Recyclable agent for treating oily sludge, preparation method and application thereof

Abstract

The present invention belongs to the technical field of preparation of agents for oily sludge, and specifically relates to a recyclable agent for treating oily sludge, a preparation method and its application. The recyclable agent for treating oily sludge is composed of the following raw materials: 2-5% magnetic responsive ionic liquid, 1-6% nonionic surfactant, 10-20% low molecular weight alcohol, 8-15% alkaline component, 0.2-1.0% flocculant, and the rest is water. The recyclable agent for treating oily sludge of the present invention is a micellar solution stably formed by magnetic responsive ionic liquid and nonionic surfactant, relying on the solubilization ability of micelles themselves for oil-soluble substances, the hydrophobicity of nonionic surfactants, and the synergistic effect between various non-covalent interactions such as π-π stacking of magnetic responsive ionic liquid and crude oil components, and has a strong removal effect on crude oil on the surface of oily sludge, and the magnetic responsive ionic liquid can be recycled and reused after treating oily sludge.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of agents for oily sludge, and specifically relates to a recoverable agent for treating oily sludge, a preparation method and application thereof. Background Art

[0002] As one of the most important energy sources in human society, oil has been used in various fields. In recent years, with the rapid development of science and technology and society, the demand for oil has increased significantly. With the increase in oil production, the pollutants it produces have also increased significantly. Oily sludge is the most important solid waste produced by the oil industry. Its components show different properties due to the different sources of crude oil, processing, and chemical reagents added during the refining process. According to incomplete statistics, the world produces more than 60 million tons of oily sludge each year, and my country's annual production of oily sludge has reached 12 million tons. The total storage capacity of oily sludge has exceeded 1 billion tons. If it is not handled properly, it will cause significant damage to the environment and human health. Therefore, oily sludge treatment technology has received much attention in recent years. At present, there are many methods for treating oily sludge, and the commonly used ones are pyrolysis, incineration, thermochemical washing, solvent extraction, biological treatment, etc. However, these methods cannot meet the environmental protection and economic requirements in the treatment of oily sludge.

[0003] The surfactant water washing method is an economical, effective, fast and easy method for treating oily sludge, and has low requirements for equipment, and has good industrial prospects. When the concentration of the surfactant aqueous solution is higher than the critical micelle concentration CMC, the oil phase will be distributed into the hydrophobic core of the micelle. The micelle has extremely low interfacial tension and has a strong penetration ability for oily sludge, which can effectively improve the extraction capacity of the oil phase. However, the intermediate aqueous phase cannot be reused after treatment by the traditional surfactant water washing method, and the treatment cost is high. Imidazole ionic liquids have a strong π-π stacking effect with the oil phase of oily sludge. Using them to treat oily sludge can significantly improve the treatment effect.

[0004] Patent CN 113772903B discloses a microemulsion for reducing the oil content of oily sludge, and its preparation method and application. The microemulsion for reducing the oil content of oily sludge is composed of the following raw materials by weight: 1 part of ionic liquid surfactant, 25-30 parts of co-surfactant, 20-25 parts of oil-soluble components and 45-50 parts of water. The microemulsion for reducing the oil content of oily sludge is an oil-in-water type, which saves costs and has a great solubilizing ability for crude oil, thereby improving the removal rate of crude oil in oily sludge. However, ionic liquids are expensive, and using them for oily sludge treatment will increase the treatment cost to a certain extent. Moreover, the large-scale use of oil-soluble components also increases the treatment cost to a certain extent and causes serious pollution to the environment. Therefore, it is necessary to explore a new type of recyclable agent for oily sludge treatment. Summary of the invention

[0005] The purpose of the present invention is to provide a recyclable agent for treating oily sludge. The recyclable agent for treating oily sludge is a micellar solution stably formed by magnetically responsive ionic liquid and non-ionic surfactant. It has a strong removal effect on crude oil on the surface of oily sludge by relying on the synergistic effect of various non-covalent interactions such as the solubilization ability of micelles themselves for oil-soluble substances, the hydrophobicity of non-ionic surfactants, and the π-π stacking of magnetically responsive ionic liquids and crude oil components. The magnetically responsive ionic liquid can be recycled after treating the oily sludge; in addition, the present invention also provides its preparation method and application.

[0006] The recyclable agent for treating oily sludge of the present invention is composed of the following raw materials, measured by mass percentage: 2-5% of magnetically responsive ionic liquid, 1-6% of nonionic surfactant, 10-20% of low molecular weight alcohol, 8-15% of alkaline component, 0.2-1.0% of flocculant, and the rest is water; wherein: the magnetically responsive ionic liquid is one of 1-vinyl-3-cyanomethylimidazole ferric bromide or 1-vinyl-3-cyanomethylimidazole ferric chloride, and the preparation method thereof is composed of the following steps:

[0007] (1) Weighing N-vinylimidazole and one of bromoacetonitrile or chloroacetonitrile and mixing them at a constant temperature with stirring, and after the reaction is completed, placing the product in a vacuum drying oven for drying to obtain a white solid product 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br) or 1-vinyl-3-cyanomethylimidazolium chloride ([CMVIM]Cl);

[0008] (2) One of 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br) or 1-vinyl-3-cyanomethylimidazolium chloride ([CMVIM]Cl) is reacted with anhydrous FeCl3 under an Ar atmosphere by stirring. After the reaction is completed, a reddish brown viscous liquid is separated while hot, and then dried to prepare 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]) or 1-vinyl-3-cyanomethylimidazolium ferric chloride ([CMVIM][FeCl4]).

[0009] in:

[0010] In step (1), the molar ratio of N-vinylimidazole to bromoacetonitrile or chloroacetonitrile is 1:1-1:2.

[0011] In step (1), the temperature for constant temperature stirring and mixing is 60-80°C, the time for stirring and mixing is 24-36 hours, the drying temperature is 30-50°C, and the drying time is 36-48 hours.

[0012] In step (2), the molar ratio of one of 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br) or 1-vinyl-3-cyanomethylimidazolium chloride ([CMVIM]Cl) to anhydrous FeCl3 is 1:1-1:1.5.

[0013] In step (2), the stirring reaction temperature is 30-50° C., the stirring reaction speed is 300-500 r / min, and the stirring reaction time is 24-48 h.

[0014] In step (2), the drying temperature is 40-60°C and the drying time is 48-64h.

[0015] The nonionic surfactant is one of propylene glycol block polyether L43, propylene glycol block polyether L44, propylene glycol block polyether L64, propylene glycol block polyether L65 or propylene glycol block polyether F68 nonionic surfactants.

[0016] The low molecular weight alcohol is one of ethanol, ethylene glycol, propylene glycol or butanol.

[0017] The alkaline component is one of sodium carbonate, sodium bicarbonate or sodium acetate.

[0018] The flocculant is one of polyaluminium chloride, polyacrylamide, polyaluminium sulfate or microbial flocculant mucopolysaccharide.

[0019] The method for preparing the recoverable agent for treating oily sludge of the present invention comprises the following steps:

[0020] ① Add the magnetically responsive ionic liquid and the non-ionic surfactant to the low molecular weight alcohol and mix them evenly by hand shaking to obtain an alcohol solution;

[0021] ② Add the flocculant and alkaline component to water in sequence and mix them evenly by hand shaking to obtain an aqueous solution;

[0022] ③ Add the alcohol solution prepared in step ① dropwise into the aqueous solution prepared in step ② for ultrasonic treatment, and mix evenly to prepare a recyclable agent for treating oily sludge.

[0023] in:

[0024] The mixing temperature in step ① is room temperature and the mixing time is 3-8 minutes.

[0025] In step ②, the mixing temperature is room temperature and the mixing time is 3-8 minutes.

[0026] The ultrasonic treatment time in step ③ is 10-20 min.

[0027] The application of the recyclable agent for treating oily sludge described in the present invention is to mix the recyclable agent for treating oily sludge with oily sludge, heat and stir, then stand for 24-36 hours, and finally centrifuge to separate the upper layer into an oil phase, a middle layer into an aqueous phase, and a lower layer into mud and sand solids; an N52 type super-strong NdFeB magnet is applied to the aqueous phase in the middle layer to make the magnetically responsive ionic liquid in the system move in a directional manner and move it out of the aqueous phase in the middle layer, thereby realizing the recovery of the magnetically responsive ionic liquid.

[0028] in:

[0029] The volume mass ratio of the recyclable agent for treating oily sludge to the oily sludge is 10:2-15:2, in units of mL / g; the heating and stirring temperature is 60°C-70°C, the heating and stirring speed is 350-500 r / min, the heating and stirring time is 30-50 min, and the magnetic field application time is 10-30 min.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The recyclable agent for treating oily sludge of the present invention uses a combination of magnetically responsive ionic liquid and non-ionic surfactant as an emulsifier, which can form a strong interaction force with the components in the oily sludge that are difficult to remove, thereby helping to reduce the oil content of the oily sludge.

[0032] (2) The recyclable agent for treating oily sludge described in the present invention comprises a magnetically responsive ionic liquid and a non-ionic surfactant to form a micellar aqueous solution, which does not require the use of an oil phase, has a small droplet size, good solution stability and good solubilizing ability, and can effectively improve the removal rate of crude oil in oily sludge. The ionic liquid can be recycled, thereby greatly reducing the treatment cost.

[0033] (3) The recyclable agent for treating oily sludge of the present invention is responsive to a magnetic field. By applying a magnetic field, the magnetically responsive ionic liquid can be recycled, thereby increasing the reuse rate of the magnetically responsive ionic liquid and reducing the treatment cost.

[0034] (4) The recyclable agent for treating oily sludge described in the present invention uses a composite system of magnetic ionic liquid and other non-ionic surfactants as surfactants to prepare micellar solutions. The advantages of micelles are combined to treat oily sludge, thereby ensuring high treatment efficiency while achieving the recycling of the agent, greatly reducing the treatment cost.

[0035] (5) The recyclable agent for treating oily sludge described in the present invention is a micellar solution stably formed by a magnetically responsive ionic liquid and a non-ionic surfactant. It relies on the synergistic effect of various non-covalent interactions such as the solubilization ability of the micelles themselves for oil-soluble substances, the hydrophobicity of the non-ionic surfactant, and the π-π stacking of the magnetically responsive ionic liquid and the crude oil components. It has a strong removal effect on the crude oil on the surface of the oily sludge, and the magnetically responsive ionic liquid can be recycled after treating the oily sludge.

[0036] (6) The method for preparing the recoverable agent for treating oily sludge of the present invention has a simple process and does not require vigorous stirring. It can be obtained by simple mixing and ultrasound.

[0037] (7) The use of the recyclable agent for treating oily sludge described in the present invention has a simple treatment method, low energy consumption, good crude oil removal effect, and a crude oil removal rate of more than 97%. In addition, due to the recycling of ionic liquids, the treatment cost is significantly reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is an appearance diagram of the recoverable agent for treating oily sludge prepared in Example 1;

[0039] Figure 2 is a diagram of the magnetically responsive ionic liquid solution recovered after treating the oily sludge in Example 1;

[0040] Figure 3 This is the appearance of solid particles after treating oily sludge in Example 4. DETAILED DESCRIPTION

[0041] The present invention is further described below with reference to the embodiments.

[0042] Example 1

[0043] The recyclable agent for treating oily sludge described in Example 1 is composed of the following raw materials, measured in mass percentage: 4% magnetically responsive ionic liquid, 3% non-ionic surfactant, 10% low molecular weight alcohol, 8% alkaline component, 0.2% flocculant, and the rest water.

[0044] in:

[0045] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazolium ferric bromide; the nonionic surfactant is propylene glycol block polyether L44 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium bicarbonate; and the flocculant is polyacrylamide.

[0046] The preparation method of 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]) comprises the following steps:

[0047] (1) Weigh N-vinylimidazole and bromoacetonitrile in a molar ratio of 1:1, and stir the mixture at 60°C for 36 hours. After the reaction is completed, place the product in a vacuum drying oven at 40°C for 40 hours to obtain a white solid product, 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br).

[0048] (2) 0.1 mol of [CMVIM]Br obtained in step (1) was mixed with 0.1 mol of anhydrous FeCl3, and the mixture was stirred at 30°C and 500 r / min for 36 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 40°C for 64 h to obtain the final product, 1-vinyl-3-cyanomethylimidazole ferric bromide ([CMVIM][FeBrCl3]).

[0049] The method for preparing a recyclable agent for treating oily sludge described in Example 1 is composed of the following steps: Weigh 4 g of [CMVIM][FeBrCl3] and 3 g of propylene glycol block polyether L44 synthesized in Example 1, respectively, add them to 10 g of ethylene glycol, and mix them by hand for 3 minutes at room temperature to prepare an alcohol solution of a surfactant. Mix 8 g of sodium bicarbonate, 0.2 g of polyacrylamide and 74.8 g of water, and mix them by hand for 3 minutes at room temperature to prepare an aqueous solution. Add the alcohol solution dropwise to the aqueous solution, and mix evenly by ultrasonication for 10 minutes to obtain a recyclable agent for treating oily sludge, as shown in the macroscopic picture. Figure 1 shown.

[0050] The application of the recyclable agent for treating oily sludge described in Example 1 is composed of the following steps: 15 mL of the recyclable agent for treating oily sludge is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 350 r / min for 30 min, and centrifuged after standing for 24 hours. The crude oil removal rate is measured to be 98.15%. The N52 super-strong NdFeB magnet is applied to the intermediate aqueous phase for 10 minutes, which can realize the recycling of the magnetically responsive ionic liquid in the intermediate aqueous phase. The appearance of the intermediate aqueous phase after recycling is as follows: Figure 2 shown.

[0051] Example 2

[0052] The recyclable agent for treating oily sludge described in Example 2 is composed of the following raw materials, measured in mass percentage: 3% magnetically responsive ionic liquid, 4% non-ionic surfactant, 12% low molecular weight alcohol, 10% alkaline component, 0.4% flocculant, and the rest is water.

[0053] in:

[0054] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazolium ferric bromide; the nonionic surfactant is propylene glycol block polyether L64 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is propylene glycol; the alkaline component is sodium carbonate; and the flocculant is polyaluminum sulfate.

[0055] The preparation method of 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]) comprises the following steps:

[0056] (1) Weigh N-vinylimidazole and bromoacetonitrile in a molar ratio of 1:1.5, and mix them at 70°C with constant stirring for 30 h. After the reaction is completed, the product is placed in a vacuum drying oven at 30°C for 48 h to obtain a white solid product, 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br).

[0057] (2) 0.1 mol of [CMVIM]Br obtained in step (1) was mixed with 0.12 mol of anhydrous FeCl3, and the mixture was stirred at 400 r / min at 40°C for 48 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 50°C for 54 h to obtain the final product, 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]).

[0058] The preparation method of the recyclable agent for treating oily sludge described in Example 2 is composed of the following steps: 3 g of [CMVIM][FeBrCl3] synthesized in Example 2 and 4 g of propylene glycol block polyether L64 are weighed respectively, added to 12 g of propylene glycol, and mixed by hand for 4 min at room temperature to prepare an alcohol solution of a surfactant. 10 g of sodium carbonate, 0.4 g of polyaluminium sulfate and 70.6 g of water are mixed, and mixed by hand for 4 min at room temperature to prepare an aqueous solution. The alcohol solution is added dropwise to the aqueous solution, and the mixture is mixed evenly by ultrasonication for 12 min to obtain a recyclable agent.

[0059] The application of the recyclable agent for treating oily sludge described in Example 2 is composed of the following steps: 14 mL of the recyclable agent is mixed with 2 g of oily sludge, stirred at 400 r / min for 50 min at 65°C, and centrifuged after standing for 30 hours. The crude oil removal rate is measured to be 97.63%. The N52 super-strong NdFeB magnet is applied to the intermediate aqueous phase for 15 minutes, so that the magnetic responsive ionic liquid can be recycled in the intermediate aqueous phase.

[0060] Example 3

[0061] The recyclable agent for treating oily sludge described in Example 3 is composed of the following raw materials, measured in mass percentage: 4% magnetically responsive ionic liquid, 4% non-ionic surfactant, 16% low molecular weight alcohol, 12% alkaline component, 0.6% flocculant, and the rest is water.

[0062] in:

[0063] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazolium ferric bromide; the nonionic surfactant is propylene glycol block polyether L43 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium carbonate; and the flocculant is polyaluminium chloride.

[0064] The preparation method of 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]) comprises the following steps:

[0065] (1) Weigh N-vinylimidazole and bromoacetonitrile in a molar ratio of 1:2, and stir the mixture at 80°C for 24 hours. After the reaction is completed, place the product in a vacuum drying oven at 50°C for 36 hours to obtain a white solid product, 1-vinyl-3-cyanomethylimidazolium bromide ([CMVIM]Br).

[0066] (2) 0.1 mol of [CMVIM]Br obtained in step (1) was mixed with 0.15 mol of anhydrous FeCl3, and the mixture was stirred at 50°C and 300 r / min for 40 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 60°C for 48 h to obtain the final product, 1-vinyl-3-cyanomethylimidazolium ferric bromide ([CMVIM][FeBrCl3]).

[0067] The preparation method of the recyclable agent for treating oily sludge described in Example 3 is composed of the following steps: 4 g of [CMVIM][FeBrCl3] synthesized in Example 3 and 4 g of nonionic surfactant propylene glycol block polyether L43 are weighed respectively, and added to 16 g of ethylene glycol, and mixed by hand for 5 min at room temperature to prepare an alcohol solution of the surfactant. 12 g of sodium carbonate, 0.6 g of polyaluminum chloride and 63.4 g of water are mixed, and mixed by hand for 5 min at room temperature to prepare an aqueous solution. The alcohol solution is added dropwise to the aqueous solution, and the mixture is mixed evenly by ultrasonication for 14 min to obtain a recyclable agent.

[0068] The application of the recyclable agent for treating oily sludge described in Example 3 is composed of the following steps: 10 mL of the recyclable agent is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 500 r / min for 40 min, and centrifuged after standing for 36 hours. The crude oil removal rate is measured to be 97.26%. The N52 super-strong NdFeB magnet is applied to the intermediate aqueous phase for 20 minutes, so that the magnetic responsive ionic liquid can be recycled in the intermediate aqueous phase.

[0069] Example 4

[0070] The recyclable agent for treating oily sludge described in Example 4 is composed of the following raw materials, measured in mass percentage: 5% magnetically responsive ionic liquid, 2% non-ionic surfactant, 18% low molecular weight alcohol, 13% alkaline component, 0.8% flocculant, and the rest is water.

[0071] in:

[0072] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazole ferric chloride; the nonionic surfactant is propylene glycol block polyether L65 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium carbonate; and the flocculant is polyaluminium chloride.

[0073] The preparation method of 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]) comprises the following steps:

[0074] (1) Weigh N-vinylimidazole and chloroacetonitrile in a molar ratio of 1:1, and stir the mixture at 80°C for 24 h. After the reaction is completed, place the product in a vacuum drying oven at 40°C for 36 h to obtain a white solid product, 1-vinyl-3-cyanomethylimidazole chloride ([CMVIM]Cl).

[0075] (2) 0.1 mol of the white solid product [CMVIM]Cl prepared in step (1) was mixed with 0.1 mol of anhydrous FeCl3, and the mixture was stirred at 30°C and 500 r / min for 24 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 40°C for 64 h to obtain the final product, 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]).

[0076] The preparation method of the recyclable agent for treating oily sludge described in Example 4 is composed of the following steps: 5 g of [CMVIM][FeCl4] synthesized in Example 4 and 2 g of propylene glycol block polyether L65 are weighed respectively, added to 18 g of ethylene glycol, and mixed by hand for 6 min at room temperature to prepare an alcohol solution of a surfactant. 13 g of sodium carbonate, 0.8 g of polyaluminium chloride and 61.2 g of water are mixed, and mixed by hand for 6 min at room temperature to prepare an aqueous solution. The alcohol solution is added dropwise to the aqueous solution, and the mixture is mixed evenly by ultrasonication for 16 min to obtain a recyclable agent.

[0077] The application of the recyclable agent for treating oily sludge described in Example 4 is composed of the following steps: 15 mL of the recyclable agent is mixed with 2 g of oily sludge, stirred at 65°C at a speed of 500 r / min for 30 min, and centrifuged after standing for 24 h. The crude oil removal rate is measured to be 98.52%. The appearance of the solid particles after oil removal is as follows: Figure 3 As shown. Applying N52 super strong NdFeB magnet in the middle water phase for 25 min can realize the recycling of ionic liquid in the middle water phase.

[0078] Example 5

[0079] The recyclable agent for treating oily sludge described in Example 5 is composed of the following raw materials, measured in mass percentage: 5% magnetically responsive ionic liquid, 1% non-ionic surfactant, 20% low molecular weight alcohol, 15% alkaline component, 1.0% flocculant, and the rest is water.

[0080] in:

[0081] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazole ferric chloride; the nonionic surfactant is propylene glycol block polyether F68 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium acetate; and the flocculant is a microbial flocculant mucopolysaccharide (Guangzhou Runqun Chemical Co., Ltd.).

[0082] The preparation method of 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]) described in Example 5 is composed of the following steps:

[0083] (1) Weigh N-vinylimidazole and chloroacetonitrile in a molar ratio of 1:1.5, and mix them at 70°C with constant stirring for 30 h. After the reaction is completed, the product is placed in a vacuum drying oven at 30°C for 48 h to obtain a white solid product, 1-vinyl-3-cyanomethylimidazole chloride ([CMVIM]Cl).

[0084] (2) 0.1 mol of the white solid product [CMVIM]Cl prepared in step (1) was mixed with 0.12 mol of anhydrous FeCl3, and the mixture was stirred at 450 r / min at 40°C for 36 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 40°C for 48 h to obtain the final product, 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]).

[0085] The preparation method of the recyclable agent for treating oily sludge described in Example 5 is composed of the following steps: 5 g of [CMVIM][FeCl4] synthesized in Example 5 and 1 g of propylene glycol block polyether F68 are weighed respectively, added to 20 g of ethylene glycol, and mixed by hand for 7 min at room temperature to prepare an alcohol solution of a surfactant. 15 g of sodium acetate, 1.0 g of microbial flocculant mucopolysaccharide and 58.0 g of water are mixed, and mixed by hand for 7 min at room temperature to prepare an aqueous solution. The alcohol solution is added dropwise to the aqueous solution, and the mixture is ultrasonically mixed for 18 min to obtain a recyclable agent.

[0086] The application of the recyclable agent for treating oily sludge described in Example 5 is composed of the following steps: 13 mL of the recyclable agent is mixed with 2 g of oily sludge, stirred at 450 r / min for 50 min at 60°C, and centrifuged after standing for 30 hours. The crude oil removal rate is measured to be 97.50%. An N52 super-strong NdFeB magnet is applied to the middle layer water phase for 30 minutes to achieve the recycling of the ionic liquid in the middle water phase.

[0087] Example 6

[0088] The recyclable agent for treating oily sludge described in Example 6 is composed of the following raw materials, measured in mass percentage: 2% magnetically responsive ionic liquid, 6% non-ionic surfactant, 14% low molecular weight alcohol, 12% alkaline component, 0.6% flocculant, and the rest is water.

[0089] in:

[0090] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazole ferric chloride; the nonionic surfactant is propylene glycol block polyether L43 (Jiangsu Hai'an Petrochemical Plant); the low molecular weight alcohol is butanol; the alkaline component is sodium carbonate; and the flocculant is polyacrylamide.

[0091] The preparation method of 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]) described in Example 6 is composed of the following steps:

[0092] (1) Weigh N-vinylimidazole and chloroacetonitrile in a molar ratio of 1:2, and stir the mixture at 60°C for 36 hours. After the reaction is completed, place the product in a vacuum drying oven at 40°C for 40 hours to obtain a white solid product, 1-vinyl-3-cyanomethylimidazole chloride ([CMVIM]Cl).

[0093] (2) 0.1 mol of the white solid product [CMVIM]Cl prepared in step (1) was mixed with 0.15 mol of anhydrous FeCl3, and the mixture was stirred at 50°C and 300 r / min for 40 h under an Ar atmosphere. After the reaction was completed, a reddish brown viscous liquid was separated while hot and dried in a vacuum oven at 60°C for 48 h to obtain the final product, 1-vinyl-3-cyanomethylimidazole ferric chloride ([CMVIM][FeCl4]).

[0094] The preparation method of the recyclable agent for treating oily sludge described in Example 6 is composed of the following steps: 2 g of [CMVIM][FeCl4] synthesized in Example 6 and 6 g of nonionic surfactant propylene glycol block polyether L43 are weighed respectively, added to 14 g of butanol, and mixed by hand for 8 min at room temperature to prepare an alcohol solution of the surfactant. 12 g of sodium carbonate, 0.6 g of polyacrylamide and 65.4 g of water are mixed, and mixed by hand for 8 min at room temperature to prepare an aqueous solution. The alcohol solution is added dropwise to the aqueous solution, and the mixture is mixed evenly by ultrasonication for 20 min to obtain a recyclable agent.

[0095] The application of the recyclable agent for treating oily sludge described in Example 6 is composed of the following steps: 12 mL of the recyclable agent is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 350 r / min for 30 min, and centrifuged after standing for 30 hours. The crude oil removal rate is measured to be 97.34%. An N52 super-strong NdFeB magnet is applied to the intermediate aqueous phase for 30 minutes to achieve the recycling of the ionic liquid in the intermediate aqueous phase.

[0096] Comparative Example 1

[0097] The preparation method of the oily sludge treatment agent described in this comparative example 1 is the same as that of Example 1, and the only difference is that the raw material composition is different. The oily sludge treatment agent described in this comparative example 1 is composed of the following raw materials in terms of mass percentage: 3% nonionic surfactant, 10% low molecular weight alcohol, 8% alkaline component, 0.2% flocculant, and the rest is water.

[0098] in:

[0099] The nonionic surfactant is propylene glycol block polyether L44 (Jiangsu Haian Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium bicarbonate; and the flocculant is polyacrylamide.

[0100] The application of the agent for treating oily sludge described in this comparative example 1 consists of the following steps: 15 mL of the agent for treating oily sludge is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 350 r / min for 30 min, allowed to stand for 24 hours and then centrifuged, and the crude oil removal rate was measured to be 69.75%.

[0101] Comparative Example 2

[0102] The preparation method of the oily sludge treatment agent described in this comparative example 2 is the same as that of Example 1, and the only difference is that the raw material composition is different. The oily sludge treatment agent described in this comparative example 2 is composed of the following raw materials by mass percentage: 4% magnetic responsive ionic liquid, 10% low molecular weight alcohol, 8% alkaline component, 0.2% flocculant, and the rest is water.

[0103] in:

[0104] The magnetically responsive ionic liquid is 1-vinyl-3-cyanomethylimidazolium ferric bromide, and its preparation method is the same as that in Example 1; the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium bicarbonate; and the flocculant is polyacrylamide.

[0105] The application of the agent for treating oily sludge described in this comparative example 2 consists of the following steps: 15 mL of the agent for treating oily sludge is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 350 r / min for 30 min, allowed to stand for 24 hours and then centrifuged, and the crude oil removal rate was measured to be 75.33%.

[0106] Comparative Example 3

[0107] The preparation method of the oily sludge treatment agent described in this comparative example 3 is the same as that of Example 1, and the only difference is that the raw material composition is different. The oily sludge treatment agent described in this comparative example 3 is composed of the following raw materials in terms of mass percentage: 4% ionic liquid, 3% nonionic surfactant, 10% low molecular weight alcohol, 8% alkaline component, 0.2% flocculant, and the rest is water.

[0108] in:

[0109] The ionic liquid is 1-hexadecyl-3-methylimidazolium bromide; the nonionic surfactant is propylene glycol block polyether L44 (Jiangsu Haian Petrochemical Plant); the low molecular weight alcohol is ethylene glycol; the alkaline component is sodium bicarbonate; and the flocculant is polyacrylamide.

[0110] The application of the recoverable agent for treating oily sludge described in this comparative example 3 is composed of the following steps: 15 mL of the agent for treating oily sludge is mixed with 2 g of oily sludge, stirred at 70°C at a speed of 350 r / min for 30 min, and centrifuged after standing for 24 hours, and the crude oil removal rate is measured to be 82.64%. The magnetic field is applied for 30 minutes, and the ionic liquid cannot be recycled.

[0111] By comparing Example 1 with Comparative Examples 1-3, it can be seen that the recyclable agent for treating oily sludge prepared in Examples 1-3 has a much better removal rate for oily sludge than Comparative Examples 1-3. In Comparative Example 1, magnetically responsive ionic liquid was not used, and the micelles obtained by using a non-ionic surfactant alone had a low solubilizing ability for crude oil in oily sludge, resulting in a low crude oil removal rate. In Comparative Example 2, since a non-ionic surfactant was not used, the micelles formed by using a magnetically responsive ionic liquid alone were small and had poor stability, so the crude oil removal rate decreased. In Comparative Example 3, 1-hexadecyl-3-methylimidazolium bromide was used instead of the magnetically responsive ionic liquid synthesized by the present invention. Due to the lack of vinyl and magnetic components, the π-π interaction between the agent and the crude oil component in the oily sludge decreased, so the oil removal rate of the agent decreased to a certain extent, and the recycling of the ionic liquid could not be achieved.

Claims

1. A recyclable agent for treating oily sludge, characterized in that: The invention is composed of the following raw materials in terms of mass percentage: 2-5% magnetic responsive ionic liquid, 1-6% nonionic surfactant, 10-20% low molecular weight alcohol, 8-15% alkaline component, 0.2-1.0% flocculant, and the rest is water; wherein the magnetic responsive ionic liquid is one of 1-vinyl-3-cyanomethylimidazole ferric bromide or 1-vinyl-3-cyanomethylimidazole ferric chloride, and the preparation method thereof is composed of the following steps: (1) Weighing N-vinylimidazole and one of bromoacetonitrile or chloroacetonitrile and mixing them at a constant temperature with stirring, and after the reaction is completed, placing the product in a vacuum drying oven for drying to obtain a white solid product, 1-vinyl-3-cyanomethylimidazole bromide or 1-vinyl-3-cyanomethylimidazole chloride; (2) reacting one of 1-vinyl-3-cyanomethylimidazole bromide or 1-vinyl-3-cyanomethylimidazole chloride with anhydrous FeCl3 under an Ar atmosphere by stirring, separating while hot after the reaction is completed to obtain a reddish brown viscous liquid, which is then dried to prepare 1-vinyl-3-cyanomethylimidazole ferric bromide or 1-vinyl-3-cyanomethylimidazole ferric chloride; in: In step (1), the molar ratio of N-vinylimidazole to bromoacetonitrile or chloroacetonitrile is 1:1-1:2; In step (1), the temperature of constant temperature stirring and mixing is 60-80°C, the stirring and mixing time is 24-36 hours, the drying temperature is 30-50°C, and the drying time is 36-48 hours; In step (2), the molar ratio of one of 1-vinyl-3-cyanomethylimidazolium bromide or 1-vinyl-3-cyanomethylimidazolium chloride to anhydrous FeCl3 is 1:1-1:1.5; In step (2), the stirring reaction temperature is 30-50°C, the stirring reaction speed is 300-500r / min, and the stirring reaction time is 24-48h; In step (2), the drying temperature is 40-60°C and the drying time is 48-64h; The nonionic surfactant is one of propylene glycol block polyether L43, propylene glycol block polyether L44, propylene glycol block polyether L64, propylene glycol block polyether L65 or propylene glycol block polyether F68 nonionic surfactants.

2. The recyclable agent for treating oily sludge according to claim 1, characterized in that: The low molecular weight alcohol is one of ethanol, ethylene glycol, propylene glycol or butanol.

3. The recyclable agent for treating oily sludge according to claim 1, characterized in that: The alkaline component is one of sodium carbonate, sodium bicarbonate or sodium acetate; The flocculant is one of polyaluminium chloride, polyacrylamide, polyaluminium sulfate or microbial flocculant mucopolysaccharide.

4. A method for preparing a recoverable agent for treating oily sludge according to claim 1, characterized in that: It consists of the following steps: ① Add the magnetically responsive ionic liquid and the non-ionic surfactant to the low molecular weight alcohol and mix them evenly by hand shaking to obtain an alcohol solution; ② Add the flocculant and alkaline component to water in sequence and mix them evenly by hand shaking to obtain an aqueous solution; ③ Add the alcohol solution prepared in step ① dropwise into the aqueous solution prepared in step ② for ultrasonic treatment, and mix evenly to prepare a recyclable agent for treating oily sludge.

5. The method for preparing a recoverable agent for treating oily sludge according to claim 4, characterized in that: In step ①, the mixing temperature is room temperature and the mixing time is 3-8 minutes; In step ②, the mixing temperature is room temperature and the mixing time is 3-8 minutes; The ultrasonic treatment time in step ③ is 10-20 min.

6. An application of the recoverable agent for treating oily sludge according to claim 1, characterized in that: The recyclable agent for treating oily sludge is mixed with the oily sludge, heated and stirred, then allowed to stand for 24-36 hours, and finally centrifuged to separate the oily sludge into muddy and sandy solids. An N52 ultra-strong NdFeB magnet is applied to the middle layer of the water phase to direct the magnetically responsive ionic liquid in the system and remove it from the middle layer of the water phase, thereby realizing the recovery of the magnetically responsive ionic liquid.

7. The use of the recoverable agent for treating oily sludge according to claim 6, characterized in that: The volume mass ratio of the recoverable reagent for treating oily sludge to the oily sludge is 10:2-15:2, expressed in mL / g.

8. The use of the recoverable agent for treating oily sludge according to claim 6, characterized in that: The heating and stirring temperature is 60°C-70°C, the heating and stirring speed is 350-500 r / min, the heating and stirring time is 30-50min, and the magnetic field application time is 10-30 min.

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