, the mass of epoxy resin accounts for 5% of the total mass of the sponge; the average pore size of the oil-absorbing sponge S5 is 240 μm, the porosity is 87%, and the open porosity is 83%; the vertical combustion grade is V-1; the contact angle to white oil is 0°, and the contact angle to water is 155.4°; the saturated adsorption capacity is 32 g / g.

[0141] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0142] Preparation Example 6

[0143] (1) Weigh 10 g of phenolic resin prepolymer solution (plasticized by Meisheng Chemical) and 1 g of hexamethylenetetramine and dissolve them in 200 mL of ethanol. Stir thoroughly to make the solution clear and transparent.

[0144] (2) taking a 200*200*150 mm porous melamine-formaldehyde sponge matrix (Xuxian Industrial), dispersing the above solution into the sponge by extrusion dispersion, so that the curing agent solution evenly infiltrates the sponge, and curing the sponge after extrusion in a vacuum oven at 110° C. and 3 kPa for 80 min to obtain a sponge containing a gel-state phenolic resin; wherein the gel-state phenolic resin sponge accounts for 1% of the total mass of the porous melamine-formaldehyde sponge matrix;

[0145] (3) The solution of step (1) is dispersed into the sponge containing the gel-like phenolic resin obtained in step (2) by extrusion dispersion, so that the solution evenly infiltrates the sponge. The extruded sponge is placed in a vacuum oven at 180° C. and 3 kPa for curing for 20 min to obtain an oil-absorbing sponge S6.

[0146] The phenolic resin accounts for 2% of the total mass of the oil-absorbing sponge S6; the average pore size of the oil-absorbing sponge is 100 μm, the porosity is 95%, the open porosity is 98%, the vertical combustion grade is V-0, the contact angle to white oil is 0°, and the contact angle to water is 153.8°; the saturated oil phase adsorption amount is 44 g / g.

[0147] Preparation Example 7

[0148] (1) Weigh 10 g of phenolic resin prepolymer solution (plasticized by Meisheng Chemical) and 1 g of hexamethylenetetramine and dissolve them in 200 mL of ethanol. Stir thoroughly to make the solution clear and transparent.

[0149] (2) A 200*200*150 mm porous melamine-formaldehyde sponge matrix (Xuxian Industrial) was measured and the above solution was dispersed into the sponge by extrusion dispersion so that the curing agent solution evenly infiltrated the sponge. The sponge after extrusion was placed in a vacuum oven at 110° C. and 3 kPa for curing for 80 min to obtain a sponge containing gel phenolic resin; the pre-cured sponge was then placed in a vacuum oven at 180° C. and 3 kPa for curing for 20 min to obtain an oil-absorbing sponge S7.

[0150] In the oil-absorbing sponge S7, the mass of phenolic resin accounts for 2% of the total mass of the oil-absorbing sponge; the average pore size of the oil-absorbing sponge S8 is 100 μm, the porosity is 95%, the open porosity is 98%, the vertical combustion grade is V-0, the contact angle to white oil is 0°, the contact angle to water is 152.7°; the saturated oil phase adsorption amount is 41 g / g.

[0151] Preparation Example 8

[0152] The method of Preparation Example 1 was followed, except that the impregnation amount of the phenolic resin prepolymer was adjusted so that the mass of the phenolic resin accounted for 7% of the total mass of the oil-absorbing sponge. The remaining conditions were the same as those of Preparation Example 1, to obtain oil-absorbing sponge D1.

[0153] In the oil-absorbing sponge D1, the mass of phenolic resin accounts for 7% of the total mass of the sponge; the average pore size of the oil-absorbing sponge D1 is 230 μm, the porosity is 73%, and the open porosity is 69%; the vertical combustion grade is V-2; the contact angle to white oil is 0°, and the contact angle to water is 158.1°; the saturated adsorption capacity is 27 g / g.

[0154] Figure 5 is the SEM photo of sponge D1. Compared with oil-absorbing sponge S1 ( Figure 2 ), the skeleton and the joints of the sponge are obviously covered with more phenolic resin, which reduces the porosity of the sponge and the corresponding saturated adsorption capacity. In addition, the phenolic resin is unevenly distributed on the surface of the skeleton, which is prone to stress concentration during the cyclic use process, resulting in skeleton collapse. Figure 6 This is a photo of the skeleton of sponge D1 after being recycled 30 times. The stacking density of the skeleton has increased significantly, resulting in a decrease in the saturated adsorption capacity.

[0155] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0156] Preparation Example 9

[0157] The method of Preparation Example 1 is followed, except that in step (2), curing is carried out under normal pressure, specifically: the sponge after extrusion is placed in an oven at 180° C. for curing for 20 minutes, and the other conditions are the same as those of Preparation Example 1, to obtain oil-absorbing sponge D2.

[0158] In the oil-absorbing sponge D2, the mass of phenolic resin accounts for 0.2% of the total mass of the sponge; the average pore size of the oil-absorbing sponge D2 is 250 μm, the porosity is 96%, and the open porosity is 98%; the vertical combustion grade is V-0; the contact angle to white oil is 0°, and the contact angle to water is 133.1°; the saturated adsorption capacity is 30 g / g.

[0159] The sponge was tested for saturated oil phase adsorption, oil phase removal rate and oil phase selective adsorption rate after 30 cycles according to the test requirements. The results are shown in Table 1.

[0160] Examples 1-7 and Comparative Examples 1-2

[0161] In such Figure 1 In the adsorption device shown, the support structure 3 is a support net, and the diameter of the opening is 10 mm;

[0162] The distance between the lower surface of the top cover 5 and the outlet 8 of the gas outlet pipeline is 10 cm; the outer diameter of the gas outlet pipeline 8 is 140 mm; and the outer diameter of the top cover 5 is 280 mm.

[0163] The oil-absorbing sponges prepared in Preparation Examples 1-7 and Preparation Examples 8-9 were respectively filled on the support net 3, with a filling height of 10 cm, and the activated carbon filling height of the activated carbon adsorption layer was 6 cm. The non-methane total hydrocarbon content was tested after 10 days and 30 days, and the results are shown in Table 2.

[0164] Comparative Example 3: No oleophilic sponge was placed on the support net 3, and the activated carbon filling height of the activated carbon adsorption layer was 6 cm. The non-methane total hydrocarbon content was tested after 10 days and 30 days, and the results are shown in Table 2.

[0165] Comparative Example 4: The support net (3) and the activated carbon adsorption layer are not filled. The non-methane total hydrocarbon content was tested after 10 days and 30 days. The results are shown in Table 2.

[0166] Table 1

[0167]

[0168]

[0169] Table 2

[0170] serial number Oil absorbing sponge 10 days (ppm) 30 days (ppm) Example 1 S1 43 38 Example 2 S2 52 38 Example 3 S3 46 29 Example 4 S4 64 72 Example 5 S5 32 63 Example 6 S6 28 28 Example 7 S7 42 45 Comparative Example 1 D1 70 67 Comparative Example 2 D2 83 103 Comparative Example 3 - 138 587 Comparative Example 4 - 650 710

[0171] It can be seen from the results in Table 2 that the tail gas adsorption device for oily sewage pool of the present invention can effectively adsorb tail gas from oily sewage pool to make it lower than the national emission standard (80ppm). Compared with the adsorption by activated carbon only, the effective time is longer and the effect is better.

[0172] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A tail gas adsorption device, characterized in that: The adsorption device comprises: A housing (7) and a receiving cavity formed around the housing (7); A support structure (3) is arranged in the accommodating cavity, wherein the bottom of the support structure (3) and the shell (7) form a gas flow cavity; the top of the support structure (3) and the shell (7) form an adsorption cavity; and the support structure (3) is provided with an opening; An adsorption material (2), a pressure plate (9), and a filler cavity (1) are arranged in the adsorption cavity and are arranged in sequence above the support structure (3); The adsorbent material (2) is used to adsorb condensable gases in the tail gas of the oily sewage pool; The pressing plate (9) presses the adsorption material (2) by lifting and lowering; The packing cavity (1) is filled with an adsorption packing for adsorbing uncondensed gas in the tail gas of the oily sewage pool; The adsorption material (2) comprises an oil-absorbing sponge, which comprises a three-dimensional porous polymer matrix and a thermosetting resin coated on the three-dimensional porous polymer matrix; the saturated adsorption capacity of the oil-absorbing sponge for the oil product is not less than 30 g / g; the saturated adsorption capacity of the oil-absorbing sponge for the oil product is still not less than 30 g / g after 30 cycles of adsorption-desorption.

2. The adsorption device according to claim 1, wherein: The adsorption device also includes: A connecting rod mechanism (6), connected to the pressing plate (9) and passing through the housing (7), and used for driving the pressing plate (9) to move up and down; and / or A top cover (5) disposed above the housing (7) to prevent rainwater or air impurities from reducing the adsorption capacity of the adsorption filler and the adsorption material; and / or A gas inlet pipeline (4) is arranged below the support structure (3) and on the shell (7), and is used for the tail gas of the oily sewage pool to enter from below the support structure (3); A gas outlet pipeline (8) is arranged above the supporting structure (1) and on the shell (7).

3. The adsorption device according to claim 1 or 2, wherein: The support structure (3) is selected from a support plate, a support mesh or a welded structure; and / or The adsorption filler is selected from at least one of activated carbon, zeolite, activated carbon fiber and coal-based adsorbent; and / or The material of the support structure (3) is selected from at least one of metal, inorganic non-metal and polymer material; and / or The diameter of the openings on the support structure (3) is preferably 5-20 mm.

4. The adsorption device according to claim 1, wherein: The mass of the thermosetting resin accounts for 0.5-5% of the total mass of the sponge; preferably 2-3%; and / or The saturated adsorption capacity of the oil-absorbing sponge for oil products is 30-50 g / g; the saturated adsorption capacity of the oil-absorbing sponge for oil products is still 30-50 g / g after being used in a desorption-adsorption cycle for 30 times.

5. The adsorption device according to claim 1 or 4, wherein: The thermosetting resin is selected from at least one of phenolic resin, epoxy resin, urea-formaldehyde resin, unsaturated polyester resin and silicone resin; preferably selected from at least one of phenolic resin, epoxy resin and silicone resin; and / or The three-dimensional porous polymer matrix is ​​selected from at least one of melamine-formaldehyde sponge, polyurethane sponge and ethylene-vinyl acetate sponge, preferably melamine-formaldehyde sponge.

6. The adsorption device according to claim 1 or 4, wherein: The pore size of the oil absorbing sponge is 10-500 μm; and / or The porosity of the oil-absorbing sponge is greater than or equal to 60%.

7. The adsorption device according to claim 1 or 4, wherein: The static plane contact angle of the surface of the oil-absorbing sponge to water in air is greater than 135°; and / or The static contact angle of the oil-absorbing sponge surface to white oil is less than 30°; and / or The UL94 vertical burning test grade of the oil absorbing sponge is above V-2.

8. The adsorption device according to claim 1 or 4, wherein: The preparation method of the oil absorbing sponge comprises: The solution containing thermosetting resin prepolymer and curing agent is dispersed into a three-dimensional porous polymer matrix, and cured under vacuum conditions to obtain the oil-absorbing sponge; the vacuum conditions include: a pressure of 0-10 kPa.

9. The adsorption device according to claim 8, wherein: The preparation method of the oil absorbing sponge comprises: (1) dispersing a solution containing a thermosetting resin prepolymer and a curing agent into a three-dimensional porous polymer matrix, and pre-curing under a first vacuum condition; (2) dispersing a solution containing a thermosetting resin prepolymer and a curing agent into the product obtained in step (1), and curing the product under a second vacuum condition; The first vacuum condition and the second vacuum condition each include: a pressure of 0-10 kPa; Pre-curing conditions include: temperature of 80-120°C; Curing conditions include: temperature of 140-180°C.

10. A method for adsorbing tail gas from an oily sewage pool, characterized in that: The method includes: The tail gas from the oily sewage pool contacts the adsorption material (2) above the support structure (3) through the opening of the support structure (3); and then contacts the adsorption filler filled in the filler cavity (1) before being discharged; After the oil-absorbing sponge is saturated with adsorption, pressure is applied through the connecting rod mechanism to cause the pressure plate (9) to descend, and the oil droplets formed by the condensable gas absorbed by the oil-absorbing sponge are discharged, flowing into the gas flow cavity from the openings of the support structure (3) and discharged; the pressure plate rises, and the oil-absorbing sponge recovers its adsorption function; preferably, the tail gas from the oil-containing sewage pool includes C5-C8 alkanes, C5-C8 olefins and aromatics.

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