A regeneration method of a selective adsorption material for oil and phenol in coal chemical wastewater

Abstract

The application discloses a kind of for coal chemical industry wastewater oil, phenol Selective adsorption material Regeneration method, comprising: step 1, saturated MOFs / particle carbon ball material and methanol are mixed with adsorption, after keeping preset desorption time, obtain the intermediate mixed system in first regeneration;Step 2, the intermediate mixed system in first regeneration is placed in ultrasonic vibration environment, to promote the desorption aggregation of adsorbed material, obtain the MOFs / particle carbon ball material after first regeneration;Step 3, the MOFs / particle carbon ball material after first regeneration and ethanol are mixed, repeat the operation of step 1, 2, obtain the MOFs / particle carbon ball material after second regeneration;Step 4, the MOFs / particle carbon ball material after second regeneration and water are mixed, repeat the operation of step 1, 2, obtain the MOFs / particle carbon ball material after third regeneration;The application can realize the rapid desorption of oil, phenol and the efficient regeneration of MOFs / particle carbon ball, and the regeneration process is simple, and the cost is low.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of coal chemical industry wastewater pretreatment, and particularly relates to a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater. BACKGROUND

[0002] The oil and phenol pollutants in coal chemical industry wastewater have high concentration, great toxicity, stable occurrence characteristics and are difficult to degrade efficiently, which brings great challenges to the harmless treatment of coal chemical industry wastewater; therefore, efficient separation and recovery of oil and phenol can not only realize high-value recovery of resource materials but also effectively reduce the burden of subsequent biochemical treatment; at present, researches have shown that MOFs / pellet carbon ball materials can exhibit efficient selective separation and recovery characteristics for oil and phenol in wastewater, and have become a very potential separation method due to their green and low-carbon separation mode; among them, adsorption efficiency is a key point of general concern for MOFs / pellet carbon ball materials, and how to realize efficient regeneration of adsorption materials, selection of regeneration mode and high-quality recovery of oil and phenol in the regeneration system are also particularly crucial for the continuous and stable operation of the entire adsorption system.

[0003] At present, traditional regeneration methods include pyrolysis regeneration, vacuum desorption regeneration, solvent extraction regeneration, displacement regeneration and chemical conversion regeneration; among them, pyrolysis regeneration and vacuum desorption regeneration require high-temperature and high-pressure regeneration conditions, have high energy consumption and high water treatment operation cost, and are difficult to be widely applied in engineering practice; solvent extraction regeneration and displacement regeneration have the problems of poor regeneration effect, secondary treatment of regeneration liquid, incomplete extraction of residual extraction agent and recovery, and possible new pollution; in addition, chemical conversion regeneration can easily damage the original special structure of the adsorbent, making the recycling performance of the adsorbent worse and difficult to be used stably and continuously for a long time.

[0004] Due to the characteristics of high emulsification degree, high viscosity and stable occurrence characteristics of oil and phenol in coal chemical industry wastewater, when MOFs / pellet carbon ball materials are used for adsorption treatment, oil and phenol and other substances are often adsorbed on the surface of the MOFs / pellet carbon ball materials, and the traditional regeneration methods have the problems of incomplete or difficult desorption, complex and tedious regeneration, poor separation effect of regeneration liquid and difficult engineering application of regeneration technology; therefore, there is an urgent need for a MOFs / pellet carbon ball regeneration method with low energy consumption, high efficiency and no secondary pollution. SUMMARY

[0005] In view of the technical problems existing in the prior art, the application provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater, so as to solve the technical problems that the process is complex and tedious, the separation effect of the regeneration liquid is poor, and the regeneration technology is difficult to be applied in engineering when the MOFs / particle carbon ball material is regenerated by using a traditional regeneration method.

[0006] To achieve the above object, the technical scheme adopted by the application is as follows:

[0007] The application provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater, which comprises the following steps:

[0008] Step 1, the selective adsorption material to be treated is mixed with methanol, and after a preset desorption time is kept, a first regeneration intermediate mixed system is obtained; wherein the selective adsorption material to be treated is a MOFs / particle carbon ball material saturated with adsorption, and the MOFs / particle carbon ball material is used for selectively adsorbing oil and phenol in coal chemical industry wastewater;

[0009] Step 2, the first regeneration intermediate mixed system is placed in an ultrasonic vibration environment to promote the desorption and aggregation of the adsorbed substances, so as to obtain a MOFs / particle carbon ball material after first regeneration and a first mixed regeneration liquid;

[0010] Step 3, the MOFs / particle carbon ball material after first regeneration is mixed with ethanol, and the operations of step 1 and step 2 are repeated, so as to obtain a MOFs / particle carbon ball material after second regeneration and a second mixed regeneration liquid;

[0011] Step 4, the MOFs / particle carbon ball material after second regeneration is mixed with water, and the operations of step 1 and step 2 are repeated, so as to obtain a MOFs / particle carbon ball material after third regeneration and a third mixed regeneration liquid.

[0012] Further, the volume ratio of the selective adsorption material to be treated to the methanol is 1:(1-3).

[0013] Further, the preset desorption time is 20-30 min.

[0014] Further, the MOFs / particle carbon ball material is formed by in-situ polymerization of an organic carbon skeleton material A and a metal organic skeleton material B;

[0015] The organic carbon skeleton material A is formed by polymerization of nonpolar monomers under the action of an initiator, a crosslinking agent, a dispersing agent and a pore adjusting agent; the nonpolar monomers include styrene, diallyl phthalate and dimethyl acrylate.

[0016] The metal organic framework material B is formed by polymerization of metal compound monomers and carboxylic organic ligands; the metal compound monomers include ferric nitrate nonahydrate, chromium nitrate nonahydrate and zinc nitrate nonahydrate; and the carboxylic organic ligands include terephthalic acid, phthalic acid and trimesic acid.

[0017] Further, the crosslinking agent uses one or more of divinylbenzene, hydroxyethyl methacrylate and N, N-methylene bisacrylamide; the dispersing agent uses one or more of polyvinyl alcohol, calcium chloride and gelatin; the pore regulator uses one or more of toluene, n-heptane and diesel; and the initiator uses one or more of dibenzoyl peroxide, azobisisobutyronitrile and persulfate.

[0018] Further, the intermediate mixed system in the primary regeneration is placed in an ultrasonic vibration environment to promote the desorption and aggregation of the adsorbed substances, so as to obtain the MOFs / particle carbon ball material after primary regeneration and a primary mixed regeneration liquid, and the process is as follows:

[0019] The ultrasonic transmitter is introduced into the intermediate mixed system in the primary regeneration, and the desorption and aggregation of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic waves emitted by the ultrasonic transmitter.

[0020] Further, the frequency of the ultrasonic transmitter is 20-40 KHz, and the acoustic intensity of the ultrasonic transmitter is 0.5-2 W / cm 2 , and the ultrasonic wave action time is 10-20 min.

[0021] Further, the volume ratio of the MOFs / particle carbon ball material after primary regeneration to the ethanol is 1:(1-3).

[0022] Further, the volume ratio of the MOFs / particle carbon ball material after secondary regeneration to water is 1:(1-3).

[0023] Further, the process further comprises a solvent regeneration step.

[0024] The process of the solvent regeneration step is as follows:

[0025] The primary mixed regeneration liquid is subjected to heating distillation treatment, and methanol, oil and phenol are separated and recovered.

[0026] The secondary mixed regeneration liquid is subjected to heating distillation treatment, and ethanol, oil and phenol are recovered.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] The application provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater, adopts methanol, ethanol and water as a regeneration solvent, and realizes rapid desorption of oil and phenol and efficient regeneration of MOFs / particle carbon balls by means of the regeneration solvent combined with ultrasonic vibration treatment, the regeneration process is simple, the cost is low, and the method is convenient for application in actual engineering; wherein, the desorption of oil and phenol is realized quickly by injecting the regeneration solvent into the MOFs / particle carbon ball material saturated with adsorption and then under the action of ultrasonic vibration; secondly, the regeneration of the MOFs / particle carbon ball material is realized for multiple times by means of different regeneration solvents combined with ultrasonic vibration, so that the regeneration efficiency of the MOFs / particle carbon ball material can be kept above 95 %; and the separation efficiency of the MOFs / particle carbon ball material after multiple regeneration for oil and phenol in wastewater is stably kept at about 80 %, which meets the water quality requirements of the pretreated oil and phenol; the wastewater after the pretreatment of oil and phenol can effectively remove toxic and harmful substances in the wastewater, significantly improve the biodegradability of the wastewater, and significantly increase the economic benefits.

[0029] Further, methanol can exhibit similar phase solubility characteristics with oil and phenol in the wastewater, can quickly realize the rapid coalescence phase solubility of oil and phenol, and then realize the rapid desorption and recovery of oil and phenol; since the boiling points of methanol and oil and phenol have great differences, the efficient regeneration of the regeneration solvent is met, and the high-quality recovery of oil and phenol in the regeneration liquid is realized.

[0030] Further, ethanol can exhibit similar phase solubility characteristics with oil and phenol in the wastewater, can quickly realize the rapid coalescence phase solubility of oil and phenol, and then realize the rapid desorption and recovery of oil and phenol; since the boiling points of ethanol and oil and phenol have great differences, the efficient regeneration of the regeneration solvent is met, and the high-quality recovery of oil and phenol in the regeneration liquid is realized.

[0031] Further, the mixed regeneration liquid after desorption realizes the separation of oil, phenol and the regeneration solvent by distillation, wherein, oil and phenol are effectively recovered as value-added products, and the regeneration solvent is used for the regeneration of the next batch of adsorption material. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 It is an apparent morphology diagram of the MOFs / particle carbon ball material before regeneration in the application.

[0033] Figure 2 It is an apparent morphology diagram of the MOFs / particle carbon ball material after regeneration in the application.

[0034] Figure 3 It is a diagram of the change of the adsorption capacity of the MOFs / particle carbon ball material with the number of cyclic regeneration.

[0035] Figure 4Figure 1 is a graph showing the change of desorption rate of MOFs / pellet carbon ball material in the present application with the number of cyclic regeneration. DETAILED DESCRIPTION

[0036] In order to make the technical problems solved by the present application, the technical solutions and beneficial effects clearer, the following specific embodiments are used to further illustrate the present application. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0037] The present application provides a regeneration method of selective adsorption material for oil and phenol in coal chemical industry wastewater, which is used in the regeneration process of MOFs / pellet carbon ball material; wherein the MOFs / pellet carbon ball material is formed by in-situ polymerization of organic carbon skeleton material A and metal organic skeleton material B; wherein the organic carbon skeleton material A is formed by polymerization of non-polar monomers under the action of initiator, crosslinking agent, dispersing agent and pore adjusting agent; the non-polar monomers include styrene, diallyl phthalate and ethylene glycol dimethacrylate; the metal organic skeleton material B is formed by polymerization of metal compound monomers and carboxylic acid organic ligands; the metal compound monomers include iron nitrate nonahydrate, chromium nitrate nonahydrate and zinc nitrate nonahydrate; the carboxylic acid organic ligands include terephthalic acid, phthalic acid and trimesic acid; the crosslinking agent uses one of divinylbenzene, hydroxyethyl methacrylate and N,N-methylene bisacrylamide; the dispersing agent uses a mixture of polyvinyl alcohol, calcium chloride and gelatin; the pore adjusting agent uses one or more of toluene, n-heptane and diesel; the initiator uses one of dibenzoyl peroxide, azobisisobutyronitrile and persulfate.

[0038] Specifically, the regeneration method of selective adsorption material for oil and phenol in coal chemical industry wastewater comprises the following steps:

[0039] Step 1, mixing the selective adsorption material to be treated with methanol, and keeping for a preset desorption time to obtain a first regeneration intermediate mixed system; wherein the selective adsorption material to be treated is a saturated MOFs / pellet carbon ball material, and the MOFs / pellet carbon ball material is used for selective adsorption of oil and phenol in coal chemical industry wastewater; wherein the volume ratio of the selective adsorption material to be treated to the methanol is 1:(1-3), and the preset desorption time is 20-30 min.

[0040] Step 2, the intermediate mixture of the first regeneration is placed in an ultrasonic vibration environment to promote the desorption and aggregation of the adsorbed substances, to obtain the MOFs / pellet carbon ball material after the first regeneration and the first mixed regeneration liquid; specifically, an ultrasonic emitter is introduced into the intermediate mixture of the first regeneration, and the desorption and aggregation of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic waves emitted by the ultrasonic emitter; wherein the frequency of the ultrasonic emitter is 20-40 KHz, the acoustic intensity of the ultrasonic emitter is 0.5-2 W / cm 2 , and the ultrasonic wave action time is 10-20 min.

[0041] Step 3, the MOFs / pellet carbon ball material after the first regeneration is mixed with ethanol, and the operations of step 1 and step 2 are repeated, to obtain the MOFs / pellet carbon ball material after the second regeneration and the second mixed regeneration liquid; wherein the volume ratio of the MOFs / pellet carbon ball material after the first regeneration to the ethanol is 1:(1-3).

[0042] Step 4, the MOFs / pellet carbon ball material after the second regeneration is mixed with water, and the operations of step 1 and step 2 are repeated, to obtain the MOFs / pellet carbon ball material after the third regeneration and the third mixed regeneration liquid; wherein the volume ratio of the MOFs / pellet carbon ball material after the second regeneration to water is 1:(1-3).

[0043] Step 5, the first mixed regeneration liquid is subjected to heating distillation treatment, to separate and recover methanol, oil and phenol; the second mixed regeneration liquid is subjected to heating distillation treatment, to recover ethanol, oil and phenol.

[0044] As shown in the accompanying Figure 1 , the accompanying Figure 1 shows the apparent morphology of the MOFs / pellet carbon ball material before regeneration; as can be seen from the accompanying Figure 1 , the MOFs / pellet carbon ball material is a small round ball with a diameter of 0.7-1.2 mm, a milky white color, a smooth surface and uniform particle size, high mechanical strength and easy separation and reuse, and it is easier to achieve efficient regeneration.

[0045] As shown in the accompanying Figure 2 , the accompanying Figure 2 shows the apparent morphology of the MOFs / pellet carbon ball material after regeneration, and as can be seen from the accompanying Figure 2 , the MOFs / pellet carbon ball material after multiple adsorption and regeneration still exhibits the initial apparent characteristics, uniform particle size, and less mechanical damage such as abrasion, which shows its potential as a durable and efficient adsorbent.

[0046] As shown in the accompanying Figure 3 , the accompanying Figure 3The figure of the change of the adsorption capacity of the MOFs / pellet carbon ball material with the number of cyclic regeneration is shown in the accompanying Figure 3 As shown in the accompanying The figure of the change of the desorption rate of the MOFs / pellet carbon ball material with the number of cyclic regeneration is shown in the accompanying

[0047] Figure 4 As shown in the accompanying Figure 4 The figure of the change of the desorption rate of the MOFs / pellet carbon ball material with the number of cyclic regeneration is shown in the accompanying Figure 4 As shown in the accompanying

[0048] Regeneration principle:

[0049] The regeneration method of the selective adsorption material for oil and phenol in coal chemical wastewater provided by the application uses methanol, ethanol and water as the regeneration solvent, realizes the rapid desorption of oil and phenol and the efficient regeneration of the MOFs / pellet carbon ball material through the combination of ultrasonic and the regeneration solvent; specifically, the regeneration solvent is injected into the MOFs / pellet carbon ball material saturated with adsorption, then the desorption of oil and phenol is realized rapidly under the action of ultrasonic, and the mixed regeneration liquid after the desorption realizes the separation of oil, phenol and the regeneration solvent through distillation; wherein, the oil and phenol are effectively recovered as value-added products, and the regeneration solvent is used for the regeneration of the next batch of adsorption material.

[0050] Due to the characteristics of high emulsification degree, large viscosity and stable occurrence of oil and phenol in coal chemical wastewater, the oil and phenol substances adhered to the surface of the MOFs / pellet carbon ball material have the problems of incomplete or difficult desorption if the traditional regeneration method is used, and the application can effectively weaken the force of oil and phenol on the adsorption material under the action of ultrasonic cavitation, thereby accelerating the diffusion and coalescence of oil and phenol, and realizing the efficient regeneration of the MOFs / pellet carbon ball material more easily.

[0051] Secondly, the regenerating solvent methanol and ethanol used in the application can be efficiently used by microorganisms in biochemical treatment and be fully degraded, and thus even if there is a small amount of solvent residue, secondary pollution caused by the solvent residue will not occur, and the increase of input cost caused by the additional carbon source in biochemical treatment is avoided.

[0052] The regeneration method can significantly improve the regeneration efficiency of the MOFs / particle carbon ball material, and the regeneration efficiency after multiple regeneration remains above 95%. Meanwhile, high-quality recovery of oil and phenol is achieved, and the recovery rate of oil and phenol is above 90%. The separation efficiency of the MOFs / particle carbon ball material after multiple regeneration for oil and phenol in wastewater is about 80%, which meets the quality requirement of the pretreated effluent of oil and phenol. The wastewater pretreated by oil and phenol can effectively remove toxic and harmful substances in the wastewater, significantly improve the biodegradability of the wastewater, and significantly increase the economic benefit.

[0053] Example 1

[0054] The embodiment 1 provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical wastewater, which comprises the following steps:

[0055] Step 1, the MOFs / particle carbon ball material saturated with adsorption is mixed with methanol at a volume ratio of 1:1, and after maintaining the desorption time for 20 min, a first regeneration mixed system is obtained.

[0056] Step 2, an ultrasonic generator is introduced into the first regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic wave, so that the MOFs / particle carbon ball material after first regeneration and a first mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 20 KHz, the acoustic intensity is 0.5 W / cm 2 , and the ultrasonic action time is 20 min; wherein the first mixed regeneration liquid is returned to a solvent regeneration and substrate recovery system for separation and recovery of methanol, oil and phenol.

[0057] Step 3, the MOFs / pellet carbon ball material after the first regeneration is mixed with ethanol at a volume ratio of 1:1, and after maintaining the desorption time for 20 min, a secondary regeneration mixed system is obtained.

[0058] Step 4, an ultrasonic generator is introduced into the secondary regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic wave, to obtain the MOFs / pellet carbon ball material after the secondary regeneration and a secondary mixed regeneration liquid; wherein the frequency of the ultrasonic generator is 40 KHz, the acoustic intensity is 2 W / cm 2 , and the ultrasonic action time is 10 min; wherein the secondary mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of ethanol, oil and phenol.

[0059] Step 5, the MOFs / pellet carbon ball material after the secondary regeneration is mixed with water at a volume ratio of 1:1, and after maintaining the desorption time for 20 min, a tertiary regeneration mixed system is obtained.

[0060] Step 6, an ultrasonic generator is introduced into the tertiary regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic wave, to obtain the MOFs / pellet carbon ball material after the tertiary regeneration and a tertiary mixed regeneration liquid; wherein the frequency of the ultrasonic generator is 20 KHz, the acoustic intensity is 0.5 W / cm 2 , and the ultrasonic action time is 15 min; wherein the tertiary mixed regeneration liquid is returned to the front end of the water inlet of the fixed bed adsorption column.

[0061] Step 7, the primary mixed regeneration liquid and the secondary mixed regeneration liquid are respectively subjected to heating distillation treatment in the solvent regeneration and substrate recovery system, to separate and recover methanol, ethanol, oil and phenol; wherein the heating distillation temperature is 75°C.

[0062] It should be noted that the solvent regeneration and substrate recovery system includes a heating temperature control device, an evaporation cooling recovery device, and a regenerated solvent storage tank; the heating temperature control device is used for heating the primary mixed regeneration liquid and the secondary mixed regeneration liquid, the evaporation cooling recovery device is used for recovering methanol or ethanol by evaporation cooling, and the regenerated solvent storage tank is used for storing the regenerated methanol or ethanol, and the separated and recovered oil and phenol substrate are discharged through a pipeline for recycling.

[0063] Example 2

[0064] The present embodiment 2 provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater, which comprises the following steps:

[0065] Step 1, the MOFs / pellet carbon ball material saturated with adsorption is mixed with methanol at a volume ratio of 1:2, and after maintaining the desorption time for 30 min, a first regeneration mixed system is obtained.

[0066] Step 2, an ultrasonic generator is introduced into the first regeneration mixed system, and under the mechanical vibration of the ultrasonic wave, the desorption and coalescence of the adsorbed substances are promoted, so that a first regenerated MOFs / pellet carbon ball material and a first mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 20 KHz, the acoustic intensity is 1 W / cm 2 , and the ultrasonic action time is 20 min; wherein the first mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of methanol, oil and phenol.

[0067] Step 3, the first regenerated MOFs / pellet carbon ball material is mixed with ethanol at a volume ratio of 1:2, and after maintaining the desorption time for 30 min, a second regeneration mixed system is obtained.

[0068] Step 4, an ultrasonic generator is introduced into the second regeneration mixed system, and under the mechanical vibration of the ultrasonic wave, the desorption and coalescence of the adsorbed substances are promoted, so that a second regenerated MOFs / pellet carbon ball material and a second mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 30 KHz, the acoustic intensity is 0.5 W / cm 2 , and the ultrasonic action time is 10 min; wherein the second mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of ethanol, oil and phenol.

[0069] Step 5, the second regenerated MOFs / pellet carbon ball material is mixed with water at a volume ratio of 1:2, and after maintaining the desorption time for 30 min, a third regeneration mixed system is obtained.

[0070] Step 6, an ultrasonic generator is introduced into the third regeneration mixed system, and under the mechanical vibration of the ultrasonic wave, the desorption and coalescence of the adsorbed substances are promoted, so that a third regenerated MOFs / pellet carbon ball material and a third mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 20 KHz, the acoustic intensity is 2 W / cm 2 , and the ultrasonic action time is 20 min; wherein the third mixed regeneration liquid is returned to the front end of the water inlet of the fixed bed adsorption column.

[0071] Step 7, the first mixed regeneration liquid and the second mixed regeneration liquid are respectively subjected to heating distillation treatment in the solvent regeneration and substrate recovery system, and methanol, ethanol, oil and phenol are separated and recovered; wherein the heating distillation temperature is 70°C.

[0072] Example 3

[0073] The embodiment 3 provides a regeneration method of a selective adsorption material for oil and phenol in coal chemical industry wastewater, comprising the following steps:

[0074] Step 1, the MOFs / pellet carbon ball material saturated with adsorption is mixed with methanol at a proportion of 1:3 in volume ratio, and after a desorption time of 30 min, a first regeneration mixed system is obtained.

[0075] Step 2, an ultrasonic generator is introduced into the first regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of ultrasonic waves, so that a first regenerated MOFs / pellet carbon ball material and a first mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 30 KHz, the acoustic intensity is 1.5 W / cm 2 , the ultrasonic action time is 15 min; wherein the first mixed regeneration liquid is returned to a solvent regeneration and substrate recovery system for separation and recovery of methanol, oil and phenol.

[0076] Step 3, the first regenerated MOFs / pellet carbon ball material is mixed with ethanol at a proportion of 1:3 in volume ratio, and after a desorption time of 30 min, a second regeneration mixed system is obtained.

[0077] Step 4, an ultrasonic generator is introduced into the second regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of ultrasonic waves, so that a second regenerated MOFs / pellet carbon ball material and a second mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 40 KHz, the acoustic intensity is 1 W / cm 2 , the ultrasonic action time is 10 min; wherein the second mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of ethanol, oil and phenol.

[0078] Step 5, the second regenerated MOFs / pellet carbon ball material is mixed with water at a proportion of 1:3 in volume ratio, and after a desorption time of 30 min, a third regeneration mixed system is obtained.

[0079] Step 6, an ultrasonic generator is introduced into the third regeneration mixed system, and the desorption and coalescence of the adsorbed substances are promoted under the mechanical vibration of ultrasonic waves, so that a third regenerated MOFs / pellet carbon ball material and a third mixed regeneration liquid are obtained; wherein the frequency of the ultrasonic generator is 25 KHz, the acoustic intensity is 2 W / cm 2 , the ultrasonic action time is 10 min; wherein the third mixed regeneration liquid is returned to the front end of the water inlet of the fixed bed adsorption column.

[0080] Step 7, the first mixed regeneration liquid and the second mixed regeneration liquid are respectively subjected to heating distillation treatment in the solvent regeneration and substrate recovery system, and methanol, ethanol, oil and phenol are separated and recovered; wherein the heating distillation temperature is 60 DEG C.

[0081] Example 4

[0082] The present example 4 provides a method for regenerating selective adsorption material of oil and phenol in coal chemical wastewater, comprising the following steps:

[0083] Step 1, mix the MOFs / pellet carbon ball material saturated with adsorption and methanol at a volume ratio of 1:2, and keep the desorption time for 25 min to obtain a first regeneration mixed system.

[0084] Step 2, introduce an ultrasonic generator into the first regeneration mixed system, promote the desorption and coalescence of the adsorbed substances under the mechanical vibration of ultrasonic waves, and obtain the MOFs / pellet carbon ball material after first regeneration and a first mixed regeneration liquid; wherein the frequency of the ultrasonic generator is 30 KHz, the acoustic intensity is 1.5 W / cm 2 , and the ultrasonic action time is 15 min; wherein the first mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of methanol, oil and phenol.

[0085] Step 3, mix the MOFs / pellet carbon ball material after first regeneration and ethanol at a volume ratio of 1:2, and keep the desorption time for 25 min to obtain a second regeneration mixed system.

[0086] Step 4, introduce an ultrasonic generator into the second regeneration mixed system, promote the desorption and coalescence of the adsorbed substances under the mechanical vibration of ultrasonic waves, and obtain the MOFs / pellet carbon ball material after second regeneration and a second mixed regeneration liquid; wherein the frequency of the ultrasonic generator is 25 KHz, the acoustic intensity is 1 W / cm 2 , and the ultrasonic action time is 15 min; wherein the second mixed regeneration liquid is returned to the solvent regeneration and substrate recovery system for separation and recovery of ethanol, oil and phenol.

[0087] Step 5, mix the MOFs / pellet carbon ball material after second regeneration and water at a volume ratio of 1:2, and keep the desorption time for 25 min to obtain a third regeneration mixed system.

[0088] Step 6, introduce an ultrasonic generator into the third regeneration mixed system, promote the desorption and coalescence of the adsorbed substances under the mechanical vibration of ultrasonic waves, and obtain the MOFs / pellet carbon ball material after third regeneration and a third mixed regeneration liquid; wherein the frequency of the ultrasonic generator is 25 KHz, the acoustic intensity is 1.5 W / cm 2 , and the ultrasonic action time is 10 min; wherein the third mixed regeneration liquid is returned to the front end of the water inlet of the fixed bed adsorption column.

[0089] Step 7, in the solvent regeneration and substrate recovery system, the primary mixed regeneration liquid and the secondary mixed regeneration liquid are respectively subjected to heating distillation treatment to separate and recover methanol, ethanol, oil and phenol; wherein the heating distillation temperature is 80℃.

[0090] Test results:

[0091] In the present application, the MOFs / pellet carbon ball material saturated with adsorption is regenerated by using the regeneration method described in the above Examples 1-4; specifically, the operating method and regeneration conditions determined in the above Examples 1-4 are used for the MOFs / pellet carbon ball material saturated with adsorption, after the reaction is completed, the water quality parameters before and after treatment are measured to reflect the implementation effect of each example; the detection results of each index under each example are shown in Table 1.

[0092] Table 1 Regeneration rate of MOFs / pellet carbon ball saturated with adsorption and recovery rate of oil and phenol under Examples 1-4

[0093] Example 1 Example 2 Example 3 Example 4 Regeneration rate (%) of MOFs / pellet charcoal ball material 97.8 96.5 95.7 98.5 Oil recovery rate (%) 92.5 94.3 92.8 91.9 Phenol recovery rate (%) 91.5 90.3 94.2 95.1

[0094] As can be seen from Table 1, the regeneration method described in the above Examples 1-4 is used for the regeneration of MOFs / pellet carbon ball saturated with adsorption and the high-quality recovery of regeneration solvents and oil and phenol in the regeneration liquid, which shows stable regeneration and separation effect, and the adsorption effect of the regenerated MOFs / pellet carbon ball is stable, which has important guiding significance for the complete harmless treatment of coal chemical industry wastewater and the green and sustainable healthy development of coal chemical industry.

[0095] The regeneration method of the selective adsorption material for oil and phenol in coal chemical industry wastewater described in the present application can realize the separation and recovery of oil and phenol in coal chemical industry wastewater, and the recovery rate of oil and phenol reaches more than 90%, and the recovery of oil and phenol is also the key to realize the harmless treatment of coal chemical industry wastewater and the sustainable development of coal chemical industry; the selective removal of oil and phenol substances by pretreatment process creates good survival conditions for the activity of microorganisms in biochemical treatment while realizing resource recovery; in addition, the present application significantly improves the regeneration efficiency of MOFs / pellet carbon ball material, and the regeneration efficiency after multiple regeneration always remains more than 95%; the separation efficiency of MOFs / pellet carbon ball material after multiple regeneration for oil and phenol in wastewater is stable at about 80%, which meets the water quality requirements of oil and phenol pretreatment effluent; the wastewater after oil and phenol pretreatment can effectively remove toxic and harmful substances in wastewater and significantly increase economic benefits.

[0096] In the present application, the oil and phenol are quickly desorbed and the MOFs / particle carbon balls are efficiently regenerated by the method of ultrasonic combination with the regenerated solvent. A certain volume of regenerated solvent is injected into the saturated MOFs / particle carbon ball adsorption material, and then the oil and phenol are quickly desorbed under the action of ultrasonic. The regenerated liquid after desorption is separated from the oil and phenol by distillation, wherein the oil and phenol are effectively recovered as value-added products, and the regenerated solvent is used for the regeneration of the next batch of adsorption material. The regenerated solvent used in the present application is also the main component of the additional carbon source in the biochemical treatment of wastewater, which can be efficiently utilized and fully degraded by microorganisms in the biochemical treatment. Therefore, even if there is a small amount of solvent residue, it will not cause secondary pollution due to the residue of the solvent, and the increase of the input cost caused by the additional carbon source in the biochemical treatment is also avoided.

[0097] Specifically, the regenerated solvent is mainly methanol and ethanol, wherein the methanol and ethanol exhibit similar phase-soluble characteristics with the oil and phenol in the wastewater, which can quickly realize the rapid coalescence of the oil and phenol, and then realize the quick desorption and recovery of the oil and phenol. The regenerated liquid after desorption can be separated from the methanol and ethanol and the oil and phenol by distillation, because the boiling points of the methanol and ethanol and the oil and phenol exhibit a large boiling point difference, and the low energy consumption required by the methanol and ethanol can realize the efficient regeneration of the regenerated solvent, and the high-quality recovery of the oil and phenol in the regenerated liquid is also realized.

[0098] The above embodiment is only one of the implementation manners of the technical scheme of the present application, and the scope of the present application is not limited to the above embodiment, but also includes any changes, substitutions and other implementation manners easily thought by those skilled in the art within the technical scope disclosed in the present application.

Claims

1. A method for regenerating a selective adsorption material for oil and phenol in coal chemical wastewater, characterized in that, Comprise the following steps: Step 1, the selective adsorption material to be treated is mixed with methanol, and after a preset desorption time, a first regeneration intermediate mixed system is obtained; wherein the selective adsorption material to be treated is a MOFs / pellet carbon ball material saturated with adsorption, and the MOFs / pellet carbon ball material is used for selectively adsorbing oil and phenol in coal chemical wastewater; The MOFs / pellet carbon ball material is formed by in-situ polymerization of an organic carbon skeleton material A and a metal organic skeleton material B; Wherein, the organic carbon skeleton material A is formed by polymerization of non-polar monomers under the action of initiators, crosslinking agents, dispersants and pore regulators; the non-polar monomers include styrene, diallyl phthalate and dimethyl acrylate glycol ester; The metal organic skeleton material B is formed by polymerization of metal compound monomers and carboxylic acid organic ligands; the metal compound monomers include iron nitrate nonahydrate, chromium nitrate nonahydrate and zinc nitrate nonahydrate; the carboxylic acid organic ligands include terephthalic acid, phthalic acid and trimesic acid; Step 2, the first regeneration intermediate mixed system is placed in an ultrasonic vibration environment to promote the desorption and aggregation of the adsorbed substances, and a first regenerated MOFs / pellet carbon ball material and a first mixed regeneration liquid are obtained; Step 3, the first regenerated MOFs / pellet carbon ball material is mixed with ethanol, and the operations of steps 1 and 2 are repeated, to obtain a second regenerated MOFs / pellet carbon ball material and a second mixed regeneration liquid; Step 4, the second regenerated MOFs / pellet carbon ball material is mixed with water, and the operations of steps 1 and 2 are repeated, to obtain a third regenerated MOFs / pellet carbon ball material and a third mixed regeneration liquid.

2. The regeneration method of the selective adsorption material for oil and phenol in coal chemical wastewater according to claim 1, characterized in that, The volume ratio of the selective adsorption material to be treated to the methanol is 1:(1-3).

3. The method according to claim 1, characterized in that, The preset desorption time is 20-30 min.

4. The method according to claim 1, characterized in that, The crosslinking agent uses one or more of divinylbenzene, hydroxyethyl methacrylate and N,N-methylene bisacrylamide; the dispersant uses one or more of polyvinyl alcohol, calcium chloride and gelatin; the pore regulator uses one or more of toluene, n-heptane and diesel; and the initiator uses one or more of dibenzoyl peroxide, azobisisobutyronitrile and persulfate.

5. The method according to claim 1, wherein the method is characterized in that, The first regeneration intermediate mixed system is placed in an ultrasonic vibration environment to promote the desorption and aggregation of the adsorbed substances, and a first regenerated MOFs / pellet carbon ball material and a first mixed regeneration liquid are obtained; the process is as follows: An ultrasonic transmitter is introduced into the first regeneration intermediate mixed system, and the desorption and aggregation of the adsorbed substances are promoted under the mechanical vibration of the ultrasonic waves emitted by the ultrasonic transmitter.

6. The method for regenerating the selective adsorption material for oil and phenol in coal chemical wastewater according to claim 5, characterized in that, The frequency of the ultrasonic emitter is 20-40 KHz, the acoustic intensity of the ultrasonic emitter is 0.5-2 W / cm 2 , and the ultrasonic action time is 10-20 min.

7. The method according to claim 1, wherein the method is characterized in that, The volume ratio of the first regenerated MOFs / pellet carbon ball material to the ethanol is 1:(1-3).

8. The method according to claim 1, wherein the method is characterized in that, The volume ratio of the second regenerated MOFs / pellet carbon ball material to water is 1:(1-3).

9. The method according to claim 1, wherein the method is characterized in that, Further comprising a solvent regeneration step; The process of the solvent regeneration step is as follows: The first mixed regeneration liquid is subjected to heating distillation treatment, and methanol, oil and phenol are separated and recovered. The secondary mixed regenerating liquid is subjected to heating distillation treatment to recover ethanol, oil and phenol.

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