NL2030494B1 - Modified magnetic particle/attapulgite composite oil-absorbing resin as well as preparation method and application thereof - Google Patents

Modified magnetic particle/attapulgite composite oil-absorbing resin as well as preparation method and application thereof Download PDF

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NL2030494B1
NL2030494B1 NL2030494A NL2030494A NL2030494B1 NL 2030494 B1 NL2030494 B1 NL 2030494B1 NL 2030494 A NL2030494 A NL 2030494A NL 2030494 A NL2030494 A NL 2030494A NL 2030494 B1 NL2030494 B1 NL 2030494B1
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oil
attapulgite
modified
modified magnetic
magnetic particles
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NL2030494A
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NL2030494A (en
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Wang Qingyun
Liu Caiyun
Song Ru
Tong Yongchun
Li Shoubo
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Univ Hexi
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil

Abstract

a modified magnetic particle/attapulgite composite oil-absorbing resin, a preparation method and application thereof, and relates to the field of oil-absorbing resin preparation. According to the invention, octadecyl methacrylate and styrene are used as monomers, double Pickering emulsion made of surface modified attapulgite and modified magnetic particle cobalt ferrite is used as a template, ammonium persulfate and potassium sulphate are used as initiators, and the modified magnetic particle/attapulgite composite oil- absorbing resin is prepared by a suspension emulsion polymerization method; the oil absorption rate reached 91.1% and 10.05%, and there was a high oil return rate and stable oil retention rate in the oil return process.

Description

Modified magnetic particle/attapulgite composite oil-absorbing resin as well as preparation method and application thereof
TECHNICAL FIELD The invention relates to the field of oil-absorbing resin preparation, in particular to a modified magnetic particle/attapulgite composite oil-absorbing resin and a preparation method and application thereof.
BACKGROUND In recent years, with the rapid development of economy, the demand for resources has also increased rapidly. As the development object of new energy, the status of ocean is rising day by day, and a series of pollution such as oil leakage accompanying the development process is becoming more and more serious. At the same time, the high-speed chemical industry's waste liquid discharge in the development process poses a threat to the environment. Therefore, controlling and treating water pollution is a serious problem that needs to be solved urgently at present.
Chemical oil-absorbing material is a very efficient oil-absorbing material, which has the advantages of high efficiency, low cost and recycling, and is widely used in water pollution treatment. This kind of synthetic resin has a porous network structure. When oil is absorbed, the task of oil absorption is completed by the hydrophobic modified lipophilic group and intermolecular force between molecules. The adsorption mechanism is mainly controlled by the diffusion of oil molecules. At the beginning of resin oil absorption, it is carried out through the solvation reaction between a small amount of oil molecules entering the interior and the molecular chains of the resin. At this time, because the amount of oil absorption is too small, it is not enough for the molecular chains to fully stretch out. When the resin oil absorption reaches a certain amount, the complete solvation reaction will occur, and the molecular chains will also fully stretch out at this time. In this process, the oil absorption rate of the resin is also the fastest. When the molecular chains stretch to the peak value, the molecular chains will gradually contract until the equilibrium state, that is, the oil absorption reaches saturation.
High oil absorption composite resin is a relatively new type of oil absorption product, and its practical application is very broad. Besides being used to treat sewage and improve the environment, it is also widely used in the preparation of slow-release materials and the production of washing products. However, at present, the adsorption rate of high oil absorption composite resin for pollutants such as fuel or oil can only reach about 500%, and the adsorption efficiency is still too low. How to improve the oil absorption rate of oil absorption composite resin is a difficult problem to be solved urgently in this field.
SUMMARY The purpose of the present invention is to provide a modified magnetic particle/attapulgite composite oil-absorbing resin as well as its preparation method and application, so as to solve the above-mentioned problems in the prior art and improve the oil absorption rate, oil return rate, oil retention rate and thermal stability of the composite oil-absorbing resin.
To achieve the above objective, the present invention provides the following scheme: One of the aims of the invention is to provide a preparation method of modified magnetic particle/attapulgite composite oil-absorbing resin, which comprises the following steps: 1, modifying attapulgite to obtain modified attapulgite; Step two, cobalt ferrite is modified to obtain modified magnetic particles; Step 3, uniformly mixing the modified magnetic particles with deionized water, octadecyl methacrylate and styrene to obtain solution A; Step 4, adding modified attapulgite, deionized water, octadecyl methacrylate and styrene into solution A, mixing evenly, adding crosslinking agent, and heating to obtain double pickering emulsion B; Dropping the mixed solution of ammonium persulfate and potassium sulphate into B, curing and drying to obtain the modified magnetic particle/attapulgite composite oil-absorbing resin.
Furthermore, in the first step, the modifier used to modify attapulgite is dodecyl mercaptan or KH570. Further, when the modifier is dodecyl mercaptan, the mass ratio of the modified magnetic particles to the modified attapulgite is 1: (4-12). Furthermore, when the modifier is KH570, the mass ratio of the modified magnetic particles to the modified attapulgite is 1: 2. Furthermore, the modifier used for modifying cobalt ferrite in step 2 is dodecyl mercaptan.
Further, in the first step, the mass volume ratio of attapulgite to modifier is 1 g: (0.1-0.5) ml; In the second step, the mass volume ratio of cobalt ferrite to modifier is 1 g: (0.1 - 0.3) ml.
Further, that mas ratio of the modified magnetic particle to deionized water, octadecyl methacrylate and styrene in step 3 is 0.05:3:1:2. Further, the mass ratio of modified attapulgite to deionized water, octadecyl methacrylate and styrene in step 4 is (0.2-0.6): 3: 1: 2. The second object of the present invention is to provide a modified magnetic particle/attapulgite composite oil-absorbing resin prepared by the above preparation method.
The third object of the present invention is to provide the application of a modified magnetic particle/attapulgite composite oil-absorbing resin in adsorbing oil pollutants in water.
The invention discloses the following technical effects: (1) in the invention, octadecyl methacrylate (CAS) and styrene (St) are used as monomers, double Pickering emulsion made of surface modified attapulgite and modified magnetic particle cobalt ferrite is used as a template, ammonium persulfate and potassium sulphate are used as initiators, and a magnetic ion/attapulgite composite oil-absorbing resin is prepared by a suspension emulsion polymerization method; the invention has the advantages of mild preparation conditions, easily available materials, difficult damage of finished products, and multiple recycling, which not only reduces the manufacturing cost, but also is environmentally friendly; (2) According to the invention, dodecyl mercaptan and KH570 are used as modifiers, and the modified attapulgite and modified magnetic particles are made into stable double pickering emulsion, so that the cobalt element in the prepared composite oil-absorbing resin is uniformly dispersed in attapulgite, and finally, the oil absorption rate of the prepared modified magnetic ion/attapulgite composite oil-absorbing resin reaches 911% and 1005%, and the oil return rate is high and stable in the oil return process.
(3) The magnetic ion/attapulgite composite oil-absorbing resin prepared by the invention does not decompose until the temperature reaches 280°C, which indicates that the oil- absorbing resin prepared by the invention has good decomposition resistance and thermal stability.
BRIEF DESCRIPTION OF THE FIGURES In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention, and for ordinary technicians in the field, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a SEM image of the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Example 1; Fig. 2 is the infrared spectrum of attapulgite, in which a is pure attapulgite prepared in Example 1, b is modified attapulgite prepared in Example 2 and c is modified attapulgite prepared in Example 1; Fig. 3 is a T-G graph of modified magnetic particle/attapulgite composite oil-absorbing resin, in which a is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Comparative Example 1, b is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Example 1, and c is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Comparative Example 2. Fig. 4 is an X-ray diffraction diagram of the modified magnetic particle/attapulgite composite oil-absorbing resin, in which a is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Comparative Example 1, b is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Example 5, c is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in
Example 1 and d is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Comparative Example 2. Fig. 5 is the infrared spectrum of modified magnetic particle/attapulgite composite oil- absorbing resin, in which a is the modified magnetic particle/attapulgite composite oil- absorbing resin prepared in Comparative Example 1, b is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Example 5, c is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Example 1, and d is the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in Comparative Example 2. Fig. 6 is the XRD spectrum of pure attapulgite and modified attapulgite prepared in Example 2, where a is pure attapulgite and b is modified attapulgite; Fig. 7 is the XRD spectrum of cobalt ferrite and modified magnetic particles prepared in Example 3; Fig. 8 is the infrared spectrum of cobalt ferrite and modified magnetic particles prepared in Example 3; Fig. 9 is a physical diagram of W/O Pickering emulsion of modified attapulgite under different oil-water ratios, in which a, b, c and d are modified attapulgite prepared in Example 1, ande, f, g and h are modified attapulgite prepared in Example 2; Fig. 10 is the W/O micrograph of the modified attapulgite prepared in Example 1 under different oil-water ratios, in which the oil-water ratios are a1:1, b2:1, c4:1 and dé: 1; Fig. 11 is the W/O micrograph of the modified attapulgite prepared in Example 2 under different oil-water ratios, in which the oil-water ratios are e 1:1, f 2:1, g 4:1 and h6: 1; Fig. 12 is a physical diagram of O/W Pickering emulsion of modified magnetic particles under different oil-water ratios, in which a1, b1, ¢1 and d1 are modified magnetic particles prepared in Example 3, and e1, f1, g1 and h1 are modified magnetic particles prepared in Example 1; Fig. 13 is an O/W micrograph of the modified magnetic particles prepared in Example 3 under different oil-water ratios, wherein the oil-water ratios are a1 1:1, b1 2:1, ¢1 3:1 and d 14: 1, Fig. 14 is an O/W micrograph of the modified magnetic particles prepared in Example 1 under different oil-water ratios, where the oil-water ratios are e1 1:1, f1 2:1, g1 3:1 and h1 4:1.
DESCRIPTION OF THE INVENTION Now, various exemplary embodiments of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of some aspects, characteristics and embodiments of the present invention.
It should be understood that the terms used in this invention are only for describing specific embodiments, and are not used to limit the invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Any stated value or intermediate 5 value within the stated range and any other stated value or every smaller range between intermediate values within the stated range are also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.
Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by the ordinary technicians in the field of this invention. Although the present invention only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials related to the documents. In case of conflict with any incorporated documents, the contents of this specification shall prevail.
Without departing from the scope or spirit of the present invention, it is obvious to those skilled in the art that many modifications and changes can be made to the specific embodiments of the present invention. Other embodiments obtained from the description of the present invention will be obvious to the skilled person. The description and example of that present invention are exemplary only.
The words “including”, "comprising", "having" and "containing" used in this paper are all open terms, that is, they mean including but not limited to.
Example 1 Step 1: Place 2800ml of distilled water in a beaker, weigh 4.2142 g of sodium pyrophosphate and dissolve in the beaker, and stir for 0.5h at 40°C. Then take 140 g of attapulgite raw soil, gradually add to it, continue to stir for 1h, and then stand for 24h to layer. The supernatant was withdrawn, and 3mol/L HCI was added dropwise until no bubbles were generated. Centrifuge the upper liquid to obtain a solid precipitate, wash with water until the precipitate is neutral, and then dry the product at 100°C to obtain purified attapulgite; weigh 1 g of purified attapulgite and place it in an agate mortar , Add 0.1 ml dodecanethiol to grind for 1h, and then put it in an oven for drying at 100°C, then modified attapulgite can be obtained.
Step 2: Accurately weigh 0.8144 g Fe(NO:)3:9H2O and 0.3538 g Co(NO3)2-6H:0, respectively dissolve them in 24mL absolute ethanol solvent, stir to dissolve and mix, then transfer to 50mL PTFE high pressure reaction kettle. React at 200°C for 10 hours. After the reactor is cooled, centrifuge to remove the supernatant. After washing with absolute ethanol and distilled water, dry at 100°C for 10 hours to obtain cobalt ferrite (CoFe;Qy4); In the bowl, add
0.1ml dodecanethiol drop by drop, grind for 1 hour and put it in an oven for drying to obtain magnetic ions. Step 3: Mix 0.05 g of modified magnetic particles with 3ml of deionized water, 1 g of stearyl methacrylate and 2 g of styrene to obtain solution A; Step 4: Add 0.4 g modified attapulgite, 3ml deionized water, 1 g octadecyl methacrylate and 2 g styrene to solution A and mix well, add 0.03 g divinylbenzene, and heat in a water bath at 70°C 10min, get double pickering emulsion B; dissolve 0.075 g ammonium persulfate and 0.188 g potassium sulphate in 34ml deionized water, slowly add dropwise to the above double pickering emulsion, solidify in a water bath for 6h and then put it in a 70°C oven for baking Dry to obtain a modified magnetic particle/attapulgite composite oil-absorbing resin. The oil absorption, oil return, and oil retention of the modified magnetic particle/attapulgite composite oil-absorbing resin are calculated by the following calculation methods. Determination of oil absorption At room temperature, weigh a certain mass of modified magnetic particles/attapulgite composite oil-absorbing resin G, immerse it in a sufficient amount of oil to be adsorbed, statically adsorb for 12 hours, and then take the composite oil-absorbing resin from the oil After the compound oil-absorbing resin no longer drips oil, the mass of the compound oil-absorbing resin after absorbing the oil is called G1. Then its oil absorption rate is as follows: e GE) C 100%
G In the formula: e is the oil absorption ratio of the composite oil-absorbing resin when the oil absorption balance is reached (g/g); Gt is the oil absorption rate of the composite oil-absorbing resin at time t (g/g); G is the mass of composite oil-absorbing resin before oil absorption (g); G1 is the mass of the composite oil-absorbing resin after its oil absorption reaches saturation (9); Determination of oil return rate Weigh a certain amount of modified magnetic particles/attapulgite composite oil-absorbing resin, immerse it in the oil to be adsorbed to reach saturation oil absorption, calculate the adsorption capacity of the composite oil-absorbing resin to the oil, and then put it in a vacuum drying oven In the middle drying, record its mass as G2, then re-absorb the oil, and then call its saturated mass as G3. Then its oil return rate is as follows: e, = 4% x 100% Determination of oil retention rate
Take a certain amount of modified magnetic particle/attapulgite composite oil-absorbing resin, with a mass of H, and place it in toluene for 24 hours. After the oil is saturated, record its mass as M. Then place the composite oil-absorbing resin in a centrifuge for 5 minutes. After taking it out, its mass is called G4.
Then its oil retention rate is as follows: e, = a x 100% Results: The SEM image of the modified magnetic particle/attapulgite composite oil- absorbing resin prepared in this example is shown in Figure 1, the TG curve is shown in Figure 3b, the X-ray diffraction diagram is shown in Figure 4c, and the infrared The spectrum is shown in Figure 5c; after calculation, the oil absorption rate of the modified magnetic particle/attapulgite composite oil-absorbing resin is 911%, the oil return rate is 1050%, and the oil retention rate is
94.86%; the infrared spectrum of the pure attapulgite prepared in this example is shown in Figure 2a, and the infrared spectrum of the modified attapulgite is shown in Figure 2c; the oil-water ratio of the modified attapulgite prepared in this example is the actual picture of W/O Pickering emulsion under the conditions of 1:1, 2:1, 4:1, 6:1 is shown in Figure 9a, b, ¢, d, and the oil-water ratio is 1:1, 2:1; the W/O microscope picture under the conditions of 4:1, 6:1 is shown in Figure 10; Figure 12e1, f1, g1, and h1 of the O/W Pickering emulsion of the modified magnetic particles prepared in this example under the conditions of oil-to-water ratio of 1:1, 2:1, 3:1, 4:1 , its O/W microscope picture under the conditions of oil-water ratio of 1:1, 2:1, 3:1, 4:1 is shown in Figure
14.
Example 2 The difference from Example 1 is that in step one, 0.1 ml of dodecanethiol is replaced with
0.5 ml of KH570, and in step four, the addition amount of modified attapulgite is 0.1 g.
Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this example had an oil absorption rate of 1005%, an oil return rate of 1090%, and an oil retention rate of 95.15%; the infrared spectrum of the modified attapulgite prepared in this example is shown in Figure 2b; the XRD spectrum of the pure attapulgite prepared in this example is shown in Figure 6a, and the XRD spectrum of the modified attapulgite is shown in Figure 6b; the actual picture of the W/O Pickering emulsion of the modified attapulgite prepared in this example at the oil-water ratio of 1:1, 2:1, 4:1, 6:1 is shown in Figure Se, f, g, and h. As shown, the W/O microscope picture under the conditions of oil-water ratio of 1:1, 2::1, 4:1, and 6:1 is shown in Figure 11.
Example 3 The difference from Example 1 is that the addition amount of dodecanethiol in step two is 0.3 ml. Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this example has an oil absorption rate of 840%, an oil return rate of 970%, and an oil retention rate of 93.15%;The XRD spectrum of the cobalt ferrite prepared in this example is shown in Figure 7a, and the infrared spectrum is shown in Figure 8a.; the XRD spectrum of the modified magnetic particles prepared in this example is shown in Figure 7b, and the infrared spectrum is shown in Figure 8b; Figure 12a1, b1, c1 and d1 of the O/W Pickering emulsion of the modified magnetic particles prepared in this example under the conditions of oil-to-water ratio of 1:1, 2:1, 4:1, and 6:1, Its O/W microscope picture under the conditions of oil-water ratio of 1:1, 2::1, 4:1, 6:1 is shown in Figure 13. Example 4 The difference from Example 1 is that the addition amount of modified attapulgite in step four is 0.2 g. Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this example had an oil absorption rate of 780%, an oil return rate of 837%, and an oil retention rate of 92.17%.
Example 5 The difference from Example 1 is that the addition amount of modified attapulgite in step 4 is
0.34q. Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this example had an oil absorption rate of 839%, an oil return rate of 972%, and an oil retention rate of 95.12%. Example 6 The difference from Example 1 is that the addition amount of modified attapulgite in step 4 is 06q. Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this example had an oil absorption rate of 763%, an oil return rate of 836%, and an oil retention rate of 96.12%. Comparative example 1 The difference from Example 1 is that the addition amount of modified attapulgite in step 4 is 01g.
Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example had an oil absorption rate of 428%, an oil return rate of 697%, and an oil retention rate of 78.53%; the T-G curve diagram of the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example is shown in Figure 3a, the X- ray diffraction diagram is shown in Figure 4a, and the infrared spectrum is shown in Figure 5a.
Comparative example 2 The difference from Example 1 is that the addition amount of modified attapulgite in step 4 is
0.7 q.
Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example had an oil absorption rate of 483%, an oil return rate of 730%, and an oil retention rate of 96.21%; the T-G curve diagram of the modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example is shown in Fig. 3c, the X- ray diffraction diagram is shown in Fig. 4d, and the infrared spectrum is shown in Fig. 5d.
Comparative example 3 The difference from Example 2 is that the addition amount of modified attapulgite in step 4 is 024g.
Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example had an oil absorption rate of 550%, an oil return rate of 630%, and an oil retention rate of 90.19%.
Comparative example 4 The difference from Example 2 is that the addition amount of modified attapulgite in step 4 is 035g.
Results: The modified magnetic particle/attapulgite composite oil-absorbing resin prepared in this comparative example had an oil absorption rate of 711%, an oil return rate of 880%, and an oil retention rate of 90.56%.
Comparative example 5 The difference from Example 1 is that the configuration of solution A in step 3 is omitted, and the configuration of emulsion B is directly carried out, specifically: Mix 0.05 g modified magnetic particles with 0.4 g modified attapulgite, 6ml deionized water, 2 g stearyl methacrylate and 4 g styrene, and 0.03 g of divinylbenzene is added, and the mixture is heated in a water bath at 70° C for 10 minutes to obtain emulsion B.
Results: The modified magnetic particles/attapulgite composite oil-absorbing resin prepared in this comparative example had an oil absorption rate of 300%, an oil return rate of 360%, and an oil retention rate of 97.76%.
It can be seen from Example 1 and Comparative Example 3 and Comparative Example 4 that when the addition amount of modified attapulgite is 0.1 g, the oil absorption rate is very high, reaching 1005%, but the addition amount of modified attapulgite increases When it reaches 0.2 g, the oil absorption rate drops sharply to 550%, and then increases the amount of modified attapulgite, and the oil absorption rate increases to 711%. It shows that the attapulgite modified with KH570 modifier has a certain effect on the oil absorption rate of the composite oil-absorbing resin, but the oil absorption rate changes disorderly with the increase of its addition, and there is no increasing or decreasing law.
It can be seen from Figure 2 that 1632 cm’ and 973 cm are the characteristic peaks of attapulgite. The KH570 modified attapulgite (b) has new peaks at 2951 cm’ and 1246 cm’, respectively. The vibration peaks of -CH3 and -CH2 indicate that the modified attapulgite has introduced organic matter on the surface, which enhances the hydrophobicity of the attapulgite; the dodecyl mercaptan-modified (c) attapulgite has a CH stretching vibration peak at 3026 cm’, a -CH2 plane swing vibration peak at 697 cm, and a smaller vibration peak at 1716 cm. -CH3 characteristic peak, indicating that dodecanethiol-modified attapulgite has a certain degree of hydrophobicity.
It can be seen from Fig. 3 that the modified magnetic particle/attapulgite composite oil- absorbing resin begins to decrease during the temperature range of 150°C ~280°C. This stage is the scission of the alkyl chain; During the temperature range from 280°C to 430°C, the quality of the modified magnetic particle/attapulgite composite oil-absorbing resin is greatly reduced. This stage is the high-speed decomposition stage of organic matter; after that, with the increase of temperature, the modified magnetic particle/attapulgite The quality of composite oil-absorbing resin no longer decreases, and gradually stabilizes. When the addition amount of modified attapulgite is 0.1 g, 0.4 g, the temperature rises to 280°C, the modified magnetic particle/attapulgite composite oil-absorbing resin is burned out, and when the addition amount of modified attapulgite increases to 0.7 g When the modified magnetic particles/attapulgite composite oil-absorbing resin is not burnt out until the temperature rises to 320°C, it can be observed that in the later high temperature stage, as the amount of modified attapulgite increases, the modified magnetic particles/ The extent of quality reduction of attapulgite composite oil- absorbing resin is reduced, indicating that the addition of modified attapulgite improves the resin’s decomposition resistance and thermal stability.
It can be seen from Figure 4 that the modified magnetic particle/attapulgite composite oil- absorbing resin has a strong characteristic diffraction peak at 20.18°, which is the diffraction peak of synthetic resin. As the amount of modified attapulgite increases, A new characteristic diffraction peak of attapulgite appeared at about 8.4°, indicating that the modified attapulgite was compounded into the oil-absorbing resin, and a characteristic diffraction peak of cobalt ferrite appeared at about 35.4°, indicating that the modified magnetic particles were compounded into the oil-absorbing resin middle.
It can be seen from Figure 5 that the modified magnetic particle/attapulgite composite oil- absorbing resin has a characteristic peak at 2800-3000 cm’, this peak is the characteristic absorption peak of styrene; at 1453 cm’ is a benzene ring The stretching vibration absorption peak of the CC bond in the middle; 1170 cm’! is the characteristic absorption peak of Co participating in the polymerization process, indicating that the modified magnetic particles enter the resin during the polymerization process; the strong peak around 698 cm’! is the characteristic absorption peak of monosubstituted benzene (the out-of-plane bending vibration of the C-H bond on the carbon frame of the benzene ring); the characteristic absorption peak caused by the stretching vibration of carbonyl -C=0 appears at 1730 cm, the absorption peak of Si-O stretching vibration frequency at 1030 cm’, and the SC bond stretching vibration peak at 758 cmt, indicating that The modified attapulgite participates in the copolymerization during the polymerization process, and the preparation of the entire resin is not a simple mechanical filling.
It can be seen from Figure 6 that there are four strong characteristic diffraction peaks at 26 of 8.5°, 21.6°, 26.7°, and 34.2°; at 8.5° is the characteristic peak of attapulgite; 26.7° is the characteristic peak of SiO2 in attapulgite. 34.2° is the characteristic peak of dolomite in attapulgite. No new characteristic peaks appeared in the attapulgite before and after the modification, indicating that the attapulgite in Example 2 was successfully modified.
It can be seen from Figure 7 that the cobalt ferrite before and after modification at 37.3° and
63.0° have characteristic peaks, which are the characteristic peaks of cobalt ferrite; a new small characteristic peak appears at 35.4° in b, but there is no position of the characteristic peak of the particle is affected, which is caused by the addition of the modifier staying in the particle, and it has no effect on the original particle structure, indicating that the modified magnetic particle is successfully prepared.
It can be seen from Figure 8 that the characteristic peaks of the cobalt ferrite metal bond appear at about 1410 cmt and 1569cm™, and the OH bond stretching vibration appears at 3400 cm, indicating the existence of active -OH groups on the surface of the nanometer cobalt ferrite.
It can be seen from Figure 10 and Figure 11 that the emulsion stability and particle uniformity of 0.1 ml dodecanethiol-modified attapulgite under the same oil-water ratio are better than those of 0.5 ml KH570 modified attapulgite. Rodstone; and with the increase of oil-water ratio, the uniformity and stability of emulsion particles will increase, and it will reach the best when the oil- water ratio is 6:1.
It can be seen from Figure 13 and Figure 14 that with the increase of the modifier dosage, the stability of the emulsion becomes worse, and the degree of particle size regulation becomes worse. The same modification condition, with the increase of oil-water ratio, the stability gradually increases, and the optimal oil-water ratio It is 4:1; as the volume fraction of the oil phase increases, the diameter of the droplets gradually changes from large to small, and the shape tends to be regular.
The above-mentioned embodiments only describe the preferred mode of the present invention, and do not limit the scope of the present invention.
Without departing from the design spirit of the present invention, those of ordinary skill in the art have made various contributions to the technical solutions of the present invention.
Variations and improvements should fall within the protection scope determined by the claims of the present invention.

Claims (10)

CONCLUSIESCONCLUSIONS 1. Een werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes, welke werkwijze de volgende stappen omvat: Stap 1: het modificeren van attapulgiet om gemodificeerd attapulgiet te verkrijgen; Stap 2: het modificeren van kobaltferriet om gemodificeerde magnetische deeltjes te verkrijgen; Stap 3: het gelijkmatig mengen van de gemodificeerde magnetische deeltjes met gedeïoniseerd water, octadecylmethacrylaat en styreen om oplossing A te verkrijgen; Stap 4: toevoeging van gemodificeerd attapulgiet, gedeioniseerd water, octadecylmethacrylaat en styreen aan oplossing A, gelijkmatig mengen, toevoegen van verknopingsmiddel, en verhitten om dubbele Pickering-emulsie B te verkrijgen; druppelen van de gemengde oplossing van ammoniumpersulfaat en kaliumsulfaat in B, uitharden en drogen om de olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes te verkrijgen.A method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles, the method comprising the steps of: Step 1: modifying attapulgite to obtain modified attapulgite; Step 2: modifying cobalt ferrite to obtain modified magnetic particles; Step 3: uniformly mixing the modified magnetic particles with deionized water, octadecyl methacrylate and styrene to obtain solution A; Step 4: Add modified attapulgite, deionized water, octadecyl methacrylate and styrene to solution A, mix evenly, add crosslinking agent, and heat to obtain Pickering double emulsion B; dripping the mixed solution of ammonium persulfate and potassium sulfate in B, curing and drying to obtain the oil-absorbing resin of a composite of modified attapulgite and modified magnetic particles. 2. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 1, met het kenmerk dat de modificator die wordt toegepast voor het modificeren van attapulgiet in stap 1 dodecylmercaptaan of KH570 is.The process for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 1, characterized in that the modifier used for modifying attapulgite in step 1 is dodecyl mercaptan or KH570. 3. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 2, met het kenmerk dat wanneer de modificator dodecylmercaptaan is, de massaverhouding van de gemodificeerde magnetische deeltjes ten opzichte van het gemodificeerde attapulgiet 1 : (4 - 12) bedraagt.The method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 2, characterized in that when the modifier is dodecyl mercaptan, the mass ratio of the modified magnetic particles to the modified attapulgite 1 : (4 - 12). 4. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 2, met het kenmerk dat wanneer de modificator KH570 is, de massaverhouding van de gemodificeerde magnetische deeltjes ten opzichte van het gemodificeerde attapulgiet 1 : 2 bedraagt.The method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 2, characterized in that when the modifier is KH570, the mass ratio of the modified magnetic particles to the modified attapulgite is is 1 : 2. 5. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 1, met het kenmerk dat de modificator die wordt toegepast om kobaltferriet in stap 2 te modificeren dodecylmercaptaan is.The method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 1, characterized in that the modifier used to modify cobalt ferrite in step 2 is dodecyl mercaptan. 6. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 1, met het kenmerk dat de massa-volumeverhouding van attapulgiet ten opzichte van de modificator die voor het modificeren van attapulgiet in stap 1 wordt gebruikt gelijk is aan 1 g : (0.1 - 0.5) ml; waarbij de massa-volumeverhouding van kobaltferriet ten opzichte van de modificator in stap 2 gelijk is aan 1g: (0.1 - 0.3) ml.The method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 1, characterized in that the mass-volume ratio of attapulgite to the modifier used for modifying attapulgite in step 1 is used equal to 1 g : (0.1 - 0.5) ml; where the mass-volume ratio of cobalt ferrite to modifier in step 2 is 1g : (0.1 - 0.3) ml. 7. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 1, met het kenmerk dat de massaverhouding van de gemodificeerde magnetische deeltjes ten opzichte van gedeïoniseerd water, octadecylmethacrylaat en styreen in stap 3 gelijk is aanThe method for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 1, characterized in that the mass ratio of the modified magnetic particles to deionized water, octadecyl methacrylate and styrene in step 3 is equals 0.05:3:1:2.0.05:3:1:2. 8. De werkwijze voor de bereiding van een olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 1, met het kenmerk dat de massaverhouding van gemodificeerd attapulgiet ten opzichte van gedeioniseerd water, octadecylmethacrylaat en styreen in stap 4 (0,2 - 06) : 3:1: 2 bedraagt.The process for preparing an oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles according to claim 1, characterized in that the mass ratio of modified attapulgite to deionized water, octadecyl methacrylate and styrene in step 4 (0 .2 - 06) : 3:1:2. 9. Olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes, bereid volgens de bereidingswijze volgens conclusie 1.An oil-absorbent resin of a composite of modified attapulgite and modified magnetic particles prepared by the method of claim 1. 10. Toepassing van de olie-absorberende hars van een composiet van gemodificeerd attapulgiet en gemodificeerde magnetische deeltjes volgens conclusie 9 voor het adsorberen van verontreinigende oliehoudende stoffen in water.Use of the oil-absorbing resin of a composite of modified attapulgite and modified magnetic particles according to claim 9 for adsorbing oil pollutants in water.
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