Magnetic response type Pickering emulsifier as well as preparation method and application thereof

Abstract

The invention relates to a magnetic response type Pickering emulsifier as well as a preparation method and application thereof, the emulsifier is a magnetic response type Pickering emulsifier, and by adopting nano-particles, high-viscosity tar obtained after acrylic acid is deeply cracked can reach a phase inversion point by using a very small amount of water; and the tar can still keep a low-viscosity state at normal temperature and can be conveyed through a pipeline or a tank car. And by using the nanoparticles, the emulsion can be kept in an emulsified state for a long time at high temperature, and the storage time is prolonged. After conveying is completed, a magnetic field can be applied to pickering emulsion of high-viscosity tar for rapid demulsification, and the high-viscosity tar can be reused. And the oil phase can be incinerated to produce steam for refining acrylic acid.

Description

Technical Field

[0001] The present invention relates to a magnetic-responsive Pickering emulsifier, a preparation method thereof, and an application thereof, which are applicable to the acrylic recombination cracking recovery process. Background Art

[0002] Acrylic acid is an unsaturated fatty acid and an important organic chemical raw material. Acrylic acid and its ester products have very wide applications, mainly involving industries such as textiles, coatings, adhesives, chemical fibers, papermaking, and leather. The most extensive application of acrylic acid currently is the production of thickeners, superabsorbent polymers, flocculants, washing aids, etc. Industrially, the most important role of acrylic acid is to synthesize acrylic esters, such as butyl acrylate, methyl acrylate, ethyl acrylate, etc. Acrylic ester products are mainly applied in fields such as coatings, plastic modification aids, and rubber. In short, acrylic acid and its esters have a wide application range and large demand, and are an important part of the current petrochemical industry.

[0003] The amount of tar (heavy components) per ton of product is the key to determining the propylene unit consumption of acrylic acid. The acrylic acid industry generally adds a recombination cracker to crack and recover the acrylic acid heavy components. However, due to limited recombination cracking technology, the tar ratio in the industry is generally 40 kg / t, and a large amount of recoverable acrylic acid still remains in the discharged heavy components, resulting in serious waste of raw materials. The key factor restricting the recovery of acrylic acid heavy components is that after continuing to reduce the tar ratio, the viscosity of the heavy components is too high and cannot be transported through low-temperature pipelines.

[0004] Chinese Patent Publication No. CN102173990 discloses a method that uses high-temperature cracking and atmospheric distillation to treat acrylic acid heavy components, but this method has a low recovery rate, and a large amount of recoverable acrylic acid remains in the discharged heavy components.

[0005] Chinese Patent Publication No. CN1140162A discloses a method for thermally cracking and recovering acrylic acid from acrylic acid heavy components without a catalyst. This high-temperature cracking method results in too high viscosity of the cracking products to be transported by pipeline. At the same time, the too high viscosity causes insoluble tar to precipitate, resulting in fouling on the wall of the cracking reactor and reducing the cracking yield.

[0006] Chinese Patent Publication No. CN102516061A uses vacuum distillation to deeply crack acrylic acid heavy components and then uses a screw extruder to process the residual heavy components, which requires high equipment material quality.

[0007] Therefore, it is necessary to seek a treatment method for acrylic acid heavy components after deep cracking to solve the above technical problems restricting the further cracking of acrylic acid heavy components. Summary of the Invention

[0008] The object of the present invention is to provide a method for treating acrylic heavy component cracked tar, which can further crack the acrylic heavy component to recover acrylic acid. The emulsifier of the present invention can emulsify the highly viscous tar after the deep cracking of the acrylic heavy component in water, so that the tar remains in a low-viscosity state at room temperature and can be transported through pipelines or by tanker trucks. At the same time, the emulsion can maintain the emulsified state at high temperature for a long time, extend the storage time, and reduce the polymerization risk.

[0009] To achieve the above object, the technical solution of the present invention is as follows:

[0010] On the one hand, the present invention provides a magnetic-responsive Pickering emulsifier, which is prepared from the following raw materials in parts by weight: magnetic nano Fe 3 O 4 5 - 10 parts, hard monomer 50 - 80 parts, acrylate 35 - 75 parts, composite emulsifier 3 - 7 parts, composite silicone 0 - 8 parts, buffer reagent 0.2 - 0.6 parts, initiator 0.2 - 1.2 parts, isopropanol 0.2 - 0.6 parts, surface activity modifier 0 - 10 parts, deionized water 185 - 320 parts.

[0011] The hard monomer is one or more combinations of styrene and α-methylstyrene in any molar ratio.

[0012] The acrylate is one or more combinations of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, and 2-ethylhexyl acrylate in any molar ratio.

[0013] The composite emulsifier is composed of a non-ionic surfactant and an anionic surfactant.

[0014] The non-ionic emulsifier is one of alkylphenol polyoxyethylene ethers, polysorbates, and alkyl polyglycosides, and the anionic emulsifier is one of sodium dodecyl cashew phenol polyoxyethylene ether sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and sodium dodecyl sulfonate.

[0015] The composite silicone is composed of γ-glycidoxypropyltrimethoxysilane and α,ω-dihydroxy-terminated polydimethylsiloxane, and the mass ratio of the two is 1:2 - 1:5.

[0016] The buffer reagent is selected from one or two of acrylic acid and sodium acrylate.

[0017] The initiator is one or more combinations of potassium persulfate and azobisisobutyronitrile in any molar ratio.

[0018] The surface active modifier is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and hexanediol diacrylate in any molar ratio combination.

[0019] The particle size of the magnetic-responsive Pickering emulsifier is 50 - 200 nm.

[0020] The solid content of the emulsifier is 20 - 90 wt%.

[0021] On the other hand, the present invention provides a method for preparing a magnetic-responsive Pickering emulsifier, and the steps include:

[0022] (1) Add magnetic nano-Fe 3 O 4 to deionized water, uniformly disperse it to form suspension A; add the hard monomer to deionized water, add the composite emulsifier to obtain pre-emulsion B; add potassium persulfate to deionized water to dissolve it to obtain initiator solution C; add the buffer reagent to deionized water to obtain buffer solution D; add the acrylate to deionized water, add the composite emulsifier to obtain pre-emulsion E;

[0023] (2) Under the protection of inert gas, heat suspension A, pre-emulsion B, part of pre-emulsion E, and part of buffer solution D, and add part of initiator solution C to obtain emulsion F;

[0024] (3) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and part of initiator solution C to emulsion F, and keep warm to obtain emulsion G;

[0025] (4) Dropwise add the composite silicone, the surface active modifier, and the remaining initiator solution C to emulsion G, keep warm to obtain emulsion H;

[0026] (5) Keep emulsion H warm and adjust the solid content of the emulsion; cool emulsion H to room temperature and adjust the pH to 7 - 8 to obtain the magnetic-responsive Pickering emulsifier.

[0027] In the present invention, in step (1), the weight portion of magnetic nano-Fe 3 O 4 is 5 - 10 parts by weight, and the weight portion of deionized water is 25 - 50 parts by weight.

[0028] In the present invention, in step (1), the weight portion of the hard monomer is 50 - 80 parts by weight, and the weight portion of deionized water is 50 - 100 parts by weight.

[0029] In the present invention, in step (1), the weight portion of the initiator is 0.2 - 1.2 parts by weight, and the weight portion of deionized water is 10 - 20 parts by weight.

[0030] In the present invention, in the step (1), the buffer reagent is 0.2 to 0.6 parts by weight, and the deionized water is 35 to 75 parts by weight.

[0031] In the present invention, in the step (1), the buffer reagent is composed of 0.1 to 0.3 parts by weight of acrylic acid and 0.1 to 0.3 parts by weight of sodium acrylate.

[0032] In the present invention, in the step (1), the acrylate is 35 to 75 parts by weight, the deionized water is 50 to 100 parts by weight, and the composite emulsifier is 3 to 7 parts by weight.

[0033] In the present invention, in the step (1), the composite emulsifier is composed of 1.5 to 4 parts by weight of non-ionic surfactant and 1.5 to 4 parts by weight of anionic surfactant.

[0034] In the present invention, in the step (2), the heating temperature is 70 - 85 °C, and the reaction time is 30 - 90 min.

[0035] In the present invention, in the step (2), the addition amount of part of the initiator solution C is 1 / 2 part by weight of the initiator solution C, the addition amount of part of the pre-emulsion E is 1 / 3 part by weight of the pre-emulsion E, and the addition amount of part of the buffer solution D is 1 / 2 part by weight of the buffer solution D.

[0036] In the present invention, in the step (3), the addition amount of part of the initiator solution C is 1 / 3 part by weight of the initiator solution C, and the dropping time of the remaining pre-emulsion E, the remaining buffer solution D and part of the initiator solution C is 0.5 - 2 h; the insulation temperature is 70 - 85 °C, and the insulation time is 1 - 3 h.

[0037] In the present invention, in the step (4), the composite silicone is 0 - 8 parts by weight, and the surface active modifier is 0 - 10 parts by weight.

[0038] In the present invention, in the step (4), the composite silicone is composed of 0 - 4 parts by weight of γ-glycidoxypropyltrimethoxysilane and 0 - 4 parts by weight of α,ω-dihydroxy-terminated polydimethylsiloxane.

[0039] In the present invention, in the step (4), the addition amount of part of the initiator solution C is 1 / 5 part by weight of the initiator solution C, and the insulation temperature after dropping the composite silicone, the surface active modifier and the remaining initiator solution C is 70 - 85 °C, and the insulation time is 1 - 2 h.

[0040] In the present invention, in the step (5), the insulation temperature is 55 - 65 °C, and the insulation time is 1 - 8 h; in the pH adjustment process, the pH regulator is preferably a base, and more preferably ammonia water.

[0041] Thirdly, the present invention also provides an application of the magnetic-responsive Pickering emulsifier prepared by the above method in the treatment of deeply cracked tar of acrylic heavy components.

[0042] Finally, the present invention provides a method for treating highly viscous tar after deep cracking of acrylic heavy components, comprising the following steps:

[0043] (1) Adding the magnetic-responsive Pickering emulsifier to the highly viscous tar after deep cracking of acrylic heavy components to make the magnetic-responsive Pickering emulsifier and the tar mix evenly;

[0044] (2) Adding water to the highly viscous tar for emulsification under high-speed stirring conditions, and stopping adding water when the emulsion completes the phase inversion;

[0045] (3) Transporting the acrylic tar emulsion to the incineration unit at normal temperature.

[0046] By applying an external magnetic field, the tar emulsion is quickly demulsified, the oil and water are separated, the magnetic-responsive Pickering emulsifier is dispersed in the water phase and discharged together, and the oil phase remains in the incineration unit for incineration treatment; the discharged water phase is simply distilled to recover the emulsifier for reuse.

[0047] In the present invention, the weight portion of the highly viscous tar added in step (1) is 100 parts, and the weight portion of the magnetic-responsive Pickering emulsifier is 5 - 10 parts;

[0048] In the present invention, the emulsification temperature in step (2) is 50 - 70 °C.

[0049] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0050] (1) The present invention dilutes the deeply cracked tar of acrylic heavy components, avoiding blockage of the conveying pipelines and equipment caused by the too high viscosity of the tar after deep cracking.

[0051] (2) The present invention uses water to dilute the deeply cracked tar of acrylic heavy components and transports it to the incineration unit, avoiding the use of organic solvents, reducing the content of VOCs in the incineration tail gas, and reducing the difficulty of tail gas treatment.

[0052] (3) The present invention uses a modified Pickering emulsifier to emulsify the deeply cracked tar of acrylic heavy components, which can reduce the amount of water required for the highly viscous tar after deep cracking of acrylic to reach the phase inversion point, and at the same time keep the tar in a low-viscosity state at normal temperature, enabling it to be transported through pipelines or by tanker trucks.

[0053] (4) The modified Pickering emulsifier used in the present invention can keep the emulsion in an emulsified state at high temperatures for a long time, extending the storage time. Compared with traditional emulsifiers, the Pickering emulsifier has a lower cost, and compared with surfactants, it causes less environmental pollution; the solid particles can be recovered and reused after the emulsion demulsifies; the Pickering emulsion has good stability, especially maintaining high stability in some relatively harsh environments.

[0054] (5) In the present invention, the Pickering emulsifier is a magnetic-responsive emulsifier, which can be quickly demulsified under the action of an external magnetic field, enabling the water and the emulsifier to be recovered separately and reused.

[0055] (6) In the present invention, the Pickering emulsifier is chemically modified to have better affinity for the acrylic heavy fraction deep cracking tar system, enhancing the emulsification effect, reducing the amount of emulsifier required to meet the transportation standard, reducing the amount of water added required for phase inversion, and reducing water resource consumption. Description of the Drawings

[0056] The specification drawings forming a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation of this application.

[0057] Figure 1 are the TEM pictures of the Pickering emulsifiers prepared in Example 1 (a) and Example 2 (b);

[0058] Figures 2-6 are the infrared spectra of the Pickering emulsifiers prepared in Examples 1-5;

[0059] Figure 7 is the particle size distribution diagram of the Pickering emulsifiers prepared in Examples 1-5;

[0060] Figure 8 is the particle size distribution diagram of the Pickering emulsifiers prepared in Example 1 and Comparative Examples 1-4;

[0061] Figure 9 is the particle size distribution diagram of the acrylic heavy fraction deep cracking tar emulsions prepared in Examples 1-5;

[0062] Figure 10 is the particle size distribution diagram of the acrylic heavy fraction deep cracking tar emulsions prepared in Example 1 and Comparative Examples 1-4. Detailed Embodiments

[0063] The present invention will be further described below through specific embodiments and accompanying drawings. The embodiments described in the present invention are only for the purpose of illustrating the present invention and do not limit the scope of the present invention.

[0064] All the reagents used in the embodiments are commercially available chemical reagents. The acrylic heavy components are taken from the acrylic acid production unit of Wanhua Chemical Group Co., Ltd. By mass content, the composition of the acrylic acid by-product heavy components is 17% acrylic acid, 55% acrylic acid dimer, 5% acetic acid, 9% maleic anhydride, 1% furfural, 4% benzaldehyde, 5% crotonic acid, 1% p-methoxyphenol, 1% hydroquinone, 1% copper dibutyldithiocarbamate, and 1% diphenylamine sulfide.

[0065] The analysis method adopts the area normalization method of gas chromatography. Chromatographic column: HP-5 (30m×0.32mm×0.25μm), injection port temperature 280°C, injection volume: 0.2μL, split ratio: 20:1, column temperature: hold at 50°C for 2 min, increase the temperature to 80°C at a rate of 5°C / min and hold for 5 min, then increase the temperature to 280°C at a rate of 15°C and hold for 10 min. Carrier gas (N2) flow rate: 2 mL / min (constant flow rate); FID detector temperature: 280°C, air flow rate: 400 mL / min, hydrogen gas fuel flow rate: 30 mL / min.

[0066] Example 1

[0067] Preparation of Pickering emulsifier:

[0068] (1) Add 5 g of magnetic nano-Fe 3 O 4 to 25 g of deionized water, stir for 10 min under the action of ultrasonic waves at 40000 Hz, and disperse it evenly to obtain suspension A;

[0069] (2) Add 50 g of styrene to 50 g of deionized water, add 0.75 g of dodecyl glucoside emulsifier and 0.75 g of sodium dodecyl cashew phenol polyoxyethylene ether sulfonate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40000 Hz to obtain pre-emulsion B;

[0070] (3) Add 0.2 g of potassium persulfate to 10 g of deionized water to obtain initiator solution C;

[0071] (4) Add 0.6 g of acrylic acid as a buffer reagent to 50 g of deionized water to obtain buffer solution D;

[0072] (5) Add 35 g of 2-ethylhexyl acrylate to 50 g of deionized water, add 0.75 g of dodecyl glucoside emulsifier and 0.75 g of sodium dodecyl cashew phenol polyoxyethylene ether sulfonate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40000 Hz to obtain pre-emulsion E;

[0073] (6) Under the protection of inert gas, heat suspension A, pre-emulsion B, 1 / 3 of pre-emulsion E, and 1 / 2 of buffer solution D to 70 °C, add 1 / 5 of initiator solution C, and react for 30 min to obtain emulsion F;

[0074] (7) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and 3 / 5 of initiator solution C to emulsion F, finish dropping within 0.5 h, and keep warm at 70 °C for 1 h to obtain emulsion G;

[0075] (8) Dropwise add 3 g of α,ω-dihydroxy-terminated polydimethylsiloxane, 1 g of γ-glycidoxypropyltrimethoxysilane, 10 g of 2-hydroxyethyl acrylate, and the remaining initiator solution C to emulsion G, and keep warm at 70 °C for 1 h to obtain emulsion H;

[0076] (9) Store emulsion H at 55 °C for 1 h, and adjust the solid content of the emulsion to 50 - 75%;

[0077] (10) Cool emulsion H to room temperature, dropwise add ammonia water to adjust the pH to 7 - 8 to obtain a magnetic-responsive Pickering emulsifier.

[0078] Preparation of emulsion:

[0079] Take 50 g of acrylic heavy fraction deep cracking tar, and add 5 g of the above Pickering emulsifier (calculated based on the solid content);

[0080] At 70 °C and a stirring speed of 500 r / min, disperse the emulsifier and tar evenly at a low speed, and continue to keep warm and stir for 30 min until the water is completely volatilized.

[0081] Increase the motor speed to 2000 r / min, slowly add deionized water, and stop adding water when the added water mass accounts for 40% of the resin mass;

[0082] Stir well for 3 min, and continue to add deionized water after the emulsion is uniform to obtain a uniform acrylic heavy fraction deep cracking tar emulsion.

[0083] Apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure that the recovery rate of the Pickering emulsifier in the water phase is 77.4%.

[0084] Example 2

[0085] Preparation of Pickering emulsifier:

[0086] (1) Add 10 g of magnetic nano-Fe 3 O 4Add it to 50 g of deionized water, stir for 10 min under the action of ultrasonic waves at 40,000 Hz, and disperse it evenly to obtain suspension A;

[0087] (2) Add 60 g of styrene to 70 g of deionized water, add 1 g of dodecylphenol polyoxyethylene ether emulsifier and 1 g of sodium dodecyl sulfate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40,000 Hz to obtain pre-emulsion B;

[0088] (3) Add 0.4 g of potassium persulfate to 12 g of deionized water to obtain initiator solution C;

[0089] (4) Add 0.4 g of acrylic acid as a buffer reagent to 50 g of deionized water to obtain buffer solution D;

[0090] (5) Add 45 g of butyl acrylate to 70 g of deionized water, add 1 g of dodecylphenol polyoxyethylene ether emulsifier and 1 g of sodium dodecyl sulfate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40,000 Hz to obtain pre-emulsion E;

[0091] (6) Under the protection of inert gas, heat suspension A, pre-emulsion B, 1 / 3 of pre-emulsion E, and 1 / 2 of buffer solution D to 75 °C, add 1 / 5 of initiator solution C, and react for 60 min to obtain emulsion F;

[0092] (7) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and 3 / 5 of initiator solution C to emulsion F, finish dropping within 1 hour, and keep warm at 80 °C for 2 h to obtain emulsion G;

[0093] (8) Dropwise add 3 g of α,ω-dihydroxy-terminated polydimethylsiloxane, 1 g of γ-glycidoxypropyltrimethoxysilane, 10 g of hydroxypropyl acrylate, and the remaining initiator solution C to emulsion G, and keep warm at 75 °C for 1.5 h to obtain emulsion H;

[0094] (9) Store emulsion H at 60 °C for 4 h and adjust the solid content of the emulsion to 50-75%;

[0095] (10) Cool emulsion H to room temperature, dropwise add ammonia water to adjust the pH to 7-8 to obtain a magnetic-responsive Pickering emulsifier.

[0096] Preparation of emulsion:

[0097] Take 50 g of acrylic heavy fraction deep cracking tar and add 5 g of the above Pickering emulsifier (calculated based on the solid content);

[0098] At 70 °C and a stirring speed of 500 r / min, disperse the emulsifier and tar evenly at a low speed, and continue to keep warm and stir for 30 min until the water is completely volatilized.

[0099] Adjust the motor speed to 2000 r / min, slowly add deionized water, and stop adding water when the added water mass accounts for 40% of the resin mass;

[0100] Stir well for 3 min. After the emulsion is uniform, continue to add deionized water to obtain a uniform acrylic heavy component deep cracking tar emulsion.

[0101] Apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir. The emulsion quickly demulsifies and phases separate. Separate the two phases and measure the recovery rate of the Pickering emulsifier in the aqueous phase to be 76.52%.

[0102] Example 3

[0103] Preparation of Pickering emulsifier:

[0104] (1) Add 8 g of magnetic nano-Fe 3 O 4 to 40 g of deionized water, stir for 10 min under the action of ultrasonic waves at 40000 Hz to disperse it evenly, and obtain suspension A;

[0105] (2) Add 70 g of α-methylstyrene to 90 g of deionized water, add 1.5 g of polysorbate 80 emulsifier and 1.5 g of sodium dodecylbenzenesulfonate, and stir for 10 min under the action of ultrasonic waves at 40000 Hz to obtain pre-emulsion B;

[0106] (3) Add 0.8 g of potassium persulfate to 12 g of deionized water to obtain initiator solution C;

[0107] (4) Add 0.2 g of acrylic acid as a buffer reagent to 50 g of deionized water to obtain buffer solution D;

[0108] (5) Add 55 g of ethyl acrylate to 90 g of deionized water, add 1.5 g of dodecyl glucoside emulsifier and 1.5 g of sodium dodecyl cashew phenol polyoxyethylene ether sulfonate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40000 Hz to obtain pre-emulsion E;

[0109] (6) Under the protection of inert gas, heat suspension A, pre-emulsion B, 1 / 3 of pre-emulsion E, and 1 / 2 of buffer solution D to 80 °C, add 1 / 5 of initiator solution C, and react for 90 min to obtain emulsion F;

[0110] (7) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and 3 / 5 of initiator solution C to emulsion F within 2 hours, keep it warm at 85 °C for 3 h to obtain emulsion G;

[0111] (8) 3 g of α,ω-dihydroxy-terminated polydimethylsiloxane, 1 g of γ-glycidoxypropyltrimethoxysilane, 10 g of 2-hydroxyethyl methacrylate and the remaining initiator solution C were added dropwise to emulsion G, and the mixture was kept at 80 °C for 2 h to obtain emulsion H;

[0112] (9) Emulsion H was stored at 65 °C for 8 h, and the solid content of the emulsion was adjusted to 50 - 75%;

[0113] (10) Emulsion H was cooled to room temperature, and ammonia water was added dropwise to adjust the pH to 7 - 8 to obtain a magnetoresponsive Pickering emulsifier.

[0114] Preparation of emulsion:

[0115] 50 g of acrylic heavy fraction deep cracking tar was taken, and 5 g of the above Pickering emulsifier (calculated based on the solid content) was added;

[0116] At 70 °C and a stirring speed of 500 r / min, the emulsifier and tar were evenly dispersed by low-speed dispersion, and stirring was continued while keeping warm for 30 min until the water was completely volatilized.

[0117] The motor speed was increased to 2000 r / min, and deionized water was slowly added. When the added water mass accounted for 40% of the resin mass, the addition of water was stopped;

[0118] After stirring thoroughly for 3 min, deionized water was continuously added after the emulsion became uniform, and a uniform acrylic heavy fraction deep cracking tar emulsion could be obtained.

[0119] An external magnetic field of 1430 - 1480 mT was applied to the emulsion and stirred. The emulsion quickly demulsified and phase-separated, and the two phases were separated. The recovery rate of the Pickering emulsifier in the aqueous phase was measured to be 71.43%.

[0120] Example 4

[0121] Preparation of Pickering emulsifier:

[0122] (1) 5 g of magnetic nano-Fe 3 O 4 was added to 25 g of deionized water, and the mixture was stirred for 10 min under ultrasonic wave action at 40000 Hz to uniformly disperse it to obtain suspension A;

[0123] (2) 50 g of styrene was added to 50 g of deionized water, 1 g of dodecyl glucoside emulsifier and 1 g of sodium dodecyl sulfonate emulsifier were added, and the mixture was stirred for 10 min under ultrasonic wave action at 40000 Hz to obtain pre-emulsion B;

[0124] (3) 1.2 g of potassium persulfate was added to 20 g of deionized water to obtain initiator solution C;

[0125] (4) Add 0.6 g of acrylic acid as a buffer reagent to 50 g of deionized water to obtain buffer solution D;

[0126] (5) Add 65 g of isobornyl acrylate to 100 g of deionized water, add 1 g of dodecyl glucoside emulsifier and 1 g of sodium dodecyl sulfonate emulsifier, and under the action of 40000 Hz ultrasonic wave and stir for 10 min to obtain pre-emulsion E;

[0127] (6) Under the protection of inert gas, heat suspension A, pre-emulsion B, 1 / 3 of pre-emulsion E, and 1 / 2 of buffer solution D to 85 °C, add 1 / 5 of initiator solution C, and react for 60 min to obtain emulsion F;

[0128] (7) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and 3 / 5 of initiator solution C to emulsion F, finish dropping within 0.5 h, and keep warm at 70 °C for 1 h to obtain emulsion G;

[0129] (8) Dropwise add 3 g of α,ω-dihydroxy-terminated polydimethylsiloxane, 1 g of γ-glycidoxypropyltrimethoxysilane, 5 g of 2-hydroxyethyl acrylate, and the remaining initiator solution C to emulsion G, and keep warm at 85 °C for 1 h to obtain emulsion H;

[0130] (9) Store emulsion H at 55 °C for 8 h, and adjust the solid content of the emulsion to 50 - 75%;

[0131] (10) Cool emulsion H to room temperature, dropwise add ammonia water to adjust the pH to 7 - 8 to obtain a magnetic-responsive Pickering emulsifier.

[0132] Preparation of emulsion:

[0133] Take 50 g of acrylic acid heavy fraction deep cracking tar, and add 3 g of the above-mentioned Pickering emulsifier (calculated based on the solid content);

[0134] At 60 °C and a stirring speed of 500 r / min, disperse the emulsifier and tar evenly at a low speed, and continue to keep warm and stir for 30 min until the water is completely volatilized.

[0135] Increase the motor speed to 2000 r / min, slowly add deionized water, and stop adding water when the added water mass accounts for 40% of the resin mass;

[0136] Stir thoroughly for 3 min, and continue to add deionized water after the emulsion is uniform to obtain a uniform acrylic acid heavy fraction deep cracking tar emulsion.

[0137] Apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure that the recovery rate of the Pickering emulsifier in the water phase is 73.41%.

[0138] Example 5

[0139] Preparation of Pickering emulsifier:

[0140] (1) Add 5 g of magnetic nano-Fe 3 O 4 to 25 g of deionized water, stir for 10 min under the action of ultrasonic waves at 40,000 Hz to disperse it evenly, and obtain suspension A;

[0141] (2) Add 50 g of styrene to 100 g of deionized water, add 1 g of dodecyl glucoside emulsifier and 1 g of dialkyl cardanol polyoxyethylene ether sulfonate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40,000 Hz to obtain pre-emulsion B;

[0142] (3) Add 1.2 g of azobisisobutyronitrile to 20 g of deionized water to obtain initiator solution C;

[0143] (4) Add 0.6 g of acrylic acid as a buffer reagent to 50 g of deionized water to obtain buffer solution D;

[0144] (5) Add 75 g of 2-ethylhexyl acrylate to 100 g of deionized water, add 1 g of dodecyl glucoside emulsifier and 1 g of dialkyl cardanol polyoxyethylene ether sulfonate emulsifier, and stir for 10 min under the action of ultrasonic waves at 40,000 Hz to obtain pre-emulsion E;

[0145] (6) Under the protection of inert gas, heat suspension A, pre-emulsion B, 1 / 3 of pre-emulsion E, and 1 / 2 of buffer solution D to 85 °C, add 1 / 5 of initiator solution C, and react for 60 min to obtain emulsion F;

[0146] (7) Dropwise add the remaining pre-emulsion E, the remaining buffer solution D, and 3 / 5 of initiator solution C to emulsion F, finish dropping within 0.5 h, and keep warm at 70 °C for 1 h to obtain emulsion G;

[0147] (8) Dropwise add 3 g of α,ω-dihydroxy-terminated polydimethylsiloxane, 1 g of γ-glycidoxypropyltrimethoxysilane, 5 g of 2-hydroxyethyl acrylate, and the remaining initiator solution C to emulsion G, and keep warm at 75 °C for 1 h to obtain emulsion H;

[0148] (9) Store emulsion H at 55 °C for 8 h and adjust the solid content of the emulsion to 50-75%;

[0149] (10) Cool emulsion H to room temperature, dropwise add ammonia water to adjust the pH to 7-8 to obtain a magnetoresponsive Pickering emulsifier.

[0150] Preparation of emulsion:

[0151] Take 50 g of the deeply cracked tar of acrylic heavy components and add 2.5 g of the above Pickering emulsifier (calculated based on the solid content).

[0152] At 50 °C and a stirring speed of 500 r / min, disperse the emulsifier and tar evenly at a low speed, and continue to stir while maintaining the temperature for 30 min until the water is completely evaporated.

[0153] Adjust the motor speed to 2000 r / min, and slowly add deionized water. Stop adding water when the mass of the added water accounts for 40% of the resin mass.

[0154] Stir well for 3 min. After the emulsion is uniform, continue to add deionized water to obtain a uniform emulsion of deeply cracked tar of acrylic heavy components.

[0155] Apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure the recovery rate of the Pickering emulsifier in the aqueous phase to be 70.24%.

[0156] Comparative Example 1

[0157] Preparation of the emulsion:

[0158] Take 50 g of the deeply cracked tar of acrylic heavy components and add 5 g of Solvay N1631 cationic tar emulsifier (calculated based on the solid content).

[0159] At 70 °C and a stirring speed of 500 r / min, disperse the emulsifier and tar evenly at a low speed, and continue to stir while maintaining the temperature for 30 min until the water is completely evaporated.

[0160] Adjust the motor speed to 2000 r / min, and slowly add deionized water. Stop adding water when the mass of the added water accounts for 40% of the resin mass.

[0161] Stir well for 3 min. After the emulsion is uniform, continue to add deionized water to obtain a uniform emulsion of deeply cracked tar of acrylic heavy components. Analyze the properties of the emulsion.

[0162] Let the emulsion of deeply cracked tar of acrylic heavy components stand until the emulsion demulsifies and phases separate. Separate the two phases, and measure the recovery rate of the emulsifier in the aqueous phase to be 35.41%.

[0163] Comparative Example 2

[0164] Refer to the method of Example 1 to prepare the Pickering emulsifier. Replace the 2-ethylhexyl acrylate in step (5) with styrene, and keep other conditions the same to prepare the Pickering emulsifier.

[0165] Refer to the method of Example 1 to prepare the deep cracking tar emulsion of acrylic heavy components, and analyze the performance of the emulsion.

[0166] Refer to the method of Example 1 to apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir it. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure that the recovery rate of the Pickering emulsifier in the aqueous phase is 80.6%.

[0167] Comparative Example 3

[0168] Refer to the method of Example 1 to prepare the Pickering emulsifier. Replace the isooctyl acrylate in step (5) with diethyl fumarate, and keep other conditions the same to obtain the Pickering emulsifier.

[0169] Refer to the method of Example 1 to prepare the deep cracking tar emulsion of acrylic heavy components, and analyze the performance of the emulsion.

[0170] Refer to the method of Example 1 to apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir it. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure that the recovery rate of the Pickering emulsifier in the aqueous phase is 79.3%.

[0171] Comparative Example 4

[0172] Refer to the method of Example 1 to prepare the Pickering emulsifier. Replace the 2-hydroxyethyl acrylate in step (8) with styrene, and keep other conditions the same to obtain the Pickering emulsifier.

[0173] Refer to the method of Example 1 to prepare the deep cracking tar emulsion of acrylic heavy components, and analyze the performance of the emulsion.

[0174] Refer to the method of Example 1 to apply an external magnetic field of 1430 - 1480 mT to the emulsion and stir it. The emulsion quickly demulsifies and phases separate. Separate the two phases, and measure that the recovery rate of the Pickering emulsifier in the aqueous phase is 65.9%.

[0175] Table 1: Multiple performance detection table of the examples and comparative examples of the present invention

[0176]

Claims

1. A magnetic-responsive Pickering emulsifier is prepared from the following raw materials in parts by weight: magnetic nano-Fe 3 O 4 5 to 10 parts, hard monomer 50 to 80 parts, acrylate 35 to 75 parts, composite emulsifier 3 to 7 parts, composite silicone 0 to 8 parts, buffer reagent 0.2 to 0.6 parts, initiator 0.2 to 1.2 parts, isopropanol 0.2 to 0.6 parts, surface activity modifier 0 - 10 parts, deionized water 185 to 320 parts.

2. The magnetic-responsive Pickering emulsifier according to claim 1, characterized in that the hard monomer is one or more of styrene and α-methylstyrene in any molar ratio combination; and / or, the acrylate is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate in any molar ratio combination.

3. The magnetic-responsive Pickering emulsifier according to claim 1 or 2, characterized in that the composite emulsifier is composed of a non-ionic surfactant and an anionic surfactant; preferably, the non-ionic emulsifier is one of alkylphenol polyoxyethylene ethers, polysorbates, alkyl polyglycosides, and the anionic emulsifier is one of sodium dodecyl cashew phenol polyoxyethylene ether sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate.

4. The magnetic-responsive Pickering emulsifier according to any one of claims 1-3, characterized in that the composite organosilicon is composed of γ-glycidoxypropyltrimethoxysilane and α,ω-dihydroxy-terminated polydimethylsiloxane, and the mass ratio of the two is 1:2 to 1:5; and / or, the buffer reagent is selected from one or two of acrylic acid and sodium acrylate; and / or, the initiator is one or more of potassium persulfate and azobisisobutyronitrile in any molar ratio combination; and / or, the surface activity modifier is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and hexanediol diacrylate in any molar ratio combination.

5. The preparation method of the magnetic-responsive Pickering emulsifier according to any one of claims 1-4, characterized in that the steps include: (1) Add magnetic nano-Fe 3 O 4 to deionized water, disperse it evenly to form suspension A; add the hard monomer to deionized water, add the composite emulsifier to obtain pre-emulsion B; add potassium persulfate to deionized water to dissolve it to obtain initiator solution C; add the buffer reagent to deionized water to obtain buffer solution D; add acrylate to deionized water, add the composite emulsifier to obtain pre-emulsion E; (2) Suspension A, pre-emulsion B, part of pre-emulsion E, and part of buffer solution D are heated under inert gas protection, and part of initiator solution C is added, and reacted to obtain emulsion F; (3) The remaining pre-emulsion E, the remaining buffer solution D, and part of the initiator solution C are added dropwise to emulsion F, and kept warm to obtain emulsion G; (4) The composite organosilicon, the surface activity modifier, and the remaining initiator solution C are added dropwise to emulsion G, and kept warm to obtain emulsion H; (5) Emulsion H is kept warm, and the solid content of the emulsion is adjusted; emulsion H is cooled to room temperature, and the pH is adjusted to 7-8 to obtain the magnetic-responsive Pickering emulsifier.

6. The preparation method according to claim 5, characterized in that the heating temperature in step (2) is 70-85 °C, and the reaction time is 30-90 min; and / or, the temperature for keeping warm in step (3) is 70-85 °C, and the holding time is 1-3 h; and / or, the temperature for keeping warm in step (4) is 70-85 °C, and the holding time is 1-2 h; and / or, the temperature for keeping warm in step (5) is 55-65 °C, and the holding time is 1-8 h.

7. Use of the magnetic-responsive Pickering emulsifier according to any one of claims 1-4 or the magnetic-responsive Pickering emulsifier prepared by the method according to claim 5 or 6 in the treatment of acrylic heavy fraction deep cracking tar.

8. A method for treating high-viscosity tar after deep cracking of acrylic heavy fractions, comprising the following steps: (1) Add the magnetic-responsive Pickering emulsifier to the high-viscosity tar after deep cracking of the acrylic heavy fraction to make the magnetic-responsive Pickering emulsifier and the tar mix evenly; (2) Add water to the high-viscosity tar for emulsification under high-speed stirring conditions, and stop adding water when the emulsion undergoes an inversion; (3) Transport the acrylic tar emulsion to the incineration unit at room temperature, and the magnetic-responsive Pickering emulsifier is selected from the magnetic-responsive Pickering emulsifier according to any one of claims 1-4 or the magnetic-responsive Pickering emulsifier prepared by the method according to claim 5 or 6.

9. The method according to claim 8, characterized in that the weight portion of the high-viscosity tar added in step (1) is 100 parts, and the weight portion of the magnetic-responsive Pickering emulsifier is 5-10 parts; the emulsification temperature in step (2) is 50-70 °C.

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