CN110760854A - Hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor and preparation method thereof - Google Patents
Hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydroxyethylidene diphosphonic acid intercalation zinc-aluminum hydrotalcite corrosion inhibitor and a preparation method thereof, wherein a mixed salt solution of zinc nitrate and aluminum nitrate is prepared, a sodium hydroxide solution is prepared, the two solutions are dropwise added into hydroxyethylidene diphosphonic acid liquid, stirring and heating in water bath are carried out while dropwise adding is carried out, after dropwise adding is finished, the reaction liquid is poured into a high-pressure reaction kettle, the high-pressure reaction kettle is placed in a vacuum drying furnace for heat preservation and aging, the high-pressure reaction kettle is taken out from the vacuum drying furnace, cooled to room temperature, centrifugally washed, and centrifugally obtained solid is placed in a vacuum drying box for drying, so that the hydroxyethylidene diphosphonic acid intercalation zinc-aluminum hydrotalcite corrosion inhibitor can be obtained. The invention uses the hydrotalcite as the nano container, so that the nano container has the characteristic of sustained and controlled release, and the problem of large loss of the corrosion inhibitor medicament is solved; meanwhile, the synergistic corrosion inhibition effect of the zinc salt, the hydroxyethylidene diphosphonic acid and other corrosion inhibitors on the seawater is utilized, so that the corrosion inhibitor has a good corrosion inhibition effect on the corrosion behavior of the carbon steel in the seawater.
Description
Technical Field
The invention relates to the technical field of corrosion inhibitors for seawater circulating cooling systems, in particular to a hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor, a preparation method and application thereof.
Background
The seawater circulating cooling technology is a cooling technology (Hou pure, seawater cooling technology, ocean technology, 2002,21 (4): 33-40) which takes original seawater as a cooling medium, is cooled once by a heat exchange device, and then is cooled by a cooling tower and is recycled; the method has the advantages of small water intake, low engineering investment and operating cost, small sewage discharge and the like, so that the utilization of seawater as industrial circulating cooling water is one of important ways for relieving the shortage of fresh water resources in coastal cities and regions in China and protecting the marine ecological environment. However, the seawater has high salt content (especially the seawater concentrated after circular cooling), complex composition and higher conductivity than that of the common fresh water by two orders of magnitude, so the corrosion problem of a cooling system is the first difficult problem to be solved by developing the seawater circular cooling technology. Aiming at the corrosion of seawater medium and considering economic cost and other factors, a cheap and easily available carbon steel material is often selected and added with a corrosion inhibitor to control the corrosion (Gaoyua, Liu vibrating method, Zhang Lihui, Lixiahui, research progress of a green carbon steel corrosion inhibitor in a seawater circulating cooling water system, application chemical industry, 2011,40(9): 1653-.
For the research on corrosion inhibitors in seawater media, formaldehyde, chromate, nitrite and other corrosion inhibitors are often adopted in the early stage; the corrosion inhibitors have high corrosion inhibition efficiency on carbon steel, but have high toxicity and serious environmental pollution and do not meet the sewage discharge standard. In consideration of the requirements of environmental protection, high efficiency and economy, low-pollution or pollution-free molybdate, tungstate, silicate, zinc salt, rare earth salt, phosphate (phosphate, polyphosphate, organic phosphonic acid and the like), a whole organic system (such as Mercaptobenzothiazole (MBT), Benzotriazole (BTA), methylbenzotriazole (TTA) and the like), natural organic matters (cassava starch, yeast, chitosan and the like) and other single cooling water corrosion inhibitors and a composite cooling water corrosion inhibitor formed by compounding two or more corrosion inhibitors are formed in sequence at home and abroad through a large number of researches from the end of the 20 th century. From the aspect of corrosion inhibition effect, due to the synergistic effect existing among different corrosion inhibitors, the corrosion inhibition effect of the composite corrosion inhibitor under the same addition concentration is better than that of a single corrosion inhibitor. For example, based on a single molybdate corrosion inhibitor, e.g., Ranunculan magnolia and the like systematically researches the corrosion inhibition effect of binary, ternary and quaternary compound corrosion inhibitors such as zinc salt, silicate, gluconate, hydroxyethylidene diphosphonic acid (HEDP) and amino trimethyl phosphonic Acid (ATMP) on the seawater medium carbon steel, and optimizes the formula of the quaternary corrosion inhibitor consisting of molybdate, zinc salt, gluconate and HEDP, wherein the corrosion inhibition efficiency reaches more than 93 percent (Ruiyan, Lumaixi, Lianghuang, Wei Yili, the corrosion inhibition effect of the molybdate compound corrosion inhibitor on the seawater medium carbon steel, corrosion and protection, 2007,28 (2): 61-64). Zinc sulfate, calcium gluconate, HEDP, silicate, tungstate, polyphosphate and the like are compounded to develop a high-efficiency green corrosion inhibitor (research on corrosion inhibition performance and corrosion inhibition behavior of a composite corrosion inhibitor in Zhouzu, Demin, Sunhui and high-temperature seawater, proceedings of China oceanic university, 2010,40 (12): 115-120) suitable for natural seawater and high-temperature seawater. Marin-Cruz and the like research the corrosion inhibition effect of single hydroxycitric acid (HPA) or HEDP and a compound corrosion inhibitor thereof on 1018 carbon steel in cooling water, and prove that the corrosion inhibition efficiency of the carbon steel can be improved by compounding the single hydroxycitric acid (HPA) or the HEDP (the corrosion inhibition effect of the carbon steel and the compound corrosion inhibitor) and the corrosion inhibition effect of the carbon steel can be improved by the Marin-Cruz J, the Camera-Sierra R, the Pech-Canul M A, the Gonzalez I, the EIS catalysis of the evolution calcium carbonate scaling in the chemical systems in the presence of inhibitors, J.solid State electrochem, 2007,11:1245 + 1252). Although the corrosion inhibition efficiency of the material in the seawater medium can be improved by developing novel corrosion inhibitors, compounding corrosion inhibitors and other methods, the existing corrosion inhibitors have the problems of large medicament loss, high cost, difficult recovery and the like. Therefore, the development of a multifunctional intelligent corrosion inhibition material which can control release and can be recycled has important significance for reducing the consumption of the corrosion inhibitor, reducing the environmental hazard of the corrosion inhibitor and improving the efficiency of the corrosion inhibitor (Zhang quan, the research progress of a slow release technology and the application of the slow release technology in the energy industry, Shanghai institute of electric power, 2013,29 (4): 355-363).
In the aspect of intelligentization of corrosion inhibitors, Kendig and the like are based on the concept of active corrosion protection or self-healing, and the corrosion inhibitors are loaded into a micron/nano container through an intercalation or encapsulation method and then released into an environmental medium through the actions of desorption, environmental pH change, ion exchange or mechanical force and the like when contacting with corrosive solution, so that the purpose of retarding the corrosion of materials is achieved (Kendig M, Hon M, War)ren L, 'Smart' correction inhibiting Coatings, progress Organic Coatings,2003,47: 183-. Common micro/nano containers comprise nano microspheres, one-dimensional nanotubes, two-dimensional nano layered materials and the like. For example, Wang et al synthesized benzoate intercalated zinc-aluminum hydrotalcite (ZnAl-BZ LDH), and added it as corrosion inhibitor into 3.5% NaCl solution, studied the release and corrosion-inhibition behavior of benzoate in solution, and played the effect of reducing the corrosion rate of Q235 steel (Wang Yi, Zhang Dun, Synthesis, catalysis, and controlled release emulsion corrosion modifier of benzoate intercalated Zn-alumina hydrotalcite hydroxides, Materials Research Bulletin,2011,46: 1963-. Hang et al studied BTSA (2-benzothiazole-succinic acid) intercalated MgAl-BTSA LDH and ZnAl-BTSA LDH on carbon steel at 3% NaCl and 3% Na2SO4Corrosion inhibition efficiency in solution (Hang Thi Xuan, Truc Trinh, Duong Nguyen Thuy, Vu Pham Gia, Hong Thai, Preparation and characterization of nanocontologiners of corrosion inhibition of coated Clay Science 2012,67-68: 18-25). Kameda et al successfully prepared HEDP intercalated LiAl hydrotalcite by coprecipitation method and analyzed Nd in HEDP macromolecular pair aqueous solution3+And Sr2+(Kameda T, ShinmouT, Yoshioka T. kinetic and equibrium studios on the uptake of Nd)3+and Sr2+byLi–Al layered double hydroxide intercalated with1-hydroxyethane-1,1-diphosphonic acid[J]Journal of Industrial and Engineering Chemistry,2016,36: 96-101). Yan Huajie et al developed a molybdate intercalated zinc aluminum cerium hydrotalcite corrosion inhibitor by coprecipitation and demonstrated its effective corrosion inhibition on carbon steel in simulated seawater media (Yan Huajie, Wang Jihui, Zhang Yu, Hu Wenbin, Preparation and inhibition properties of molybdenum intercalated ZnAlcalaied double hydroxide, Journal of Alloys and Compounds,2016,678: 171-.
Disclosure of Invention
The invention overcomes the defects in the prior art, and the prior corrosion inhibitor has the problems of large medicament loss, high cost, difficult recovery and the like, and provides the hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor, the preparation method and the application thereof; meanwhile, the synergistic corrosion inhibition effect of the zinc salt, the hydroxyethylidene diphosphonic acid and other corrosion inhibitors on the seawater is utilized, so that the corrosion inhibitor has a good corrosion inhibition effect on the corrosion behavior of the carbon steel in the seawater.
The purpose of the invention is realized by the following technical scheme.
A hydroxyl ethylidene diphosphonic acid intercalation zinc-aluminum hydrotalcite corrosion inhibitor and a preparation method thereof are carried out according to the following steps:
step 1, weighing zinc nitrate (Zn (NO)3)2) Aluminum nitrate (Al (NO)3)3) Solids removal by CO2The deionized water is prepared into a mixed salt solution with the molar concentration of 0.4-0.6mol/L (namely the concentration of two metal ions is 0.4-0.6 mol/L);
step 2, weighing sodium hydroxide (NaOH) solid, and removing CO2Preparing sodium hydroxide solution with the molar concentration of 1.8-2.5mol/L by using the deionized water;
and 5, taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature of 20-25 ℃, centrifuging the obtained suspension, washing with deionized water to be neutral, drying the centrifuged solid in a vacuum drying oven at 30-90 ℃ for 10-30h, and grinding to obtain the hydroxyethylidene diphosphonic intercalation zinc-aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor.
In step 1, Zn in a mixed salt solution2+And Al3+The molar ratio is (1.5-4.0): and 1, the molar concentration of the mixed salt solution is 0.5 mol/L.
In step 2, the molar concentration of the sodium hydroxide solution is 1-2.0 mol/L.
In step 3, hydroxyethylidene diphosphonic acid (HEDP) liquid is mixed with aluminum ions (Al)3+) In a molar ratio of 1: (1-3), the water bath temperature is 25-80 ℃, the protective gas adopts nitrogen, argon or helium, the liquid for controlling the pH of the reaction liquid is ammonia water, and the concentration of the ammonia water is 1-5 mol/L.
In the step 4, the temperature of the vacuum drying furnace is 80-160 ℃, and the aging time is 10-36 h.
In the step 5, the temperature of the vacuum drying oven is 40-80 ℃, and the drying time is 12-24 h.
Testing slow release and corrosion inhibition functions of the hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor:
(1) sustained and controlled release characteristics
Weighing 0.4g of hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite material, soaking in 200ml of room-temperature 3.5% NaCl solution, and stirring; and measuring the change curve of the content of the phosphorus element in the solution along with the soaking time by using an inductively coupled plasma mass spectrometer, and converting the change curve into a release curve of HEDP ions in a NaCl solution, as shown in figure 1. The amount of the released HEDP ions is increased along with the increase of the soaking time; within 60 minutes from the start of release, the amount of HEDP ions released rapidly increased; after 6 hours of soaking, substantially complete release of HEDP ions was achieved. Therefore, the synthesized hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor material has obvious sustained and controlled release characteristics.
(2) Good corrosion inhibition performance
The adopted area is 1cm2The Q235 steel sample after grinding and polishing treatment is used as a working electrode, a saturated calomel electrode and a platinum sheet are respectively used as a reference electrode and an auxiliary electrode, and then an Autolab 302F electrochemical workstation is utilized to measure a polarization curve and an electrochemical impedance spectrum of the Q235 steel in 3.5 percent NaCl and 3.5 percent NaCl +2g/L ZnAl-HEDP LDH solution,as shown in fig. 2 and 3. As can be seen from FIG. 2, after ZnAl-HEDP LDH is added into 3.5% NaCl solution, the corrosion potential of Q235 steel is obviously shifted positively, and the corrosion current density is obviously reduced; the corrosion inhibition rate of the ZnAl-HEDP LDH material calculated according to the corrosion current varies between 40 and 70 percent. As can be seen from FIG. 3, after ZnAl-HEDP LDH is added into 3.5% NaCl solution, the impedance modulus of Q235 steel is obviously increased, and the corrosion inhibition rate of the ZnAl-HEDP LDH material calculated according to the impedance modulus is changed between 40% and 75%. Namely, the synthesized hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor material has good corrosion inhibition effect on the corrosion behavior of carbon steel in seawater.
The invention has the beneficial effects that: the hydroxyl ethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor takes hydrotalcite as a nano container, so that the developed corrosion inhibition material has the characteristics of slow and controlled release; and the synergistic corrosion inhibition effect of the zinc salt, the hydroxyethylidene diphosphonic acid and other corrosion inhibitors on the seawater is utilized, so that the corrosion inhibitor has a good corrosion inhibition effect on the corrosion behavior of the carbon steel in the seawater.
Drawings
FIG. 1 is the hydroxyethylidene diphosphonic acid release profile of hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor in 3.5% NaCl solution.
FIG. 2 is a polarization curve of Q235 steel in a corrosion inhibitor solution of 3.5% NaCl, 3.5% NaCl +2g/L hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite (ZnAl-HEDP LDH).
FIG. 3 is the electrochemical impedance spectrum of Q235 steel in 3.5% NaCl, 3.5% NaCl +2g/L hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor solution.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the examples, Zn (NO)3)2·6H2O、Al(NO3)3·9H2O and NaOH are produced by Yueli chemical Co., Ltd, Tianjin; HEDP is produced by Shanghai Aladdin Biotechnology Ltd; all chemicals were analytically pure.
Example 1
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 1.5:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.5mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.0mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:3.0 and called solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 35 ℃ for incubation. Then, simultaneously dropwise adding the solution A and the solution B into a three-necked bottle containing the solution C, stirring at high speed by using an electric stirrer in the dropwise adding process, and introducing N2And controlling the pH value of the solution to be about 9 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at the temperature of 80 ℃ for heat preservation and aging for 12 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at 40 ℃ for 12h, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 2
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 2.0:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.5mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.0mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) Weighing hydroxyethylidene bis (II) in a ratio of 1.0:2.0Phosphonic acid 25ml, called C solution.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 50 ℃ for incubation. Then, simultaneously dropwise adding the solution A and the solution B into a three-necked bottle containing the solution C, stirring at high speed by using an electric stirrer in the dropwise adding process, and introducing N2And controlling the pH value of the solution to be about 10 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 120 ℃ for heat preservation and aging for 24 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at 60 ℃ for 16h, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 3
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 2.5:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.5mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.0mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:1.0 and referred to as solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 60 ℃ for incubation. Then, simultaneously dropwise adding the solution A and the solution B into a three-necked bottle containing the solution C, stirring at high speed by using an electric stirrer in the dropwise adding process, and introducing N2And controlling the pH value of the solution to be about 11 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 140 ℃ for heat preservation and aging for 20 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 20 hours, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 4
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 3.0:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.5mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.0mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:3.0 and called solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 80 ℃ for incubation. Then, simultaneously dropwise adding the solution A and the solution B into a three-necked bottle containing the solution C, stirring at high speed by using an electric stirrer in the dropwise adding process, and introducing N2And controlling the pH value of the solution to be about 9 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 160 ℃ for heat preservation and aging for 30 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at the temperature of 80 ℃ for 16h, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 5
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 4.0:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into mixed salt concentrateA mixed salt solution having a degree of 0.5mol/L and a volume of 50ml was referred to as solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.0mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:2.0 and called solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 70 ℃ for incubation. Then, simultaneously dropwise adding the solution A and the solution B into a three-necked bottle containing the solution C, stirring at high speed by using an electric stirrer in the dropwise adding process, and introducing N2And controlling the pH value of the solution to be about 10 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 100 ℃ for heat preservation and aging for 36 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at 50 ℃ for 24 hours, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 6
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 4.0:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.4mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water of (2) is prepared into NaOH solution with the concentration of 1.8mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:4.0 and called solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 50 ℃ for incubation. And then, dropwise adding the solution A and the solution B into a three-neck flask containing the solution C at the same time, stirring at a high speed by using an electric stirrer in the dropwise adding process, introducing argon, and controlling the pH value of the solution to be about 10 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 70 ℃ for heat preservation and aging for 40 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at the temperature of 30 ℃ for 30 hours, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
Example 7
(1) According to n (Zn)2+)/n(Al3+) Weighing Zn (NO) at a ratio of 1.5:13)2·6H2O and Al (NO)3)3·9H2O, by CO removal2The deionized water is prepared into a mixed salt solution with the mixed salt concentration of 0.6mol/L and the volume of 50ml, and the mixed salt solution is called solution A.
(2) Weighing a certain amount of NaOH, and removing CO2The deionized water is prepared into NaOH solution with the concentration of 2.5mol/L and the volume of 25ml, and the NaOH solution is called B solution.
(3) According to the formula n (HEDP)/n (Al)3+) 25ml of hydroxyethylidene diphosphonic acid was weighed out at a ratio of 1.0:1.0 and referred to as solution C.
(4) The solution C was transferred to a 250ml three-necked flask and placed in a water bath to heat to 60 ℃ for incubation. And then, dropwise adding the solution A and the solution B into a three-neck flask containing the solution C at the same time, stirring at a high speed by using an electric stirrer in the dropwise adding process, introducing argon, and controlling the pH value of the solution to be about 9 by using ammonia water until the dropwise adding process is finished.
(5) And (3) quickly pouring the reaction slurry into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 180 ℃ for heat preservation and aging for 9 hours.
(6) And taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature, centrifuging the obtained suspension, washing with deionized water to be neutral, drying in a vacuum drying oven at the temperature of 90 ℃ for 10 hours, and further grinding to obtain the ZnAl-HEDP LDH corrosion inhibitor material.
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 hydroxyethylidene diphosphonic acid intercalated zinc-aluminum hydrotalcite corrosion inhibitor is characterized in that: the method comprises the following steps:
step 1, weighing zinc nitrate and aluminum nitrate solids, and removing CO2Preparing a mixed salt solution with the molar concentration of 0.4-0.6mol/L by using the deionized water;
step 2, weighing sodium hydroxide solid, and removing CO2Preparing sodium hydroxide solution with the molar concentration of 1.8-2.5mol/L by using the deionized water;
step 3, taking hydroxyethylidene diphosphonic acid liquid, wherein the molar ratio of the hydroxyethylidene diphosphonic acid liquid to aluminum ions is 1: (1-4) putting the hydroxyethylidene diphosphonic acid liquid into a reaction container, heating in a water bath, dropwise adding the mixed salt solution prepared in the step (1) and the sodium hydroxide solution prepared in the step (2) into the reaction container, stirring, introducing protective gas into the reaction container, and controlling the pH of the reaction liquid to be 9-11 in the dropwise adding process;
step 4, after the dropwise addition is finished, pouring the reaction liquid into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 70-180 ℃ for heat preservation and aging for 9-40 h;
and 5, taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature of 20-25 ℃, centrifuging the obtained suspension, washing with deionized water to be neutral, drying the centrifuged solid in a vacuum drying oven at 30-90 ℃ for 10-30h, and grinding to obtain the hydroxyethylidene diphosphonic intercalation zinc-aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor.
2. The hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 1, which is characterized in that: in step 1, Zn in a mixed salt solution2+And Al3+The molar ratio is (1.5-4.0): 1, the molar concentration of the mixed salt solution is 0.5mol/L, and in the step 2, the molar concentration of the sodium hydroxide solution is 1-2.0 mol/L.
3. The hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 1, which is characterized in that: in step 3, the molar ratio of the hydroxyethylidene diphosphonic acid liquid to the aluminum ions is 1: (1-3), the water bath temperature is 25-80 ℃, the protective gas adopts nitrogen or argon or helium, and the liquid for controlling the pH of the reaction liquid is ammonia water.
4. The hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 1, which is characterized in that: in step 4, the temperature of the vacuum drying furnace is 80-160 ℃, the aging time is 10-36h, and in step 5, the temperature of the vacuum drying oven is 40-80 ℃, and the drying time is 12-24 h.
5. The preparation method of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor as claimed in any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
step 1, weighing zinc nitrate and aluminum nitrate solids, and removing CO2Preparing a mixed salt solution with the molar concentration of 0.4-0.6mol/L by using the deionized water;
step 2, weighing sodium hydroxide solid, and removing CO2Preparing sodium hydroxide solution with the molar concentration of 1.8-2.5mol/L by using the deionized water;
step 3, taking hydroxyethylidene diphosphonic acid liquid, wherein the molar ratio of the hydroxyethylidene diphosphonic acid liquid to aluminum ions is 1: (1-4) putting the hydroxyethylidene diphosphonic acid liquid into a reaction container, heating in a water bath, dropwise adding the mixed salt solution prepared in the step (1) and the sodium hydroxide solution prepared in the step (2) into the reaction container, stirring, introducing protective gas into the reaction container, and controlling the pH of the reaction liquid to be 9-11 in the dropwise adding process;
step 4, after the dropwise addition is finished, pouring the reaction liquid into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and placing the high-pressure reaction kettle in a vacuum drying furnace at 70-180 ℃ for heat preservation and aging for 9-40 h;
and 5, taking the high-pressure reaction kettle out of the vacuum drying furnace, cooling to room temperature of 20-25 ℃, centrifuging the obtained suspension, washing with deionized water to be neutral, drying the centrifuged solid in a vacuum drying oven at 30-90 ℃ for 10-30h, and grinding to obtain the hydroxyethylidene diphosphonic intercalation zinc-aluminum hydrotalcite (ZnAl-HEDP LDH) corrosion inhibitor.
6. The preparation method of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 5, which is characterized by comprising the following steps: in step 1, Zn in a mixed salt solution2+And Al3+The molar ratio is (1.5-4.0): the molar concentration of the mixed salt solution is 0.5mol/L, and in the step 2, the molar concentration of the sodium hydroxide solution is 2.0 mol/L.
7. The preparation method of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 5, which is characterized by comprising the following steps: in step 3, the molar ratio of the hydroxyethylidene diphosphonic acid liquid to the aluminum ions is 1: (1-3), the water bath temperature is 25-80 ℃, the protective gas adopts nitrogen or argon, and the liquid for controlling the PH of the reaction solution is ammonia water.
8. The preparation method of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 5, which is characterized by comprising the following steps: in the step 4, the temperature of the vacuum drying furnace is 80-160 ℃, and the aging time is 10-36 h.
9. The preparation method of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor according to claim 5, which is characterized by comprising the following steps: in the step 5, the temperature of the vacuum drying oven is 40-80 ℃, and the drying time is 12-24 h.
10. The use of the hydroxyethylidene diphosphonic acid intercalated zinc aluminum hydrotalcite corrosion inhibitor as defined in any one of claims 1 to 4 in retarding corrosion of a seawater circulating cooling system, wherein: the release amount of the hydroxyethylidene diphosphonic acid ions is rapidly increased within 60min from the beginning of the release, the hydroxyethylidene diphosphonic acid ions are completely released after the hydroxyethylidene diphosphonic acid ions are soaked for 6 hours, and the corrosion inhibition rate of the hydroxyethylidene diphosphonic acid intercalation zinc-aluminum hydrotalcite corrosion inhibitor is 40-75%.
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