CN111607796A - Controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and preparation method thereof - Google Patents
Controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a controllable-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and a preparation method thereof, and FeCl is used3·6H2O, crystalline sodium acetate, ethylene glycol, Zn (NO)3)2·6H2O、Al(NO3)3·9H2O、Ce(NO3)3·9H2Preparing magnetic zinc-aluminum-cerium hydrotalcite (Fe) with MBT intercalation by using O, 2-mercaptobenzothiazole, NaOH and methanol as raw materials through an ion exchange method3O4@ ZnAlce-MBT LDH). Nanocapacitor effect and Fe using hydrotalcite3O4The superparamagnetic is characterized in that a 2-mercaptobenzothiazole intercalated magnetic zinc-aluminum-cerium hydrotalcite corrosion inhibitor material is synthesized by adopting an ion exchange method; simultaneously, the release behavior of the corrosion inhibitor is controlled by using an external magnetic field so as to improve the magnetic control release behavior of the corrosion inhibitorThe corrosion resistance and the service life of the carbon steel in a seawater circulating cooling system.
Description
Technical Field
The invention relates to the technical field of corrosion inhibitors for seawater circulating cooling systems, in particular to a controllable-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and a preparation method thereof.
Background
The seawater circulation cooling technology is an important technology of directly utilizing seawater to replace fresh water as a cooling medium, thereby saving fresh water resources and reasonably and efficiently utilizing seawater resources (spac, tremie, gao li, hou yu, wang wei zhen, yin jian hua, application of corrosion electrochemical technology in a seawater circulation cooling system, ocean development and management, 2018,35(4): 98-105). However, in the seawater circulation cooling system, the corrosion of metal equipment often causes serious economic and safety problems. Therefore, the corrosion of metal equipment in the seawater circulating cooling system is very important to solve. The common method for solving the corrosion of equipment in seawater comprises the following steps: (1) adopting corrosion-resistant materials, including aluminum brass, copper nickel, titanium and the like; (2) coating an organic coating on the surface of the metal equipment; (3) adding corrosion inhibitor (research progress of seawater corrosion inhibition on carbon steel, environmental science and technology, 2010,33(12F): 368-. The corrosion inhibitor technology becomes an important anticorrosion technology when carbon steel is used as metal equipment in circulating cooling water due to the advantages of good corrosion inhibition performance, low cost, economy, high efficiency and the like (Xinhua, hypersensitive property, Liangxinhua, molybdate composite corrosion inhibitor researches the corrosion inhibition performance and mechanism of carbon steel in seawater, environmental science and technology, 2007,30(4): 23-26).
In recent years, the corrosion inhibitor is loaded in a nano container to attract people's extensive attention, specifically, the corrosion inhibitor is loaded in the nano container, and the action force between the corrosion inhibitor and the nano container is utilized to slowly release the corrosion inhibitor from the nano container, so that the corrosion inhibitor has the functions of slow and continuous release and long-term high-efficiency corrosion inhibition, and the problems existing in the traditional method of adding the corrosion inhibitor once or for many times are solved. Common nano-containers comprise polyelectrolyte microcapsules, hydrotalcite compounds (LDHs), mesoporous silica nano-microspheres, Halloysite Nanotubes (HNTs) and the like. Wherein the LDHs are compounds assembled by interaction of a positively charged host laminate and a negatively charged interlayer anion through non-covalent bonds, also known as layered double hydroxides (Meng Zilin, Zhang Yihe, Zhang Qian, Chen Xue, Liu Leipeng, Komarneni S ridhar, LvFengzhu, Novel synthesis of Layered Double Hydroxides (LDHs) from zinc hydroxide, Applied Surface Science,2017,396: 799-. The general formula is [ M ]2+ 1-xM3+ x(OH)2]x+(An-)x/n·mH2O (wherein M)2+、M3+A divalent and trivalent metal cation, respectively, A is an interlayer anion having a valence of-n, and x is M3+M is the number of hydrated water). The specific anion exchangeable property of LDHs enables the LDHs to be used as a nano container to load different Corrosion inhibitors, thereby realizing the controlled release of the Corrosion inhibitors (Xu Junbo, Cao Yunqing, Fan Lu, Hu Jiming, A One-Step preparation of inhibited-loaded silicon nanocontainers for self-healing coatings, rotation Science,2018,140: 349-362). Miao et al synthesized HEDP intercalated Zn-Al-Ce hydrotalcite corrosion inhibitor by coprecipitation method and studied its corrosion inhibition effect on carbon steel in NaCl (Miao Mengyao, Wang Jihui, Hu Wenbin, Synthesis, catalysis inhibition of ZnAlce layered double hydroxide intercalated with 1-hydroxynaphthalene-1, 1-diphosphonic acid, Colloids and Surfaces A,2018,543: 144-. Li and the like prepared a nitrate ion and molybdate intercalated zinc-aluminum hydrotalcite material and studied the corrosion resistance to carbon steel. (Li Weihua, Liu Ang, Tian Huiwen, Wang Dapeng, Controlled release of later and molybdate interconnected in Zn-Al-layered double hydroxide and primers applications, Cold and interface Communications,2018,24: 18-23).
In recent years, Fe3O4The superparamagnetism can be widely applied to the fields of medicine, catalysis, adsorption and the like, and the high saturation magnetization of the superparamagnetism can enable the superparamagnetism to quickly respond to an external magnetic field (Li Yan, Bi Haoyu, Li Hui, MaoXiaming, Liang Yaqin, Synthesis, characterization, and supplemented releaseproperty of Fe3O4@(enrofloxacin-layered double hydroxides)nanocomposite,Materials Science&Engineering C,2017,78: 886-. At present, Fe having a core-shell structure has been synthesized3O4Is a composite material with a core and LDH as a shell layer, thereby realizing the target location (Zhang Hui, Pa) of the drugnDengk, Duan Xue, Synthesis, chromatography, and magnetic controlled releaseviewer of novel core-Shell structural magnetic in-interconnected LDHnanohybrids, The Journal of Physical Chemistry C,2009,113(28): 12140-. In addition, Zhao et al convert Fe3O4In combination with LDH, for adsorbing phthalate contaminants in water (ZHao Xiao, Liu Shuanggliu, Wang Peifang, Tang Zhi, Niu Hongyun, Cai Yaqi, Wu Fengchang, Wang Hao, Meng Wei, Giesy John p, Surfactant-modified flow like layered double hydroxy-coated magnetic nanoparticles for the prevention of contamination of phthalate front water samples, Journal of Chromatography A,2015,1414: 22-30). However, Fe3O4Research for corrosion has been relatively rare. Considering that the environmental pollution problem of the corrosion inhibitor is still serious, if the magnetic material Fe is used3O4The composite material is compounded with LDH loaded with corrosion inhibitor to make the composite material have magnetic responsiveness, thereby achieving the performances of targeted release and recycling, reducing the pollution to the environment and further realizing the reutilization. And further controls the release of the corrosion inhibitor under the external magnetic field, so that the corrosion inhibitor can be continuously and slowly released to play a long-acting role.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides a controllable-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and a preparation method thereof aiming at the problems of corrosion of metal equipment in a seawater circulating cooling system and environmental pollution caused by a corrosion inhibitor, and utilizes the nano-container effect of hydrotalcite and Fe3O4The superparamagnetic is characterized in that a 2-mercaptobenzothiazole intercalated magnetic zinc-aluminum-cerium hydrotalcite corrosion inhibitor material is synthesized by adopting an ion exchange method; and simultaneously, the release behavior of the corrosion inhibitor is controlled by using an external magnetic field, so that the corrosion resistance and the service life of the carbon steel in a seawater circulating cooling system are improved through the magnetic control release behavior of the corrosion inhibitor.
The purpose of the invention is realized by the following technical scheme.
Controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor and preparation method thereofMethod with FeCl3·6H2O, crystalline sodium acetate (CH)3COONa·3H2O), ethylene glycol, Zn (NO)3)2·6H2O、Al(NO3)3·9H2O、Ce(NO3)3·9H2Preparing magnetic zinc-aluminum-cerium hydrotalcite (Fe) intercalated with MBT (sodium niobate titanate) by using O, 2-Mercaptobenzothiazole (MBT), NaOH and methanol as raw materials through an ion exchange method3O4@ ZnAlce-MBT LDH) corrosion inhibitor material, which is prepared according to the following steps:
step 1, uniformly dispersing ferroferric oxide in a mixed solution of methanol and water to obtain a uniform suspension, and adding Zn (NO) into the suspension3)2·6H2O is dissolved and dispersed in the suspension, wherein n (Zn)2+)/n(Fe3O4) 1 to 1, adding ferroferric oxide and Zn (NO)3)2·6H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5).
In step 1, n (Zn)2+)/n(Fe3O4)＝(1-30):1。
In step 1, the volume ratio of methanol to water is (1-5): 1.
in the step 1, the solution is dissolved and dispersed for 10-20min under stirring or ultrasonic treatment at 20-30 ℃.
Step 2, adding Al (NO)3)3·9H2O and Ce (NO)3)3·9H2Dissolving and dispersing O in a mixed solution of methanol and water to obtain a mixed salt solution, wherein n (Zn)2+)/n(Al3+)＝(1-6):1，n(Al3+)/n(Ce3+) 1 in case of (4-9), Al (NO) is added3)3·9H2O and Ce (NO)3)3·9H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5).
In step 2, n (Zn)2+)/n(Al3+)＝(2-5):1。
In step 2, n (Al)3+)/n(Ce3+)＝(5-8):1。
In step 2, the volume ratio of methanol to water is (1-5): 1.
in step 2, stirring or ultrasonic dissolving and dispersing at 20-30 deg.C for 10-20 min.
And 3, dissolving and dispersing sodium hydroxide in the methanol solution to obtain an alkali liquor, wherein inert protective gas is kept introduced into the mixed solution in the process of adding NaOH to avoid the influence of carbon dioxide and oxygen, and the molar concentration of the sodium hydroxide methanol solution is 0.6-1.0 mol/L.
In step 3, the molar concentration of the sodium hydroxide methanol solution is 0.8 mol/L.
And 4, simultaneously dropwise adding the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 into the suspension obtained in the step 1, keeping introducing inert protective gas into the mixed solution in the dropwise adding process so as to avoid the influence of carbon dioxide and oxygen, keeping mechanical stirring for dispersing, and keeping the pH value of the solution to be 7-12 after dropwise adding.
In step 4, high-speed mechanical stirring is adopted for 300-500 r/min.
In step 4, uniform dropping is adopted, and the dropping time is controlled to be 1-3h, preferably 1.5-3 h.
In the step 4, the volume ratio of the suspension obtained in the step 1, the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 is (4-6): (2-4): (3-5), and the pH value of the solution is controlled to be 8.5-11 after the dropwise addition is finished.
Step 5, transferring the reaction slurry obtained in the step 4 into a high-pressure reaction kettle, then placing the high-pressure reaction kettle into a drying box at 50-120 ℃ for aging, separating the obtained product by using a Ru Fe B permanent magnet, centrifugally washing the product to be neutral by using ethanol, drying the product for 20-24 hours in the drying box at 50-70 ℃, and grinding the product to obtain Fe3O4@ZnAlCe-NO3 --LDH。
In step 5, the aging temperature is 60-100 ℃.
In the step 5, the aging time is 10-36 h.
In step 6, the molar concentration of the MBT methanol aqueous solution is 0.1-0.5mol/L, Fe3O4@ZnAlCe-NO3The mass of the LDH is 0.1-0.8 g.
The ferroferric oxide is prepared according to the following steps: 2.7g FeCl was weighed3·6H2O with 7.2g CH3 COONa.3H2O, dissolved in 60ml of ethylene glycol; slowly dripping 1ml of polyethylene glycol, stirring to form a uniform solution, transferring the uniform solution to a high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying box at the temperature of 100-200 ℃ for reaction for 10-18 h. Separating the obtained black product with Ru Fe-B permanent magnet, washing with deionized water and ethanol for 3 times respectively, drying in a drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4Specific references Fan Ting, Pan Dengke, Zhang Hui. study on Formation Mechanism and Structure evaluation of neural Mono persedFe3O4 nanoparticles with Controlled particles Sizes [ J].Ind.eng.chem.res,2011,50(15):9009-9018。
The invention has the beneficial effects that: the MBT intercalation magnetic zinc-aluminum-cerium hydrotalcite corrosion inhibitor takes hydrotalcite as a nano container and utilizes Fe3O4The prepared corrosion inhibitor material has good corrosion inhibition performance, targeting positioning, magnetic control release and recycling performance for a long time, and the specific experimental data are as follows:
(1) weighing 0.2g of MBT intercalation magnetic zinc aluminum cerium hydrotalcite material to be dispersed in 100ml of 3.5 percent NaCl solution according to the magnetic control release characteristic, and mechanically stirring; the change of the concentration of the MBT released in the solution in the absence of a magnetic field along with the soaking time is measured by an ultraviolet-visible spectrophotometer, and then the release curve of the MBT is drawn, as shown in figure 4. The amount of MBT released increases with the increase of the soaking time; under the condition of no magnetic field, the release speed of the corrosion inhibitor is higher, and under the condition of an external magnetic field, the release speed is obviously slower than that under the condition of no magnetic field, the release amount of the corrosion inhibitor is reduced within the same release time, and the release time is obviously prolonged. Therefore, the synthesized MBT intercalation magnetic zinc-aluminum-cerium hydrotalcite corrosion inhibition material has obvious magnetic control release performance.
(2) The exposed area of the corrosion inhibition performance which is good for a long time and is packaged by epoxy resin is 1cm2The Q235 steel sample is used as a working electrode, a saturated calomel electrode and a platinum sheet are respectively used as a reference electrode and a counter electrode, and the Q235 steel is measured by using an Autolab 302 electrochemical workstation at 3.5% NaCl, 3.5% NaCl and 2g/L Fe3O4The electrochemical impedance spectrum of the @ ZnAlce-MBT LDH solution under the condition of applying a magnetic field is shown in figure 5. As can be seen from the figure, after the synthesized corrosion inhibitor is added into the 3.5 percent NaCl solution, the capacitive arc radius of the Q235 steel is obviously increased, and the corrosion inhibition efficiency is continuously increased along with the prolonging of the release time. Fe calculated by impedance fitting3O4And the corrosion inhibition rate of the @ ZnAlce-MBT LDH is 73.46 percent when the release time is 48 hours. Namely, the synthesized MBT intercalated magnetic zinc-aluminum-cerium hydrotalcite corrosion inhibitor material has a long-term good corrosion inhibition effect on the corrosion behavior of carbon steel in seawater.
(3) The target positioning and recovery performance is that 0.5g of MBT intercalated magnetic zinc-aluminum-cerium hydrotalcite sample is uniformly dispersed in deionized water or ethanol, a magnet is placed beside the sample, the sample can be gathered in 10s, the synthesized sample has high paramagnetism, and the target positioning and rapid recovery performance can be realized by using an external magnetic field.
(4) The released MBT intercalated magnetic zinc-aluminum-cerium hydrotalcite material is dried, sintered in a box furnace at 450 ℃ and re-dispersed in an MBT methanol aqueous solution to be stirred at a high speed for 24 hours. As shown in fig. 6, the layered structure of the hydrotalcite disappears after sintering, and the layered structure of the original hydrotalcite is restored after the hydrotalcite is dispersed in the MBT solution, which indicates that the magnetic hydrotalcite structure intercalated with the corrosion inhibitor can be reconstructed, and the corrosion inhibitor still has high corrosion inhibition efficiency through electrochemical impedance spectroscopy test. The good recycling performance of the synthesized MBT intercalation magnetic zinc-aluminum-cerium hydrotalcite material is demonstrated.
Drawings
FIG. 1 is Fe3O4Transmission photographs of @ ZnAlce-MBT LDH;
FIG. 2 is Fe3O4The XRD pattern of @ ZnAlce-MBT LDH;
FIG. 3 is Fe3O4An infrared spectrogram of @ ZnAlce-MBT LDH;
FIG. 4 is Fe3O4The release curve of @ ZnAlce-MBT LDH in 3.5% NaCl solution of MBT, wherein MF ON is applied magnetic field; MF OFF is no magnetic field applied;
FIG. 5 shows the results of the evaluation of Q235 steels in 3.5% NaCl and 3.5% NaCl +2g/L Fe3O4Electrochemical impedance spectroscopy in a @ ZnAlce-MBT LDH solution;
FIG. 6 is Fe3O4XRD patterns after release, sintering and redispersion in MBT solution of @ ZnAlce-MBT LDH.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Wherein FeCl3·6H2O, ethylene glycol, Zn (NO)3)2·6H2O is produced by the Guangdong chemical research institute of Tianjin; the crystallized sodium acetate is produced by chemical reagent science and technology limited of Fengshan ship in Tianjin; al (NO)3)3·9H2O、Ce(NO3)3·9H2O, MBT and NaOH are manufactured by Shanghai Aladdin Biotechnology Ltd; methanol was produced by chemical reagents ltd of mimiuiou, tianjin; all chemicals were analytically pure.
Example 1
(1) 2.7g FeCl was weighed3·6H2O，7.2g CH3COONa·3H2O, dissolved in 60ml of ethylene glycol, stirred to form a uniform yellow solution, transferred to an autoclave, and placed in a 160 ℃ drying oven for reaction for 18 h. Separating the obtained product with Ru Fe-B permanent magnet, repeatedly washing with deionized water and ethanol, drying in a drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4。
(2) 0.174g of Fe was weighed out3O4Dispersing in 100ml methanol, and ultrasonic treating for 15min to obtain uniform suspension. Transferring the suspension into a four-mouth bottle, stirring at room temperature, and continuously introducing N during stirring2。
(3) According to n (Zn)2+)/n(Fe3O4) Weighing Zn (NO) at a ratio of 2.03)2·6H2O, in n (Zn)2+)/n(Al3+) Ratio of 4:1, n (Al)3+)/n(Ce3+) Weigh Al (NO) at a ratio of 5:13)3·9H2O and Ce (NO)3)3·9H2O, Zn (NO)3)2·6H2O，Al(NO3)3·9H2O and Ce (NO)3)3·9H2O was dissolved in 60ml of methanol and referred to as A solution.
(4) Weighing a certain amount of NaOH to prepare a methanol solution with the concentration of 0.8mol/L, which is called as a B solution.
(5) Adding the solution A and the solution B into the four-mouth bottle dropwise simultaneously, continuously mechanically stirring in the dropwise adding process and introducing N2And controlling the pH value of the reaction solution to be 8.5 by using the solution B.
(6) After completion of the dropwise addition, the resulting reaction slurry was transferred to an autoclave, which was then placed in a drying oven at 60 ℃ for aging for 24 hours. Separating the obtained product with Ru Fe-B permanent magnet, centrifuging with ethanol, washing to neutrality, drying in drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4@ZnAlCe-NO3LDH。
(7) Weighing a certain amount of MBT to prepare 0.1mol/L methanol aqueous solution (V)Methanol/VWater (W)1:1), quantitative Fe3O4@ZnAlCe-NO3LDH is dispersed in the solution, stirred at high speed for 24h, and N is continuously introduced during stirring2. Centrifugally washing the obtained suspension with ethanol and deionized water, drying in a drying oven at 60 deg.C for 24h, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
As can be seen from FIG. 1, Fe3O4The surface of the magnetic particles is uniformly wrappedA layer of hydrotalcite, Fe3O4The diameter of the magnetic particles is about 380nm, and the thickness of the hydrotalcite is about 50-60 nm.
As can be seen from FIG. 2, Fe is present3O4The standard characteristic peaks (JCPDS #88-0866) of (A) correspond to the (111), (220), (222), (400), (422), (511) and (440) crystal planes, respectively. In addition to this, characteristic diffraction peaks of (003), (006), (012), (018), and (113) of the layered structure of hydrotalcite appear. And each crystal face diffraction peak is very sharp, which reflects that the product has good layered structure and crystal structure.
From FIG. 3, 581cm-1The peak at (A) is due to the vibrational peak of Fe-O. 3439cm-1The strong broad peak belongs to the symmetric stretching peak of O-H on LDH and water between LDH layers. 1630cm-1The peak at (B) represents the stretching vibration of the hydroxyl group O-H and the bending vibration of interlayer water. 1485cm-1，1109cm-1，1056cm-1Is the peak of N ═ C-S, 426cm-1Is the vibration absorption peak of M-O (M represents a metal). The synthesis of MBT intercalated magnetic zinc-aluminum-cerium hydrotalcite is illustrated.
As described above, it was demonstrated that Fe having good crystallinity was synthesized3O4The core is the LDH of the MBT corrosion inhibitor intercalation layer, and the shell is the magnetic corrosion inhibitor composite material.
Example 2
(1) 2.7g FeCl was weighed3·6H2O，7.2g CH3COONa·3H2O, dissolved in 60ml of ethylene glycol, stirred to form a uniform yellow solution, transferred to an autoclave, and placed in a 200 ℃ drying oven for reaction for 16 h. Separating the obtained product with Ru Fe-B permanent magnet, repeatedly washing with deionized water and ethanol, drying in a drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4。
(2) 0.174g of Fe was weighed out3O4Dispersing in 100ml methanol, and ultrasonic treating for 15min to obtain uniform suspension. Transferring the suspension into a four-mouth bottle, stirring at room temperature, and continuously introducing N during stirring2。
(3) According to n (Zn)2+)/n(Fe3O4) Weighing Zn (NO) in a ratio of 10.03)2·6H2O, in n (Zn)2+)/n(Al3+) Ratio of 2:1, n (Al)3+)/n(Ce3+) Weigh Al (NO) at 6:1 ratio3)3·9H2O and Ce (NO)3)3·9H2O, Zn (NO)3)2·6H2O，Al(NO3)3·9H2O and Ce (NO)3)3·9H2O was dissolved in 60ml of methanol and referred to as A solution.
(4) Weighing a certain amount of NaOH to prepare a methanol solution with the concentration of 0.8mol/L, which is called as a B solution.
(5) Adding the solution A and the solution B into the four-mouth bottle dropwise simultaneously, continuously mechanically stirring in the dropwise adding process and introducing N2And controlling the pH value of the reaction solution to be 11 by using the solution B.
(6) After completion of the dropwise addition, the resulting reaction slurry was transferred to an autoclave, which was aged in a drying oven at 70 ℃ for 28 hours. Separating the obtained product with Ru Fe-B permanent magnet, centrifuging with ethanol, washing to neutrality, drying in drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4@ZnAlCe-NO3LDH。
(7) Weighing a certain amount of MBT to prepare 0.2mol/L methanol aqueous solution (V)Methanol/VWater (W)1:1), quantitative Fe3O4@ZnAlCe-NO3 -Dispersing LDH in the solution, stirring at high speed for 18h, and continuously introducing N during stirring2. Centrifugally washing the obtained suspension with ethanol and deionized water, drying in a drying oven at 60 deg.C for 24h, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
Example 3
(1) 2.7g FeCl was weighed3·6H2O，7.2g CH3COONa·3H2O, dissolved in 60ml of ethylene glycol, stirred to form a uniform yellow solution, transferred to an autoclave, and placed in a 180 ℃ drying oven for reaction for 14 h. Separating the obtained product with Ru Fe-B permanent magnet, repeatedly washing with deionized water and ethanol, drying in a drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4。
(2) 0.174g of Fe was weighed out3O4Dispersing in 100ml methanol, and ultrasonic treating for 15min to obtain uniform suspension. Transferring the suspension into a four-mouth bottle, stirring at room temperature, and continuously introducing N during stirring2。
(3) According to n (Zn)2+)/n(Fe3O4) Weighing Zn (NO) at a ratio of 5.03)2·6H2O, in n (Zn)2+)/n(Al3+) Ratio of 5:1, n (Al)3+)/n(Ce3+) Weighing Al (NO) in a ratio of 7:13)3·9H2O and Ce (NO)3)3·9H2O, Zn (NO)3)2·6H2O，Al(NO3)3·9H2O and Ce (NO)3)3·9H2O was dissolved in 60ml of methanol and referred to as A solution.
(4) Weighing a certain amount of NaOH to prepare a methanol solution with the concentration of 0.8mol/L, which is called as a B solution.
(5) Adding the solution A and the solution B into the four-mouth bottle dropwise simultaneously, continuously mechanically stirring in the dropwise adding process and introducing N2And controlling the pH value of the reaction solution to be 10 by using the solution B.
(6) After completion of the dropwise addition, the resulting reaction slurry was transferred to an autoclave, which was aged in a drying oven at 80 ℃ for 18 hours. Separating the obtained product with Ru Fe-B permanent magnet, centrifuging with ethanol, washing to neutrality, drying in drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4@ZnAlCe-NO3LDH。
(7) Weighing a certain amount of MBT to prepare 0.5mol/L methanol aqueous solution (V)Methanol/VWater (W)1:1), quantitative Fe3O4@ZnAlCe-NO3 -Dispersing LDH in the solution, stirring at high speed for 12h, and continuously introducing N during stirring2. Centrifugally washing the obtained suspension with ethanol and deionized water, drying in a drying oven at 60 deg.C for 24h, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
Example 4
(1) 2.7g FeCl was weighed3·6H2O，7.2g CH3COONa·3H2O, dissolved in 60ml of ethylene glycol, stirred to form a uniform yellow solution, transferred to an autoclave, and placed in a 200 ℃ drying oven for 12 hours. Separating the obtained product with Ru Fe-B permanent magnet, repeatedly washing with deionized water and ethanol, drying in a drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4。
(2) 0.174g of Fe was weighed out3O4Dispersing in 100ml methanol, and ultrasonic treating for 15min to obtain uniform suspension. Transferring the suspension into a four-mouth bottle, stirring at room temperature, and continuously introducing N during stirring2。
(3) According to n (Zn)2+)/n(Fe3O4) Weighing Zn (NO) at a ratio of 30.03)2·6H2O, in n (Zn)2+)/n(Al3+) Ratio of 3:1, n (Al)3+)/n(Ce3+) Weighing Al (NO) in a ratio of 8:13)3·9H2O and Ce (NO)3)3·9H2O, Zn (NO)3)2·6H2O，Al(NO3)3·9H2O and Ce (NO)3)3·9H2O was dissolved in 60ml of methanol and referred to as A solution.
(4) Weighing a certain amount of NaOH to prepare a methanol solution with the concentration of 0.8mol/L, which is called as a B solution.
(5) Adding the solution A and the solution B into the four-mouth bottle dropwise simultaneously, continuously mechanically stirring in the dropwise adding process and introducing N2And controlling the pH value of the reaction solution to be 9.5 by using the solution B.
(6) After completion of the dropwise addition, the resulting reaction slurry was transferred to an autoclave, which was then placed in a drying oven at 100 ℃ for aging for 36 hours. Separating the obtained product with Ru Fe-B permanent magnet, centrifuging with ethanol, washing to neutrality, drying in drying oven at 60 deg.C for 24 hr, and grinding to obtain Fe3O4@ZnAlCe-NO3LDH。
(7) Weighing a certain amount of MBT to prepare 0.4mol/L methanol aqueous solution (V)Methanol/VWater (W)1:1), quantitative Fe3O4@ZnAlCe-NO3LDH dispersed in the above solutionStirring at high speed for 16h, and continuously introducing N during stirring2. Centrifugally washing the obtained suspension with ethanol and deionized water, drying in a drying oven at 60 deg.C for 24h, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A controllable-release magnetic zinc-aluminum-cerium hydrotalcite loaded 2-mercaptobenzothiazole corrosion inhibitor is characterized in that: the method comprises the following steps:
step 1, uniformly dispersing ferroferric oxide in a mixed solution of methanol and water to obtain a uniform suspension, and adding Zn (NO) into the suspension3)2·6H2O is dissolved and dispersed in the suspension, wherein n (Zn)2+)/n(Fe3O4) 1 to 1, adding ferroferric oxide and Zn (NO)3)2·6H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5);
step 2, adding Al (NO)3)3·9H2O and Ce (NO)3)3·9H2Dissolving and dispersing O in a mixed solution of methanol and water to obtain a mixed salt solution, wherein n (Zn)2+)/n(Al3+)＝(1-6):1，n(Al3+)/n(Ce3+) 1 in case of (4-9), Al (NO) is added3)3·9H2O and Ce (NO)3)3·9H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5);
step 3, dissolving and dispersing sodium hydroxide in a methanol solution to obtain an alkali liquor, wherein inert protective gas is kept introduced into the mixed solution in the process of adding NaOH to avoid the influence of carbon dioxide and oxygen, wherein the molar concentration of the sodium hydroxide methanol solution is 0.6-1.0 mol/L;
step 4, simultaneously dripping the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 into the suspension obtained in the step 1, keeping introducing inert protective gas into the mixed solution in the dripping process so as to avoid the influence of carbon dioxide and oxygen and keeping mechanical stirring for dispersion, wherein the pH value of the solution is 7-12 after the dripping is finished;
step 5, transferring the reaction slurry obtained in the step 4 into a high-pressure reaction kettle, then placing the high-pressure reaction kettle into a drying box at 50-120 ℃ for aging, separating the obtained product by using a Ru Fe B permanent magnet, centrifugally washing the product to be neutral by using ethanol, drying the product for 20-24 hours in the drying box at 50-70 ℃, and grinding the product to obtain Fe3O4@ZnAlCe-NO3 --LDH；
And 6, preparing a methanol aqueous solution with the concentration of 0.1-0.5mol/L by using MBT, wherein the volume ratio of methanol to water is (1-5): 1, taking the Fe prepared in the step 53O4@ZnAlCe-NO3Dispersing LDH in the above solution, stirring at high speed for 12-24 hr while continuously introducing inert protective gas, centrifuging the obtained suspension with ethanol and deionized water, drying in a drying oven at 50-70 deg.C for 20-24 hr, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
2. The controlled-release magnetic zinc-aluminum-cerium hydrotalcite supported 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in step 1, n (Zn)2+)/n(Fe3O4) 1, the volume ratio of methanol to water is (1-5): 1, stirring or ultrasonically dissolving and dispersing at the temperature of 20-30 ℃ for 10-20 min.
3. The controlled-release magnetic zinc-aluminum-cerium hydrotalcite supported 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in step 2, n (Zn)2+)/n(Al3+)＝(2-5):1，n(Al3+)/n(Ce3+) 1, the volume ratio of methanol to water is (1-5): 1, inStirring or ultrasonically dissolving and dispersing at 20-30 deg.C for 10-20 min; in step 3, the molar concentration of the sodium hydroxide methanol solution is 0.8 mol/L.
4. The controlled-release magnetic zinc-aluminum-cerium hydrotalcite supported 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in the step 4, high-speed mechanical stirring is adopted for 300-500 revolutions per minute, uniform dropping is adopted, the dropping time is controlled to be 1-3 hours, preferably 1.5-3 hours, the volume ratio of the suspension obtained in the step 1, the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 is (4-6): 2-4): 3-5, and the pH of the solution after the dropping is controlled to be 8.5-11.
5. The controlled-release magnetic zinc-aluminum-cerium hydrotalcite supported 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in the step 5, the aging temperature is 60-100 ℃, and the aging time is 10-36 h; in step 6, the molar concentration of the MBT methanol aqueous solution is 0.1-0.5mol/L, Fe3O4@ZnAlCe-NO3The mass of the LDH is 0.1-0.8 g.
6. The method for preparing the controlled-release magnetic zinc-aluminum-cerium hydrotalcite-supported 2-mercaptobenzothiazole corrosion inhibitor as described in claims 1 to 5, is characterized in that: the method comprises the following steps:
step 1, uniformly dispersing ferroferric oxide in a mixed solution of methanol and water to obtain a uniform suspension, and adding Zn (NO) into the suspension3)2·6H2O is dissolved and dispersed in the suspension, wherein n (Zn)2+)/n(Fe3O4) 1 to 1, adding ferroferric oxide and Zn (NO)3)2·6H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5);
step 2, adding Al (NO)3)3·9H2O and Ce (NO)3)3·9H2Dissolving and dispersing O in a mixed solution of methanol and water to obtainMixed salt solution of n (Zn)2+)/n(Al3+)＝(1-6):1，n(Al3+)/n(Ce3+) 1 in case of (4-9), Al (NO) is added3)3·9H2O and Ce (NO)3)3·9H2And keeping introducing inert protective gas into the mixed solution in the O process to avoid the influence of carbon dioxide and oxygen, wherein the volume ratio of methanol to water is (1-10): (1-5);
step 3, dissolving and dispersing sodium hydroxide in a methanol solution to obtain an alkali liquor, wherein inert protective gas is kept introduced into the mixed solution in the process of adding NaOH to avoid the influence of carbon dioxide and oxygen, wherein the molar concentration of the sodium hydroxide methanol solution is 0.6-1.0 mol/L;
step 4, simultaneously dripping the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 into the suspension obtained in the step 1, keeping introducing inert protective gas into the mixed solution in the dripping process so as to avoid the influence of carbon dioxide and oxygen and keeping mechanical stirring for dispersion, wherein the pH value of the solution is 7-12 after the dripping is finished;
step 5, transferring the reaction slurry obtained in the step 4 into a high-pressure reaction kettle, then placing the high-pressure reaction kettle into a drying box at 50-120 ℃ for aging, separating the obtained product by using a Ru Fe B permanent magnet, centrifugally washing the product to be neutral by using ethanol, drying the product for 20-24 hours in the drying box at 50-70 ℃, and grinding the product to obtain Fe3O4@ZnAlCe-NO3 --LDH；
And 6, preparing a methanol aqueous solution with the concentration of 0.1-0.5mol/L by using MBT, wherein the volume ratio of methanol to water is (1-5): 1, taking the Fe prepared in the step 53O4@ZnAlCe-NO3Dispersing LDH in the above solution, stirring at high speed for 12-24 hr while continuously introducing inert protective gas, centrifuging the obtained suspension with ethanol and deionized water, drying in a drying oven at 50-70 deg.C for 20-24 hr, and grinding to obtain Fe3O4@ZnAlCe-MBT LDH。
7. The controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor according to claim 1The preparation method is characterized by comprising the following steps: in step 1, n (Zn)2+)/n(Fe3O4) 1, the volume ratio of methanol to water is (1-5): 1, stirring or ultrasonically dissolving and dispersing at the temperature of 20-30 ℃ for 10-20 min.
8. The preparation method of the controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in step 2, n (Zn)2+)/n(Al3+)＝(2-5):1，n(Al3+)/n(Ce3+) 1, the volume ratio of methanol to water is (1-5): 1, stirring or ultrasonically dissolving and dispersing at 20-30 ℃ for 10-20 min; in step 3, the molar concentration of the sodium hydroxide methanol solution is 0.8 mol/L.
9. The preparation method of the controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in the step 4, high-speed mechanical stirring is adopted for 300-500 revolutions per minute, uniform dropping is adopted, the dropping time is controlled to be 1-3 hours, preferably 1.5-3 hours, the volume ratio of the suspension obtained in the step 1, the mixed salt solution obtained in the step 2 and the alkali liquor obtained in the step 3 is (4-6): 2-4): 3-5, and the pH of the solution after the dropping is controlled to be 8.5-11.
10. The preparation method of the controlled-release magnetic zinc-aluminum-cerium hydrotalcite-loaded 2-mercaptobenzothiazole corrosion inhibitor according to claim 1, characterized in that: in the step 5, the aging temperature is 60-100 ℃, and the aging time is 10-36 h; in step 6, the molar concentration of the MBT methanol aqueous solution is 0.1-0.5mol/L, Fe3O4@ZnAlCe-NO3The mass of the LDH is 0.1-0.8 g.
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