Amine liquor oil removal recovery unit and recovery method

Abstract

The present application relates to amine liquid oil removal technical field, provide a kind of amine liquid oil removal recovery device, the device includes: first shell and the first containing cavity formed around the shell;Sealingly arranged in first containing cavity baffle, baffle bottom and the first shell form buffer cavity;Baffle top and the first shell form storage cavity;Baffle top is provided with second shell, baffle and second shell form adsorption filter cavity;Adsorption material is arranged in adsorption filter cavity is arranged in adsorption filter cavity and is placed on adsorption material above pressure plate;The baffle and the pressure plate are provided with opening;Connecting rod mechanism, with the pressure plate is connected, and it is through first shell, second shell;The first shell is provided with oil-removing amine liquid outlet, waste oil outlet and oil-containing amine liquid import that communicate the first containing cavity.This device is used for amine liquid oil removal, and oil removal efficiency is high, and amine liquid recovery rate is high.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of amine liquid oil removal, and particularly relates to an amine liquid oil removal and recovery device and a recovery method. BACKGROUND

[0002] As a mature technology with high efficiency and simple operation, amine liquid desulfurization technology is widely used in the fields of flue gas, coal gas and petroleum desulfurization. Compared with traditional selective desulfurization solvents, the compound amine liquid formula mainly composed of N-methyldiethanolamine (MDEA) has the advantages of high stability, good desulfurization selectivity, low regeneration energy consumption and low price. However, MDEA is prone to foaming in the presence of oil phase, which affects the safe and stable operation of the absorption tower, the regeneration tower and even the entire desulfurization system.

[0003] Currently, there are two measures to deal with amine liquid foaming. One is to add a defoaming agent. However, the defoaming agent itself is also a surfactant, and as the accumulation of oil phase in the amine liquid, the risk of amine liquid foaming gradually increases. The gradually accumulated impurities also cause fluctuations in the working conditions of the desulfurization system. The other method is amine liquid purification, that is, periodically discharging liquid at fixed points to discharge most of the oil phase and a small amount of amine liquid. However, this method causes waste of amine liquid and impact on downstream wastewater treatment devices.

[0004] In view of the above shortcomings of the conventional methods for avoiding amine liquid foaming, it is urgent to develop an amine liquid oil removal and recovery device to avoid amine liquid foaming and recover amine liquid. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art in dealing with amine liquid foaming, such as oil phase accumulation and amine liquid waste, and provides an amine liquid oil removal and recovery device. The device is used for amine liquid oil removal, has high oil removal efficiency and high amine liquid recovery rate, and avoids the problems of resource waste and increased water treatment cost caused by conventional treatment methods.

[0006] To achieve the above-mentioned purpose, the present application provides an amine liquid oil removal and recovery device, which comprises:

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

[0008] A partition plate sealingly arranged in the first containing cavity, the bottom of the partition plate forming a buffer cavity with the first housing, and the top of the partition plate forming a storage cavity with the first housing;

[0009] A second housing is arranged above the partition plate, and the partition plate and the second housing form an adsorption and filtration cavity;

[0010] An adsorption material is arranged in the adsorption and filtration cavity and used for adsorbing oil phase in the amine liquid; the adsorption material has super-hydrophobic and super-oleophilic properties;

[0011] a pressing plate arranged in the adsorption filtering cavity and placed above the adsorption material, the pressing plate extruding the adsorption material by lifting and lowering; the partition plate and the pressing plate are provided with openings to provide a flow channel for the fluid, so that the fluid can enter the adsorption filtering cavity from the buffer cavity through the partition plate, and then enter the storage cavity through the pressing plate;

[0012] a connecting rod mechanism connected with the pressing plate and penetrating through the first shell and the second shell to drive the pressing plate to lift and lower;

[0013] the first shell is provided with a triolein outlet, a waste oil outlet and a triolein inlet communicating with the first containing cavity; the triolein outlet is arranged above the partition plate, and the waste oil outlet and the triolein inlet are arranged below the partition plate.

[0014] The second aspect of the present application provides an amine solution oil removal and recovery method, which comprises:

[0015] (1) opening the triolein inlet and the triolein outlet, closing the waste oil outlet, and allowing the triolein to enter the buffer cavity from the triolein inlet; the triolein flows into the adsorption filtering cavity through the openings of the partition plate, and the oil phase in the triolein is adsorbed by the adsorption material in the adsorption filtering cavity to obtain triolein; the triolein flows out through the openings of the pressing plate and enters the storage cavity, and is discharged from the triolein outlet;

[0016] (2) when the adsorption material is saturated, closing the triolein inlet and the triolein outlet, opening the waste oil outlet, driving the connecting rod mechanism to lower, and allowing the pressing plate to extrude the adsorption material to discharge the oil phase in the adsorption material, and allowing the oil phase to flow into the buffer cavity through the openings of the partition plate and be discharged from the waste oil outlet;

[0017] (3) after the oil phase is discharged, driving the connecting rod mechanism to rise, so that the adsorption material has adsorption capacity again, and repeating step (1).

[0018] Through the above technical solution, the amine solution oil removal and recovery device of the present application has high oil removal efficiency and high amine solution recovery rate. Especially when the adsorption material comprises the oil absorption sponge of the present application, the adsorption material has super-hydrophobic and super-oleophilic properties, and has strong adsorption capacity for the oil phase. The super-oleophilic property of the sponge material realizes the separation of the oil phase and the water phase in the flowing triolein, and the oil phase is adsorbed in the porous structure of the sponge due to its stronger affinity with the sponge material. The oil absorption sponge is used for triolein oil removal, has high selective adsorption capacity for the oil phase, large adsorption capacity for the oil phase and can be recycled, and the adsorption capacity does not decrease substantially after 30 cycles of use. The pressing plate in the amine solution oil removal and recovery device extrudes the oil phase adsorbed by the oil absorption sponge, and the sponge material can be separated from the oil phase due to its high resilience, so that the sponge material can be reused.

[0019] The sponge itself has very excellent flame-retardant properties, and provides safety guarantee for sampling link of petroleum and chemical industry. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a structural schematic diagram of an amine liquid oil removal and recovery device provided by a preferred embodiment of the present application;

[0021] Figure 2 is a scanning electron microscope (SEM) image of the oil absorption sponge prepared in Preparation Example 1;

[0022] Figure 3 is a scanning electron microscope (SEM) image of the oil absorption sponge prepared in Preparation Example 1 after 30 cycles;

[0023] Figure 4 is a scanning electron microscope (SEM) image of the porous melamine-formaldehyde sponge matrix in Preparation Example 1;

[0024] Figure 5 is a scanning electron microscope (SEM) image of the oil absorption sponge prepared in Preparation Example 8;

[0025] Figure 6 is a scanning electron microscope (SEM) image of the oil absorption sponge prepared in Preparation Example 8 after 30 cycles.

[0026] BRIEF DESCRIPTION OF DRAWINGS

[0027] 1 - link mechanism 2 - second housing

[0028] 3 - partition 4 - deoiled amine liquid outlet

[0029] 5 - waste oil outlet 6 - adsorption material

[0030] 7 - first housing 8 - oil-containing amine liquid inlet

[0031] 9 - pressing plate DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are provided as approximations. Any numerical value, however, can inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The endpoints of the ranges of values (as well as the values themselves) are not to be understood as limited to the precise values provided. The approximate values are provided to more accurately reflect the ranges actually measured.

[0033] In the present invention, the orientation words such as "upper", "lower", "left", "right" are generally referred to the upper, lower, left and right shown in the drawings, and "inner", "outer" are referred to the inner and outer relative to the contour of the components themselves, unless otherwise stated.

[0034] The first aspect of the present application provides an amine liquid oil removal recovery device, which comprises:

[0035] A first housing 7 and the housing surround to form a first containing cavity;

[0036] A partition plate 3 is sealingly arranged in the first containing cavity, the bottom of the partition plate 3 and the first housing 7 form a buffer cavity, and the top of the partition plate 3 and the first housing 7 form a storage cavity;

[0037] A second housing 2 is arranged above the partition plate 3, and the partition plate 3 and the second housing 2 form an adsorption filter cavity;

[0038] An adsorption material 6 is arranged in the adsorption filter cavity and used for adsorbing oil phase in the amine liquid; the adsorption material 6 has super-hydrophobic and super-oleophilic properties;

[0039] A pressing plate 9 is arranged in the adsorption filter cavity and placed above the adsorption material 6, the pressing plate 9 extrudes the adsorption material 6 by lifting and lowering; the partition plate 3 and the pressing plate 9 are provided with openings to provide a flow channel for fluid, so that the fluid can enter the adsorption filter cavity from the buffer cavity through the partition plate 3 and then enter the storage cavity through the pressing plate 9;

[0040] A connecting rod mechanism 1 is connected with the pressing plate 9 and penetrates through the first housing 7 and the second housing 2, and is used for driving the pressing plate 9 to lift and lower;

[0041] The first housing 7 is provided with a de-oiled amine liquid outlet 4, a waste oil outlet 5 and an oil-containing amine liquid inlet 8 which communicate with the first containing cavity; the de-oiled amine liquid outlet 4 is arranged above the partition plate 3, and the waste oil outlet 5 and the oil-containing amine liquid inlet 8 are arranged below the partition plate 3.

[0042] The second housing 2 is coaxially arranged inside the first housing 7 and located inside the storage cavity.

[0043] In the present application, the material of the partition plate 3 has a wide selection range, as long as it can withstand the pressure generated in the extrusion process and is not deformed; according to a preferred embodiment of the present application, the material of the partition plate 3 is selected from one of metal, polymer material or ceramic material; preferably at least one of 304 stainless steel and ABS.

[0044] According to a preferred embodiment of the present application, the opening diameters of the partition plate 3 and the pressing plate 9 are 5-20 mm and 10-30 mm respectively.

[0045] According to a preferred embodiment of the present application, the second housing 2 is welded to the area above the opening of the partition plate 3 to prevent the waste oil from polluting the de-oiled amine liquid pipeline during the extrusion process.

[0046] In the application, the connecting rod mechanism 1 is used to drive the pressing plate 9 to lift, the pressing plate 9 is lowered to compress and extrude the adsorbing material 6, and the oil phase adsorbed by the adsorbing material 6 is discharged; the pressing plate 9 is raised, and the adsorbing material 6 is used again to absorb the oil phase in the oil amine liquid by relying on the elasticity of the adsorbing material 6; according to a preferred embodiment of the application, the driving stroke of the connecting rod mechanism 1 is set to be 5%-80% of the thickness of the adsorbing material 6, preferably 50%-80%.

[0047] According to a preferred embodiment of the application, the adsorbing material 6 comprises an oil-absorbing sponge, the oil-absorbing sponge comprises a three-dimensional porous polymer matrix and a thermosetting resin coated on the three-dimensional porous polymer matrix; the saturated adsorption amount of the oil-absorbing sponge to oil products is not less than 30g / g; and the saturated adsorption amount of the oil-absorbing sponge to oil products is still not less than 30g / g after 30 times of adsorption-desorption cycle use.

[0048] The oil-absorbing sponge in the application has super-hydrophobic and super-oil-wetting properties on the basis of maintaining the high elasticity and high porosity of the original three-dimensional porous polymer matrix, and has good elasticity and strong adsorption capacity to oil products.

[0049] According to a preferred embodiment of the application, the mass of the thermosetting resin accounts for 0.5-5% of the total mass of the sponge, preferably 2-3%.

[0050] According to a preferred embodiment of the application, the saturated adsorption amount of the oil-absorbing sponge to oil products is 30-50g / g.

[0051] The oil-absorbing sponge in the application has strong selectivity to oil products in oil-containing sewage, large adsorption capacity to oil products and can be recycled, and the adsorption capacity is basically not attenuated after 30 times of recycling, according to a preferred embodiment of the application, the saturated adsorption amount of the oil-absorbing sponge to oil products is still 30-50g / g after 30 times of desorption-adsorption cycle use.

[0052] In the application, the thermosetting resin has a wide selection range, and the conventional thermosetting resin in the art can meet the requirements of the application, according to a preferred embodiment of the application, the thermosetting resin is selected from at least one of phenolic resin, epoxy resin, urea-formaldehyde resin, unsaturated polyester resin and organic silicon resin; preferably selected from at least one of phenolic resin, epoxy resin and organic silicon resin.

[0053] In the application, 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 application, 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.

[0054] In the present application, the pore size of the oil absorption sponge can be selected in a wide range. According to a preferred embodiment of the present application, the pore size of the oil absorption sponge is 10-500 μm, preferably 100-400 μm.

[0055] In the present application, the porosity of the oil absorption sponge can be selected in a wide range. According to a preferred embodiment of the present application, the porosity of the oil absorption sponge is greater than or equal to 60%, preferably greater than or equal to 90%.

[0056] The oil absorption sponge according to the present application has superhydrophobic and superoleophilic properties. According to a preferred embodiment of the present application, the static planar contact angle of the oil absorption sponge surface with water in air is greater than 135°, preferably greater than 145°.

[0057] The oil absorption sponge according to the present application has superhydrophobic and superoleophilic properties. According to a preferred embodiment of the present application, the static contact angle of the oil absorption sponge surface with white oil is less than 30°, preferably 0-20°, more preferably 0°.

[0058] The oil absorption sponge according to the present application also has flame retardant properties. According to a preferred embodiment of the present application, the UL94 vertical burning test grade of the oil absorption sponge is V-2 or above, preferably V-1 or above, more preferably V-0.

[0059] The oil absorption sponge having the aforementioned features of the present application can achieve the purpose of the present application, and there is no special requirement for the preparation method thereof. According to a preferred embodiment of the present application, the present application provides a preparation method of the oil absorption sponge according to the present application, which comprises:

[0060] The solution containing thermosetting resin prepolymer and curing agent is dispersed into the three-dimensional porous polymer matrix, and the oil absorption sponge is obtained by curing under vacuum. The preparation method according to the present application 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, by dispersing (e.g. extrusion absorption dispersion, spray absorption dispersion) the solution containing thermosetting resin prepolymer and curing agent into the three-dimensional porous polymer matrix and then curing under vacuum.

[0061] In the present application, the dispersion method of dispersing the solution containing thermosetting resin prepolymer and curing agent into the three-dimensional porous polymer matrix is not particularly limited, as long as it can be uniformly dispersed. According to a preferred embodiment of the present application, the dispersion method is extrusion absorption dispersion, spray absorption dispersion, preferably extrusion absorption dispersion.

[0062] In the present application, the extrusion absorption dispersion refers to extruding the three-dimensional porous polymer matrix, placing it in a solution containing thermosetting resin prepolymer and curing agent, absorbing and recovering to the original morphology, then extruding a certain proportion, discharging the excess solution and making it uniformly dispersed.

[0063] In the present application, the spray absorption dispersion refers to uniformly dispersing a certain amount of thermosetting resin prepolymer and curing agent solution to the surface of the three-dimensional porous polymer matrix in the form of spraying, waiting for absorption and then heating and curing.

[0064] In the present application, the curing pressure can be selected in a wide range. According to a preferred embodiment of the present application, the pressure is 0-10 kPa, preferably 3-5 kPa.

[0065] In the present application, the curing conditions can be selected in a wide range. According to a preferred embodiment of the present application, the curing conditions include: the temperature is 80-200℃, preferably 100-180℃; the curing time can be reasonably adjusted according to actual needs, preferably the time is 5-120 min, more preferably 20-100 min.

[0066] According to a preferred embodiment of the present application, the preparation method of the oil absorption sponge comprises:

[0067] (1) dispersing the solution containing thermosetting resin prepolymer and curing agent into the three-dimensional porous polymer matrix, and pre-curing under the first vacuum condition;

[0068] (2) dispersing the solution containing thermosetting resin prepolymer and curing agent into the product obtained in step (1), and curing under the second vacuum condition;

[0069] The first vacuum condition and the second vacuum condition each include: the pressure is 0-10 kPa;

[0070] The pre-curing condition includes: the temperature is 80-120℃;

[0071] The curing condition includes: the temperature is 140-180℃.

[0072] In the present application, by pre-curing the thermosetting resin prepolymer, the temperature of the sponge as a whole is uniform, the internal thermosetting resin reaches the gel state, adheres to the three-dimensional porous polymer matrix skeleton, and the vacuum condition is conducive to the gas outside of the thermosetting resin in the gel state, and better combines with the sponge skeleton. Then the solution containing thermosetting resin prepolymer and curing agent is dispersed onto the three-dimensional porous polymer matrix containing gel-state thermosetting resin, and cured to obtain an oil absorption sponge, which is conducive to the uniform distribution of thermosetting resin on the sponge skeleton, thereby maintaining the elasticity of the three-dimensional porous polymer matrix, improving the cyclic use performance of the oil absorption sponge, and the adsorption capacity is basically not attenuated under the condition of 30 times of cyclic use.

[0073] According to a preferred embodiment of the present application, 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 maintaining the elasticity of the three-dimensional porous polymer matrix and improving the recycling performance of the oil absorption sponge.

[0074] In the present application, the pre-curing time in step (1) is not particularly limited and 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 application, the pre-curing time is 40-90 min.

[0075] In the present application, the curing time in step (2) is 20-100 min.

[0076] According to a preferred embodiment of the present application, the mass concentration of the thermosetting resin prepolymer in the solution containing the thermosetting resin prepolymer and the curing agent is 0.02-0.6 g / mL, preferably 0.03-0.5 g / mL, and more preferably 0.05-0.3 g / mL.

[0077] According to a preferred embodiment of the present application, the mass of the curing agent in the solution containing the thermosetting resin prepolymer and the curing agent accounts for 1-10% of the mass of the thermosetting resin prepolymer, and preferably 5-10%.

[0078] In the present application, the solvent in the solution containing the thermosetting resin prepolymer and the curing agent can be selected from a wide range, as long as it can dissolve the thermosetting resin prepolymer and the curing agent. According to a preferred embodiment of the present application, the solvent in the solution containing the thermosetting resin prepolymer and the curing agent is selected from at least one of water, C1-C4 alcohol and C1-C4 ketone; and preferably ethanol and / or acetone.

[0079] In the present application, the curing agent in the solution containing the thermosetting resin prepolymer and the curing agent can be selected from a wide range, as long as it can form the thermosetting resin with the thermosetting resin prepolymer. According to a preferred embodiment of the present application, the curing agent is selected from at least one of organic acid, acid anhydride, boron trifluoride, aliphatic polyamine and aromatic polyamine; and preferably at least one of benzene sulfonic acid, hexamethylene tetramine and m-phenylenediamine.

[0080] The second aspect of the present application provides an amine solution oil removal and recovery method, which comprises:

[0081] (1) Open the oil-containing amine liquid inlet 8 and the oil-removing amine liquid outlet 4, and close the sludge outlet 5. The oil-containing amine liquid enters the buffer chamber from the oil-containing amine liquid inlet 8; it flows into the adsorption and filtration chamber through the opening of the partition plate 3. The oil phase in the oil-containing amine liquid is adsorbed by the adsorption material 6 in the adsorption and filtration chamber to obtain the oil-removing amine liquid; the oil-removing amine liquid flows out through the opening of the pressure plate 9, enters the storage chamber, and is discharged from the oil-removing amine liquid outlet 4.

[0082] (2) When the adsorbent material 6 is saturated with adsorption, the oil-containing amine liquid inlet 8 and the oil-removing amine liquid outlet 4 are closed, the sludge outlet 5 is opened, the linkage mechanism 1 is driven to descend, so that the pressure plate 9 squeezes the adsorbent material 6 and discharges the oil phase in the adsorbent material 6. The oil phase flows into the buffer chamber through the opening of the partition plate 3 and is discharged from the sludge outlet 5.

[0083] (3) After removing the oil phase, drive the linkage mechanism 1 to rise, so that the adsorbent material 6 regains its adsorption capacity, and repeat step (1). In this invention, the oil phase adsorbed by the adsorbent material is desorbed by the pressure plate in the amine liquid de-oiling and recovery device. Combined with the high resilience of the adsorbent material, the adsorbent material and the oil phase can be separated, thereby realizing the reuse of the adsorbent material; and the amine liquid recovery rate is high, and the oil removal efficiency is greater than 90%.

[0084] In this invention, there is no particular limitation on the method of driving the linkage mechanism 1 to rise and fall, as long as the lifting and falling of the linkage mechanism 1 can be controlled, for example, it can be driven manually, pneumatically, or electro-hydraulicly, preferably electro-hydraulically.

[0085] According to a preferred embodiment of the present invention, the maximum load driving the linkage mechanism 1 is greater than 20kN to ensure that there is sufficient force to fully compress the adsorbent material and the desorbed oil phase.

[0086] In this invention, there is no particular limitation on the processing capacity of the oil-containing amine solution. According to a preferred embodiment of this invention, the processing capacity of the oil-containing amine solution is 3 to 5 t / h.

[0087] The present invention will be described in detail below through embodiments.

[0088] In the following embodiments, the structural schematic diagram of the amine liquid oil removal and recovery device is shown below. Figure 1 As shown, the amine liquid oil removal and recovery device includes:

[0089] The first housing 7 and the housing surround the formed first receiving cavity;

[0090] A partition 3 is sealed within the first receiving cavity; the bottom of the partition 3 forms a buffer cavity with the first housing 7; the top of the partition 3 forms a storage cavity with the first housing 7.

[0091] A second shell 2 is arranged above the baffle plate 3, and the baffle plate 3 and the second shell 2 form an adsorption filtering cavity; the second shell 2 is welded to the area above the opening of the baffle plate 3;

[0092] An adsorption material 6 is arranged in the adsorption filtering cavity and used for adsorbing oil phase in amine solution; the adsorption material 6 has super-hydrophobic and super-oleophilic properties;

[0093] A pressing plate 9 is arranged in the adsorption filtering cavity and placed above the adsorption material 6, and the pressing plate 9 extrudes the adsorption material 6 by lifting and lowering;

[0094] A connecting rod mechanism 1 is connected with the pressing plate 9 and penetrates through the first shell 7 and the second shell 2, and is used for driving the pressing plate 9 to lift and lower; the baffle plate 3 and the pressing plate 9 are provided with openings, which provide a flow channel for fluid, so that the fluid can enter the adsorption filtering cavity from the buffer cavity through the baffle plate 3, and then enter the storage cavity through the pressing plate 9;

[0095] The first shell 7 is provided with an oil-free amine liquid outlet 4, a waste oil outlet 5 and an oil-containing amine liquid inlet 8 which communicate with the first containing cavity; the oil-free amine liquid outlet 4 is arranged above the baffle plate 3, and the waste oil outlet 5 and the oil-containing amine liquid inlet 8 are arranged below the baffle plate 3;

[0096] The opening diameter of the baffle plate 3 is 10 mm, and the material of the baffle plate 3 is 304 stainless steel;

[0097] The opening diameter of the pressing plate 9 is 10 mm;

[0098] In the following examples, the vertical combustion test level is tested according to the UL94 flame retardant test method.

[0099] In the following examples, the saturated oil phase adsorption capacity and the saturated oil phase adsorption capacity after 30 cycles are tested by the following steps: weighing the mass m1 of the sponge to be tested, placing it in a beaker containing 200 mL of toluene, weighing the mass m2 of the sponge after adsorption saturation, and the saturated oil phase adsorption capacity (Ф) is Ф=m1 / m2. The saturated oil phase adsorption capacity after 30 cycles is first saturated with toluene, mechanically extruded to no oil phase natural dripping, repeated 30 times, and then the test steps are consistent with the saturated oil phase adsorption capacity.

[0100] In the following examples, the water contact angle parameter is measured by the EASY DROP contact angle tester of KRUSS Company in Germany, the measurement range is 1-180°, the resolution is ±0.1°, the static contact angle measurement mode is adopted, the fixed volume of water droplet or white oil droplet is 2 μL each time, the droplet is dropped on the sponge, the initial contact angle is calculated as the contact angle measurement value of the surface of the sponge, and the average value is calculated by parallel measurement for 6 times.

[0101] In the following examples, the oil phase removal rate and selective adsorption rate of the oil-containing wastewater are determined by the following steps: 1000 mL of the same batch of oil-containing wastewater (oil content 10%, oil phase composition C7-C9) is taken, 10 g of the sample to be tested is weighed and placed in the above oil-containing wastewater for adsorption for 10 min. The volume V1 and oil phase content C1 of the remaining oil-containing wastewater are tested. The oil phase removal rate (β) is β = (1-C1V1 / 100) x 100%; the oil phase selective adsorption rate (θ) is θ = (100-C1V1) / (1000-V1).

[0102] In the following examples, the oil removal efficiency test is performed by the following steps: the oil phase content of the oil-containing amine solution before and after passing through the amine solution oil removal recovery device is tested under the same flow rate and temperature. The oil phase content before passing through is C1, the oil phase content after passing through is C2, and the oil removal efficiency (η) is η = (1-C2 / C1) x 100%.

[0103] In the following examples, the amine solution foaming height and defoaming time test refers to the industry standard SY / T6538-2016 "Formulated Selective Desulfurization Solvent". The foaming tube experiment is used to determine the foaming height and defoaming time of the amine solution: nitrogen gas with a flow rate of 300 mL / min is used as the disturbance gas, and the experimental temperature is 40°C. Nitrogen gas is introduced into the foaming tube, and the foaming height H is recorded after the foam height in the tube stabilizes. Stop the nitrogen gas and start timing, stop timing when the foam disappears and the water surface is exposed, and get the defoaming time T. The higher the foaming height, the longer the defoaming time, and the better the foam stability.

[0104] In the following examples, the porosity of the porous melamine-formaldehyde sponge matrix (Xuexian Industry) is 95%, and the average pore size is 100 μm;

[0105] The porosity of the porous melamine-formaldehyde sponge matrix (Beiyou Building Materials) is 96%, and the average pore size is 250 μm.

[0106] Preparation Example 1

[0107] (1) 10 g of phenolic resin prepolymer solution (Meisheng Chemical Plasticization) and 1 g of hexamethylenetetramine are dissolved in 200 mL of ethanol, and the solution is stirred thoroughly to make it clear and transparent;

[0108] (2) A 200*200*150 mm porous melamine-formaldehyde sponge matrix (Xuexian Industry) is measured, and the above solution is dispersed into the sponge by extrusion dispersion, so that the curing agent solution uniformly infiltrates the sponge. The sponge after extrusion is placed in a 180°C, 3kPa vacuum oven for curing for 20 min to obtain oil-absorbing sponge S1.

[0109] The phenolic resin accounts for 2% of the total mass of the oil absorption sponge S1. The average pore size of the oil absorption sponge S1 is 100 μm, the porosity is 95%, the open porosity is 98%, the vertical combustion level is V-0, the contact angle with white oil is 0°, the contact angle with water is 152.3°, the saturated oil phase adsorption capacity is 40 g / g, and the saturated oil phase adsorption capacity after 30 cycles is 38 g / g.

[0110] The saturated oil phase adsorption capacity, oil phase removal rate and oil phase selective adsorption rate of the sponge after 30 cycles according to the test requirements are tested, and the results are shown in Table 1.

[0111] The SEM image of the oil absorption sponge S1 is shown in Figure 2 , and compared with the melamine-formaldehyde sponge matrix (SEM image as Figure 4 ), the size of the porous framework of the oil absorption sponge is slightly larger than that of the unmodified framework, which indicates that the phenolic resin is uniformly solidified on the surface of the porous melamine-formaldehyde sponge matrix framework, has a through hole, thereby making the oil absorption sponge have strong selectivity to oil in oil-containing wastewater and large adsorption capacity for oil.

[0112] Figure 3 The SEM image of the oil absorption sponge S1 after 30 cycles is shown in Figure 2 , and compared with the melamine-formaldehyde sponge matrix (SEM image as ), the size of the porous framework of the oil absorption sponge is slightly larger than that of the unmodified framework, which indicates that the phenolic resin is uniformly solidified on the surface of the porous melamine-formaldehyde sponge matrix framework, has a through hole, thereby making the oil absorption sponge have strong selectivity to oil in oil-containing wastewater and large adsorption capacity for oil.

[0113] Preparation Example 2

[0114] (1) 10 g of phenolic resin prepolymer solution (Meisheng Chemical Plasticization) and 0.3 g of hexamethylenetetramine and 0.2 g of m-xylylenediamine were dissolved in 200 mL of ethanol, and the solution was stirred thoroughly to make it clear and transparent.

[0115] (2) A porous melamine-formaldehyde sponge matrix (Xuexian Industry) with a size of 200*200*150 mm was used. The above-mentioned solution was dispersed into the sponge by extrusion dispersion, so that the curing agent solution uniformly infiltrated the sponge. The sponge after extrusion was placed in a vacuum oven at 140°C for 100 min to solidify, and the oil absorption sponge S2 was obtained.

[0116] The phenolic resin accounts for 3% of the total mass of the oil absorption sponge S2. The average pore size of the oil absorption sponge S2 is 100 μm, the porosity is 95%, and the open porosity is 98%. The vertical combustion level is V-1, the contact angle with white oil is 0°, the contact angle with water is 153.2°, the saturated adsorption capacity is 38 g / g, and the saturated oil phase adsorption capacity after 30 cycles is 37 g / g.

[0117] The saturated oil phase adsorption capacity, oil phase removal rate and oil phase selective adsorption rate of the sponge after 30 cycles according to the test requirements are tested, and the results are shown in Table 1.

[0118] Preparation Example 3

[0119] (1) 10 g of an epoxy resin prepolymer solution (Witco) and 0.6 g of hexamethylenetetramine were weighed and dissolved in 200 mL of acetone, and the solution was stirred sufficiently to make it clear and transparent.

[0120] (2) A porous melamine-formaldehyde sponge substrate (Beiyu Building Materials) with a size of 200*200*150 mm was used, and the above solution was dispersed into the sponge by using a spray dispersion method, so that the curing agent solution uniformly infiltrated the sponge. The sponge after extrusion was placed in a 150°C, 5 kPa vacuum oven for curing for 20 min, to obtain oil absorption sponge S3.

[0121] In the oil absorption sponge S3, the mass of the epoxy resin accounted for 3% of the total mass of the sponge; the average pore size of the oil absorption sponge S3 was 250 μm, the porosity was 96%, and the open porosity was 98%; the vertical burning rating was V-0; the contact angle with white oil was 0°, and the contact angle with water was 151.1°; the saturated adsorption capacity was 40 g / g; and the saturated oil phase adsorption capacity after 30 cycles was 35 g / g.

[0122] The sponge was subjected to the tests of the saturated oil phase adsorption capacity, oil phase removal rate, and oil phase selective adsorption rate after 30 cycles according to the test requirements, and the results are shown in Table 1.

[0123] Preparation Example 4

[0124] According to the method of Preparation Example 3, except that the volume of the porous melamine-formaldehyde sponge substrate was 400*400*150 mm; and the other conditions were the same as those in Preparation Example 3, oil absorption sponge S4 was obtained.

[0125] In the oil absorption sponge S4, the mass of the epoxy resin accounted for 0.5% of the total mass of the sponge; the average pore size of the oil absorption sponge S4 was 250 μm, the porosity was 92%, and the open porosity was 93%; the vertical burning rating was V-0; the contact angle with white oil was 0°, and the contact angle with water was 146°; the saturated adsorption capacity was 37 g / g; and the saturated oil phase adsorption capacity after 30 cycles was 33 g / g.

[0126] The sponge was subjected to the tests of the saturated oil phase adsorption capacity, oil phase removal rate, and oil phase selective adsorption rate after 30 cycles according to the test requirements, and the results are shown in Table 1.

[0127] Preparation Example 5

[0128] According to the method of Preparation Example 3, except that 20 g of an epoxy resin prepolymer solution (Witco) and 1.2 g of hexamethylenetetramine were weighed and dissolved in 200 mL of acetone; and the other conditions were the same as those in Preparation Example 3, oil absorption sponge S5 was obtained.

[0129] The oil absorption sponge S5 has 5% of epoxy resin by mass based on the total mass of the sponge; the average pore size of the oil absorption sponge S5 is 240 μm, the porosity is 87%, and the open porosity is 83%; the vertical combustion rating is V-1; the contact angle with white oil is 0°, the contact angle with water is 155.4°; the saturated oil phase adsorption capacity is 32 g / g; and the saturated oil phase adsorption capacity after 30 cycles is 30 g / g.

[0130] The saturated oil phase adsorption capacity, oil phase removal rate, and oil phase selective adsorption rate of the sponge after 30 cycles were tested according to the test requirements, and the results are shown in Table 1.

[0131] Preparation Example 6

[0132] (1) 10 g of a phenolic resin prepolymer solution (Meisheng Chemical Plasticization) and 1 g of hexamethylenetetramine were dissolved in 200 mL of ethanol, and the solution was stirred thoroughly to make it clear and transparent;

[0133] (2) A porous melamine-formaldehyde sponge substrate (Xuexian Industry) with a size of 200*200*150 mm was prepared, and the solution in step (1) was dispersed into the sponge by extrusion dispersion, so that the curing agent solution uniformly infiltrated the sponge. The sponge after extrusion was placed in a vacuum oven at 110°C and 3 kPa for 80 min to cure, to obtain a sponge containing gelatinous phenolic resin. The gelatinous phenolic resin sponge accounted for 1% of the total mass of the porous melamine-formaldehyde sponge substrate;

[0134] (3) The solution in step (1) was dispersed into the sponge containing gelatinous phenolic resin obtained in step (2) by extrusion dispersion, so that the solution uniformly infiltrated the sponge. The sponge after extrusion was placed in a vacuum oven at 180°C and 3 kPa for 20 min to cure, to obtain an oil absorption sponge S6.

[0135] The phenolic resin accounted for 2% of the total mass of the oil absorption sponge S6; the average pore size of the oil absorption sponge was 100 μm, the porosity was 95%, the open porosity was 98%, the vertical combustion rating was V-0, the contact angle with white oil was 0°, and the contact angle with water was 153.8°; the saturated oil phase adsorption capacity was 44 g / g; and the saturated oil phase adsorption capacity after 30 cycles was 43 g / g.

[0136] Preparation Example 7

[0137] (1) 10 g of a phenolic resin prepolymer solution (Meisheng Chemical Plasticization) and 1 g of hexamethylenetetramine were dissolved in 200 mL of ethanol, and the solution was stirred thoroughly to make it clear and transparent;

[0138] (2) Measure 200*200*150mm porous melamine-formaldehyde sponge matrix (Xuexian Industry), and disperse the above solution into the sponge by extrusion dispersion to make the curing agent solution uniformly infiltrate the sponge. The sponge after extrusion is placed in a 110°C, 3kPa vacuum oven to cure for 80min to obtain a sponge containing gelated phenolic resin. Then the pre-cured sponge is placed in a 180°C, 3kPa vacuum oven to cure for 20min to obtain oil absorbing sponge S7.

[0139] 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 100μm, the porosity is 95%, the open porosity is 98%, the vertical combustion grade is V-0, the contact angle with white oil is 0°, and the contact angle with water is 152.7°; the saturated oil phase adsorption capacity is 41g / g; the saturated oil phase adsorption capacity after 30 cycles is 40g / g.

[0140] Preparation Example 8

[0141] According to the method of Preparation Example 1, except that the impregnation amount of phenolic resin prepolymer is adjusted so that the mass of phenolic resin accounts for 7% of the total mass of the oil absorbing sponge, and the other conditions are the same as those in Preparation Example 1, an oil absorbing sponge D1 is obtained.

[0142] 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 230μm, the porosity is 73%, and the open porosity is 69%; the vertical combustion grade is V-2; the contact angle with white oil is 0°, and the contact angle with water is 158.1°; the saturated adsorption capacity is 27g / g; the saturated oil phase adsorption capacity after 30 cycles is 20g / g.

[0143] Figure 5 The SEM photo of the sponge D1, compared with the oil absorbing sponge S1( Figure 2 ), the skeleton and the skeleton junction of the sponge are obviously covered with more phenolic resin, so that the porosity of the sponge decreases, and the corresponding saturated adsorption capacity also decreases. Moreover, the distribution of phenolic resin on the surface of the skeleton is uneven, and stress concentration easily occurs during the recycling process, leading to the collapse of the skeleton. Figure 6 The photo of the skeleton of the sponge D1 after 30 cycles, the bulk density of the skeleton obviously increases, leading to the decrease of the saturated adsorption capacity.

[0144] The saturated oil phase adsorption capacity, oil phase removal rate and oil phase selective adsorption rate of the sponge after 30 cycles according to the test requirements are tested, and the results are shown in Table 1.

[0145] Preparation Example 9

[0146] According to the method of Preparation Example 1, except that in step (2), the solidification was carried out under normal pressure, specifically, the sponge after extrusion was placed in an oven at 180℃ for 20 min, and the other conditions were the same as those in Preparation Example 1, to obtain an oil-absorbing sponge D2.

[0147] In the oil-absorbing sponge D2, the mass of the phenolic resin accounted for 0.2% of the total mass of the sponge; the average pore size of the oil-absorbing sponge D2 was 250 μm, the porosity was 96%, the open porosity was 98%; the vertical combustion rating was V-0; the contact angle with white oil was 0°, and the contact angle with water was 133.1°; the saturated adsorption capacity was 30 g / g; and the saturated oil phase adsorption capacity after 30 cycles was 20 g / g.

[0148] The saturated oil phase adsorption capacity, oil phase removal rate and oil phase selective adsorption rate of the sponge after 30 cycles were tested according to the test requirements, and the results are shown in Table 1.

[0149] Examples 1-7 and Comparative Examples 1-2

[0150] The oil-absorbing sponges prepared in Preparation Examples 1-7 and Preparation Examples 8-9 were filled in the adsorption and filtration cavity, and then amine liquid recovery was carried out, and the recovery method was as follows:

[0151] The oil-containing amine liquid filtration condition: open the oil-containing amine liquid inlet 8 and the oil-free amine liquid outlet 4, close the waste oil outlet 5, the oil-containing amine liquid enters the buffer cavity from the oil-containing amine liquid inlet 8; flows into the adsorption and filtration cavity from the opening of the partition plate 3, and the oil phase in the oil-containing amine liquid is adsorbed by the adsorption material 6 in the adsorption and filtration cavity to obtain the oil-free amine liquid; the oil-free amine liquid flows out from the opening of the pressing plate 9, enters the storage cavity, and is discharged from the oil-free amine liquid outlet 4;

[0152] The oil removal condition: after the sponge is saturated with adsorption, the oil-containing amine liquid inlet 8 and the oil-free amine liquid outlet 4 are closed, the waste oil outlet 5 is opened, the connecting rod mechanism 1 is driven to descend, the pressing plate 9 extrudes the adsorption material 6, the oil phase in the adsorption material 6 is discharged, and the oil phase flows into the buffer cavity from the opening of the partition plate 3 and is discharged from the waste oil outlet 5; after the oil phase is removed, the connecting rod mechanism 1 is driven to rise, so that the adsorption material 6 has adsorption capacity again, and the oil-containing amine liquid filtration is carried out again.

[0153] The treatment capacity of the oil-containing amine liquid was 3 t / h; the connecting rod mechanism 1 was driven, the maximum stroke of the connecting rod mechanism 1 was 80% of the thickness of the sponge, and the maximum load was 20 kN. The treated oil-free amine liquid was tested for foaming height and defoaming time, and the results are shown in Table 2.

[0154] Comparative Example 3

[0155] According to the method of Example 3, the oil-absorbing sponge filled was an unmodified porous melamine-formaldehyde sponge matrix (Beiyujiancai) D3, and the other conditions were the same as those in Example 3.

[0156] Table 2

[0157] Number Oil absorption sponge Oil removal efficiency % Foaming height (cm) Defoaming time (s) Example 1 S1 92.6 2.4 2.7 Example 2 S2 93.4 2.5 2.7 Example 3 S3 94.5 2.3 2.6 Example 4 S4 85.3 2.7 3.2 Example 5 S5 91.2 2.5 2.9 Example 6 S6 95.0 2.0 2.4 Example 7 S7 94.8 2.2 2.5 Comparative Example 1 D1 83.2 3.1 3.5 Comparative Example 2 D2 75.6 3.6 4.2 Comparative Example 4 D3 20.7 5.1 5.8

[0158] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. An amine liquid oil removal and recovery device, characterized in that, The device includes: a first housing (7) and a first receiving cavity formed around the first housing (7); A partition (3) is sealed within the first receiving cavity. The bottom of the partition (3) forms a buffer cavity with the first housing (7); the top of the partition (3) forms a storage cavity with the first housing (7). A second housing (2) is provided above the partition (3), and the partition (3) and the second housing (2) form an adsorption filtration chamber; The adsorbent material (6) disposed in the adsorption filtration chamber is used to adsorb the oil phase in the amine solution; the adsorbent material (6) has superhydrophobic and superoleophilic properties; A pressure plate (9) is placed inside the adsorption filtration chamber and above the adsorbent material (6). The pressure plate (9) presses the adsorbent material (6) by lifting and lowering. The partition plate (3) and the pressure plate (9) are provided with openings to provide a flow channel for the fluid, so that the fluid can enter the adsorption filtration chamber from the buffer chamber through the partition plate (3) and then enter the storage chamber through the pressure plate (9). A linkage mechanism (1) is connected to the pressure plate (9) and passes through the first housing (7) and the second housing (2) to drive the pressure plate (9) to lift and lower. The first housing (7) is provided with an oil-removing amine liquid outlet (4), a sludge oil outlet (5) and an oil-containing amine liquid inlet that are connected to the first receiving chamber. (8); the degreasing amine liquid outlet (4) is located above the partition plate (3), and the sludge oil outlet (5) and the oil-containing amine liquid inlet (8) are located below the partition plate (3); the adsorbent material (6) 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 is not less than 30 g / g; the saturated adsorption capacity of the oil-absorbing sponge for oil is still not less than 30 g / g after 30 cycles of adsorption-desorption; the mass of the thermosetting resin accounts for 0.5-5% of the total mass of the sponge; the pore size of the oil-absorbing sponge is 10-500 μm; the porosity of the oil-absorbing sponge is greater than or equal to 60%; the preparation method of the oil-absorbing sponge includes: dispersing a solution containing thermosetting resin prepolymer and curing agent into a three-dimensional porous polymer matrix, and curing it under vacuum conditions to obtain the oil-absorbing sponge; the vacuum conditions include: pressure of 0-10 kPa.

2. The recycling device according to claim 1, wherein, The thermosetting resin accounts for 2-3% of the total mass of the sponge; and / or The saturated adsorption capacity of the oil-absorbing sponge for oil is 30-50 g / g; the saturated adsorption capacity of the oil-absorbing sponge for oil remains 30-50 g / g after 30 cycles of desorption-adsorption.

3. The recycling device according to claim 1, wherein, The thermosetting resin is selected from at least one of phenolic resin, epoxy resin, urea-formaldehyde resin, unsaturated polyester 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.

4. The recycling device according to claim 1 or 3, wherein, The thermosetting resin is selected from at least one of phenolic resin, epoxy resin and silicone resin.

5. The recycling apparatus according to claim 1 or 3, wherein, The three-dimensional porous polymer matrix is ​​melamine-formaldehyde sponge.

6. The recycling device according to claim 1, wherein, The surface of the oil-absorbing sponge has a static planar contact angle with water in air greater than 135°; and / or The static contact angle of the oil-absorbing sponge surface with white oil is <30°; and / or The oil-absorbing sponge has a UL94 vertical burning test rating of V-2 or higher.

7. The recycling device according to claim 1, wherein, The method for preparing the oil-absorbing sponge includes: (1) Disperse the solution containing thermosetting resin prepolymer and curing agent into a three-dimensional porous polymer matrix and pre-cur it under a first vacuum condition; (2) Disperse the solution containing thermosetting resin prepolymer and curing agent into the product obtained in step (1) and cure it 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: a temperature of 80-120℃; Curing conditions include a temperature of 140-180℃.

8. The recycling device according to claim 1, wherein, The material of the partition (3) is selected from one of metal, polymer, or ceramic materials; and / or The driving stroke of the linkage mechanism (1) is set to 5%-80% of the thickness of the adsorbent material (6).

9. The recycling device according to claim 1, wherein, Curing conditions include: temperature of 80~200℃ and curing time of 5~120 min.

10. A method for oil removal and recovery from amine solution, characterized in that, The method is carried out in the recycling apparatus according to any one of claims 1-9, and the method includes: (1) Open the oil-containing amine liquid inlet (8) and the oil-removing amine liquid outlet (4), and close the sludge outlet (5). The oil-containing amine liquid enters the buffer chamber from the oil-containing amine liquid inlet (8); it flows into the adsorption filtration chamber through the opening of the partition plate (3). The oil phase in the oil-containing amine liquid is adsorbed by the adsorption material (6) in the adsorption filtration chamber to obtain the oil-removing amine liquid; the oil-removing amine liquid flows out through the opening of the pressure plate (9), enters the storage chamber, and is discharged from the oil-removing amine liquid outlet (4). (2) When the adsorbent material (6) is saturated, close the oil-containing amine liquid inlet (8) and the oil-removing amine liquid outlet (4), open the sludge outlet (5), drive the linkage mechanism (1) to descend, so that the pressure plate (9) squeezes the adsorbent material (6) and discharges the oil phase in the adsorbent material (6). The oil phase flows into the buffer chamber through the opening of the partition plate (3) and is discharged from the sludge outlet (5). (3) After removing the oil phase, drive the linkage mechanism (1) to rise, so that the adsorbent material (6) regains its adsorption capacity, and repeat step (1).

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