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Section 4. Chemistry
Ergasheva Saodat, Kurbanbaeva Sanobar, Badriddinova Farida, Kadirov Baxodir, Tashkent Chemical-technological institute E-mail: Ulug85bek77@mail.ru
SYNTHESIS OF CU: ZN-HEDP AND COMPOSITIONS WITH A BIOCIDE ACTIVITY BASED ON THEM
Abstract. For the normal functioning of technological schemes with a closed water circulation, it is necessary to prevent not only corrosion and scaling, but also biofouling. It should be in view of the fact that the problem of biofoulingis considered as such and as a problem of microbiological corrosion. Thus, the reaction of obtaining inhibitors with universal properties based on HEDP and CFR, in the ratio of initial reagents CFR: HEDP: Cu: Zn = 0.5: 2: 0.25: 0.75 - 0.5: 2: 0.75: 0.25. It has been established that when using CFR as a synergistic component, it is possible to increase the effectiveness of corrosion inhibition of copper-zinc complexes of HEDP by 2-4 times, which explains the advantage of synergistic efficiency.
Keywords: normal functioning, obtaining inhibitors, universal properties, synergistic component, corrosion inhibition.
Introduction. For the normal functioning of technological schemes with a closed water circulation, it is necessary to prevent not only corrosion and scaling, but also biofouling. It should be in view of the fact that the problem ofbiofoulingis considered as such and as a problem of microbiological corrosion.
Biological impurities - algae, mold, fungi penetrate with water into heat exchangers and pipelines, contaminating their surface. The contamination reduces the efficiency of heat exchange; contribute to the development of corrosion, which, in turn, reduces the service life of the water-cooling system. To eliminate these phenomena, bactericides of directional action are used. Both oxidizing and non-oxidizing agents are used. The most common
bactericides-oxidants include chlorine and bromine. These substances in most cases provide a high level of protection against microorganisms.
Currently, more effective drugs are being developed with fewer restrictions on application. However, for certain specific cases, special compositions are offered. Thus, the authors [1; 2] consider the composition content containing NTF and or HEDP, polyacrylamide (PAA) and Zn2+ as a corrosion inhibitor for structural steels in neutral aqueous solutions as well as biocidal. A biocidal composition for suppressing the vital activity of sulfate-reducing bacteria is offered, containing a synergistic mixture of the preparation, obtained by the interaction of hexa-methylenetetramine with a light fraction of waste
production of glycerol ("Bactericide LPE-11B") and formalin at ratios of 1: 9-9: 1. It is indicated that the minimum effective concentration of a biocide is 270 mg/l [3]. The use of the product of the interaction of hexamethylenetetraamine and monochlo-roacetic acid as a reagent to suppress the growth of microorganisms [4].
Isothiazolone is used as biocides in the new multi-component compositions - citric acid / PF (HEDP) / polymer acrylate. It is shown that a new inhibitor can reduce corrosion, prevent scaling and growth of microbes in the tested conditions [5].
Along with sisothiazoline, quaternary phospho-nium salts, dichloroiso- and trichloroisocyanuric acids, glutaraldehyde are also used to reduce the problems of biofouling of circulating systems [6]. Scale inhibitors include NTF, PBTC, polyacrylic acid, phosphono-sulfuric acid; corrosion - HEDP, phosphinosulfonic acids, etc.
Company Nalco suggests using natural products as a biocide, in particular, oils extracted from eucalyptus and the growth of tea crops. The composition contains a mixture of oils, and in specific versions of the preparation can be applied in concentrations from 1 to 250 mg/l [7]. For the same purpose, it is offered to dose reagents such as ammonium salts of polydimethyldiallyl chloride, polydimethyldiallyl-bromide, polydecyldi-methyl-halides, etc. into water. It is indicated that the molecular weight does not have a noticeable effect on the effectiveness of preparations, the preferred area is from 10.000 to 3.000.000, the concentration in water can reach 1000 mg/l [8]. It was established that when trichloroisocyanurate (1) is used as a biocide, active oxidizing agents in the form of OH-, HO- and active oxygen, destroying bacteria, algae, etc. are formed in water. In the experiments, the bacteria content in water was 105-106 ml; under the influence of (1) and exposure for 12 hours, complete inactivation was observed. Also, the authors found that (1) and phosphonates are compatible preparations [9].
NTF compositions with Zn (2+) and various additives as synergistic fragments are used as scale inhibitors and corrosion inhibitors. As an additive to Zn-NTF, the following are used: N'-eran-N,N1,N-trimethyl ammonium bromide (CTAB) [10]; EDTP, aminoethylidenediphosphonic acid [11]; phthalic anhydride [12; 13].
Another biocide and biodegradable dispersant includes alkyl dimethyl- benzyl ammonium chloride, dialkyldimethylammonium chloride, propylene glycol [14].
To prevent the formation of bacterial deposits
[15], for example, in the paper industry, it is offered to introduce into the water cationic polyelectrolytes - 1,1-oxybis (2-chloroethane) and / or epichlorohy-drin with amines, N-methylmethanamine or ammonia. The preferred concentration of the composition is 0.5-50 mg/l.
Currently, the literature describes several thousand chemical compounds with biocide properties, however, in practice, for security reasons, only hundreds of them are used. Every year, dozens ofbiocide preparations are removed from production due to low antimicrobial activity or high toxicity.
Experimental part.
The method of obtaining zincate-HEDP. The technique is carried out in the following sequence: the water in the calculated amount is poured in the reactor - a heat-resistant glass, and 1g of glycerin is add. The mixture is stirred for 1-2 minutes. Then 2/3 of the calculated amount of HEDP is add. The temperature at the same time should be 30-35 °C. After that, zinc oxide is sent to the reactor, stirred until complete dissolution and obtaining a clear liquid. Then, the calculated amount of finely-ground sodium hydroxide is added to the reaction mixture and vigorous agitation is continued.
At the same time the temperature is controlled in the range of20-25 °C. Then, the remaining 1/3 part of HEDP is added to the reactor. The solution, losing white color, gradually becomes transparent. The finished product is cooled to room temperature for
stabilization and stored under these conditions for 30-60 minutes. The yield is 98.2%.
The method of obtaining the copper complex HEDP. A calculated amount of 110.0 ml of water, 1.0-3.0 g of glycerin (or citric acid), 1.0-3.0 g of extraction phosphoric acid is poured into a glass, mixed and the calculated amount of copper oxide is added, heated up to 50-75 °C until complete dissolution of copper oxide. In a separate beaker, 15 g of HEDP is dissolved in 21.0 ml of water and 4.5 g of hydroxycine is added. The reaction is carried out at room temperature. The reaction mass is maintained for 20-30 minutes.
Then, with intensive transfer, the solution prepared in the first glass is added to the reaction mass. A clear blue solution is obtained in quantitative yield. Obtaining an inhibitor with biocide activity. The suggested method of obtaining a multipurpose inhibitor is carried out in three stages: stage No. 1, obtaining Cu-HEDP; stage No. 2, production of Zn-HEDP and stage No. 3 of preparation of a mixture of Cu-HEDP with Zn-HEDP ("ICSB-UNI-1") and preparation of a composition with the addition of synergistic activity of the component - carbamide-formaldehyde resin (CFR).
The composition and structure of the obtained product "ICSB-UNI-1" is established by various physical-chemical methods of analysis.
ICSB-UNI-1 was analyzed on an "Agilent Technology" chromatography-mass spectrometry GC / MS AT 5973N using the "DRUGSP-SHORT.M" method using a 30 m x 0.25 mm capillary column with 5% phenylmethylsiloxane at an injector temperature of280 °C, sample size 1 ml. Comparison with the basic data of the device proves that the obtained "ICSB-UNI-B" has high purity. The infrared spec-
trometer "ICS-UNI-B", which was taken on an Agilent Technology FTIR-640 instrument with a recording range of4000-400 cm - 1 and the number of scans is 12, a band is present at 1250-1300 cm - 1 related to localized bond P = O; the band at 2500-2700 cm - 1 refers to the stretching vibrations of the group of the fully deprotonated PO3 group; there are also bands at 1180-1240 and 2500-2700 cm - 1 related to the stretching vibrations of the P - O (H) bond of the protonated phosphate groups, which indicates that the complexes are partially protonated; the intense band at 1042 cm - 1 refers to the stretching vibrations of the Cu - O bond; the band at 650-750 cm - 1 to the stretching vibrations of the C - P bond, the intense band at 570-550 cm - 1 to the stretching vibrations of the Zn - O bond; the absorption bands at 480-460 cm - 1 to the deformation vibrations - O - P - O. This allows us to conclude that the coordination of the PO3 group with the Zn atom occurs with the localized n-bond P = O, the oxygen atoms in the PO3 group do not equal rights.
Results and discussion. As was shown earlier, multipurpose reagents can be created on the basis of organophosphonates. However, due to the relatively high cost of such products, as well as the lack of raw materials for the production of products of this type in our republic, the possibility of overcoming this situation is to create a relatively inexpensive, most effective composition containing organophosphonates in the amount of30-40% from the total mass of the reagent.For this purpose, compositions obtained on the basis of the copper-zinc complex HEDP with the addition of CFR were studied. Inhibiting properties of the composition are presented in (table 1 and 2).
Table 1. - The influence of the composition «ICSB-UNI-1» and CFR on the corrosion rate of steel grade St. 3, water hardness 8.9 mg/l
№ Inhibitor Inhibitor con- Average mass Corrosion veloc- Protective
components centration, g/l loss, g ity, g/m2«an hour effect,%
1 2 3 4 5 6
1. Without inhibitor - 0.0390 0.750 -
1 2 3 4 5 6
2. "IKSB-UNI-1": CFR (1:1) 4.0 6.0 0.0097 0.0086 0.249 0.221 75.1 77.9
8.0 10.0 0.0054 0.0038 0.138 0.097 95.1 97.9
4.0 0.0075 0.148 80.3
3. "IKSB-UNI-1": 6.0 0.0056 0.112 85.1
CFR (2:1) 8.0 0.0016 0.034 95.5
10.0 0.0008 0.017 97.7
4.0 0.0073 0.172 77.0
4. "IKSB-UNI-1": 6.0 0.0054 0.151 79.9
CFR (3:1) 8.0 0.0015 0.091 87.8
10.0 0.0008 0.075 90.0
From the data presented in (table 1 and 2), it cantly increased. The protective effect against steel
can be seen that with the addition of CFR to the corrosion when using reagents "ICSB-UNI-1" and
composition "ICSB-UNI-1", the efficiency of the CFS is more than 97% in water of hardness 8.9 mg/l
initial reagent as a corrosion inhibitor can be signifi- and more than 94% in water of hardness 12.9 mg/l.
Table 2.- The influence of the composition "IKSB-UNI-1" and CFR on the corrosion rate of steel grade St. 3, water hardness 12.9 mg/l
№
Inhibitor components
Inhibitor concentration, g/l
Average mass loss, g
Corrosion velocity, g/m2«an hour
Protective effect,%
1.
Without inhibitor
0.0390
0.750
2.
"ICSB-UNI-": CFR (1:1)
4.0 6.0 8.0 10.0
0.0121 0.0061 0.0050 0.0034
0.310 0.156 1.282 0.087
68.9 84.3
87.1
91.2
"ICSB-UNI-": CFR KOC (2:1)
4.0 6.0 8.0 10.0
0.0110 0.0048 0.0032 0.0023
0.282 0.123 0.082 0.058
71.7
87.6
91.7 94.1
"ICSB-UNI-": CFR (3:1)
4.0 6.0 8.0 10.0
0.0109 0.0047 0.0031 0.0023
0.279 0.120 0.079 0.058
62.8 87.9 92.0 94.2
Experiments on the inhibition of the vital activity of microorganisms (biofouling) were carried out on the basis of standard algological requirements in the following order: objects of experience (or research) were carried out in microalgae Chlorella vulgaris, as
well as in E. Clara cultures belonging to the Euglena Ehr family. Experiments were performed in standard living food conditions for cultures. Table 3 shows the results of the same cultures grown in a tough food environment.
Table 3.- The biological effect of preparations on the growth of E. Clara in a hard food environment
Reagent dose Lysis area sizes (sm)
"ICSB-UNI-": CFR(1:1) "ICSB-UNI": CFR (2 : 1)
0.1 0.42 ± 0.03 0.23 ± 0.04
0.3 0.60 ± 0.05 0.67 ± 0.03
0.5 0.90 ± 0.07 0.98 ± 0.05
0.7 0.96 ± 0.08 -
Control - -
The results ofthe experiment show a dramatic effect of any amount of the preparation applied to the column of cultures planted in a hard food environment. Here, a separate indicator is "ICSB-UNI-1", in which the concentration acts lethally at 0.5 m. When analyzing these results, the inhibitory effect ofthese preparations up to 92-96% "ICSB-UNI-1"on algae development that it is shown the presence of formaldehyde residues in the composition of this product is explained.
The effect of biomass formation was studied by conducting the same experiments on Scenedes-
musoblianus cultures (Fig. 3). A certain concentration of "IKSB-UNI-1" is significantly reduced by 4-5 days of growing the biomass of these crops.
This is a result of the negative effects of the preparation, this decreases the vitality of the cells and destroys the main breeding cells.
In the control variant in the opposite position for 18-19 days of cultivation, the vitality of the cells was at the level of the proposed requirements, and the preservation of certain sizes of biomass was observed.
A
Figure 1. Performance of "ICSB-UNI at the growth of Chlorellavulgaris (1-0.1 ml/l, 2-0.3 ml/l,
It has been established that compositions containing only zinc in their composition are not a biocide and are not capable of suppressing the growth of microorganisms; the increase in the composition ofthe propor-
Growth time, day B
- 1"+CFR by different concentrations cell: A - control, B - experiment, 3-0.5 ml/l, 4-0.7 ml/l)
tion of copper compared with the molar fraction of zinc increases the biocidal effectiveness ofthe composition (100% of the dead microorganisms), which confirms the role of copper in the compositions obtained.
Conclusion. Thus, the reaction of obtaining in- effectiveness of corrosion inhibition of copper-zinc hibitors with universal properties based on HEDP complexes of HEDP by 2-4 times, which explains and CFR, in the ratio of initial reagents CFR: the advantage of synergistic efficiency. At the same HEDP: Cu: Zn = 0.5: 2: 0.25: 0.75 - 0.5: 2 : 0.75: time, "ICSB-UNI-1", taken with Cu: Zn in 0.25: 0.75 : 0.25. It has been established that when using CFR as ratios, effectively suppresses the vital activity of mia synergistic component, it is possible to increase the croorganisms and, accordingly, biofouling.
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