Abstract:
The present invention relates to a composition for preventing deposition of inorganic salts. It comprises 5.0-50.0% by weight of a phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula: ##STR1## wherein n=1 to 20; 5.0 to 10.0% by weight of 1,3-diaminopropanol-2 and/or a derivative of 1,3-diaminopropanol-2 of the general formula: ##STR2## wherein n=1 to 20; 3.0-30.0% by weight of hydrochloric acid, 3.0-7.0% by weight of an alkali metal chloride, 0.5-2.5% by weight of a product of interaction of benzyl chloride, chlorobenzyl chloride, benzylidene chloride or a mixture of these chlorinated compounds with hexamethylenetetramine at a molar ratio thereof equal to 1:0.25-0.45 respectively; 0.5-4.0% by weight of a water-soluble organic solvent and water being the balance. The protective effect of the composition against deposition of inorganic salts is as high as 100%. The freezing point is as low as -100° C., thus enabling the use of the composition under arctic climate conditions without the necessity of adding costly antifreeze agents.

Description:
FIELD OF THE INVENTION 
     The present invention relates to compositions for preventing deposition of inorganic salts from aqueous solutions on metal surfaces and can be useful in the systems of return water supply, distillers for mineralized waters, in processes of oil and natural gas extraction, transportation and preconditioning. 
     BACKGROUND OF THE INVENTION 
     Known in the art are compositions for preventing deposition of inorganic salts comprising aminomethylenephosphonic compounds and surfactant additives. Thus, U.S. Pat. No. 3,467,192 Cl. 166-279 (1968) teaches the use, as the aminomethylenephosphonic compound, of nitrilotrimethylenephosphonic acid of the formula: ##STR3## and as the surfactant--a compound of the formula: ##STR4## 
     Also known in the art is a composition for preventing deposition of inorganic salts comprising polyethylenepolyamine-N-methylenephosphonic acid of the general formula: ##STR5## wherein n=1 to 14 and polyacrylamide (cf. U.S. Pat. No. 3,483,925 Cl. 166-279, 1968). 
     Furthermore, also known in the art is a process for preventing deposition of inorganic salts with the use of an aminomethylenephosphonic acid for the general formula: ##STR6## wherein n=1 to 5, (cf. USSR Inventor&#39;s Certificate No. 789434, Int. Cl. 3  CO2 F 5/14, E 21 B 43/12, 1980). 
     However, the above-discussed processes provide but an insufficient protective effect against deposition of inorganic salts. Furthermore, the use of polyacrylamide in the above-described compositions involves considerable difficulties in the preparation of working solutions of this particular compound from a gel-like commercial product. The manufacture of an aqueous solution of polyacrylamide requires a special equipment which inevitably causes inefficient labour- and power expenditures. 
     The closest prior art composition most resembling that of the present invention in the subject matter and the effect obtained is a composition for preventing deposition of inorganic salts comprising a phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula: ##STR7## wherein n=1 to 5, and also 1,3-diaminopropanol-2 and/or a derivative of 1,3-diaminopropanol-2 of the general formula: ##STR8## wherein n=2 to 5, hydrochloric acid, sodium chloride and water, the components being present in the following proportions, percent by weight: 
     
         ______________________________________phosphonomethylated derivative of 1,3-diami-                      5.0-20.0nopropanol-2 of the general formula (I)1,3-diaminopropanol-2 and/or a deriva-                     3.0-7.0tive of 1,3-diaminopropanol-2 of the gene-ral formula (II)hydrochloric acid          3.0-30.0sodium chloride           3.0-7.0water                     to 100(cf. USSR Inventor&#39;s Certificate No. 834334, Int. Cl..sup.3 E 21 B43/00, 1981).______________________________________ 
    
     However, this composition possesses but an insufficient protective effect against deposition of inorganic salts and is difficult to handle under winter-weather conditions, since the minimum freezing temperature of the composition is -35° C. The latter condition to a considerable extent restricts the possibility for using this composition in regions with arctic climate, or requires the use of costly antifreeze components. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide such a composition for preventing deposition of inorganic salts which would possess an improved protective effect. 
     It is another object of the present invention to provide such a composition for preventing deposition of inorganic salts which would have a lower freezing temperature. 
     These and other objects of the present invention are accomplished by the provision of a composition for preventing deposition of inorganic salts comprising a phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula: ##STR9## wherein n=1 to 20 and also 1,3-diaminopropanol-2 and/or a 1,3-diaminopropanol-2 derivative of the general formula: ##STR10## wherein n=2 to 20, hydrochloric acid, an alkali metal chloride and water; the composition according to the present invention additionally contains a product of interaction of benzyl chloride, chlorobenzylchloride or benzylidenechloride or a mixture of these chlorinated compounds with hexamethylenetetramine in a molar ratio thereof of 1:0.25-0.45 respectively and a water-soluble organic solvent, the components being present in the following proportions, percent by weight: 
     
         ______________________________________phosphonomethylated derivative of 1,3-diami-                   5.0-50.0nopropanol-2 of the general formula (I)1,3-diaminopropanol-2 and/or a 1,3-diami-                    5.0-10.0nopropanol-2 derivative of the generalformula (II)hydrochloric acid        3.0-30.0alkali metal chloride   3.0-7.0product of interaction of benzyl chloride,                   0.5-2.5benzylidene chloride or chlorobenzylchloride or a mixture of these chlorinatedcompounds with hexamethylenetetraminewater-soluble organic solvent                   0.5-4.0water                   the balance.______________________________________ 
    
     It is preferable to use, as the water-soluble organic solvent, diacetone alcohol, methanol, ethanol, methylethylketone, dimethylformamide, triethylamine. 
     Owing to the introduction of the product of interaction of hexamethylenetetramine with the above-mentioned benzylhalides, the composition according to the present invention makes it possible to considerably improve the protective effect against deposition of inorganic salts in aqueous systems as compared to the prior art compositions. 
     Thus, at the low limit of concentrations of the components of a known composition according to the USSR Inventor&#39;s Certificate No. 834334, the protective effect against deposition of calcium sulphate is only 46.6%, whereas that of the composition according to the present invention is as high as 63.8%. 
     A similar result is obtained at the upper limit of concentrations of the components of both compositions. Thus, for the USSR Inventor&#39;s Certificate referred to, the protective effect is 86.5%, whereas for the present invention it is 99.6%. 
     The composition according to the present invention has a freezing point as low as -100° C. which enables the use of the composition under arctic climate conditions without introducing any costly antifreeze agents. 
     The reduction of the lower limit of concentrations of the components of the composition according to the present invention is inexpedient, since this results in a lowered protective effect and the composition gets deprived of the advantages over the prior art ones. 
     Increasing the upper limit of concentrations of the components of the composition according to the present invention is also inexpedient, since already at the above-specified concentrations of the components the protective effect is equal to 100%. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The composition for preventing deposition of inorganic salts according to the present invention is prepared by a conventional method through dissolution of the starting components in an aqueous solution of hydrochloric acid. 
     The component employed in the composition according to the present invention, namely phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula (I) is prepared by modifying 1,3-diaminopropanol-2 and/or a derivative of 1,3-diaminopropanol-2 of the general formula (II) with formaldehyde and phosphorus trichloride at the temperature of 45° C., followed by precipitation of the desired product from the reaction mass by methanol. 
     The product is a white crystalline compound well-soluble in water, insoluble in alcohols, acetone; it possesses properties of a strong acid. 
     The procedure for the preparation of the phosphonomethylated derivative of 1,3-diaminopropanol-2 is described in the USSR Inventor&#39;s Certificate No. 876666, Int. Cl. 3  C 08 G 79/04, C 08 J 5/20. 
     The components of the composition according to the present invention, i.e. 1,3-diaminopropanol-2 and/or a derivative of 1,3-diaminopropanol-2 of the general formula (II) is prepared by reacting epichlorohydrin with a substantial excess of ammonia taken in the form of an aqueous solution, followed by heating of the reaction mass at a temperature of from 10° to 30° C. for a period of from 1/4 to 6 hours, neutralization of the formed hydrochloric acid with an alkali metal hydroxide, such as sodium hydroxide, and distilling-off the excess of the aqueous solution of ammonia. 
     The method for the preparation of 1,3-diaminopropanol-2 and/or the 1,3-diaminopropanol-2 derivative of the general formula II is disclosed in U.S. Pat. No. 4,432,553 Cl. 260-585. 
     The product additionally contained in the composition according to the present invention is prepared by reacting benzyl chloride, chlorobenzyl chloride or benzylidene chloride or a mixture of these chlorinated compounds with hexamethylenetetramine in the presence of a caustic alkali at a molar ratio therebetween of 1:0.25-0.45:2.2-3.6 respectively and at a temperature within the range of from 100° to 125° C. 
     The product comprises a transparent yellow-brown liquid. 
     The procedure for the preparation of a product of interaction of hexamethylenetetramine with the above-specified benzylhalides is described in USSR Inventor&#39;s Certificate No. 469771, Int. Cl. 2  C 23 F 11/10. 
     The composition according to the present invention can be useful in systems of return water supply, distillers for mineralized waters, as well as in processes of oil and natural gas extraction, transportation and preconditioning. 
     For example, in exploitation of petroleum fields some embodiments are possible for the introduction of the composition according to the present invention (scaling inhibitor) into the production wells; 
     1. Continuous dispensing of the composition into the annular space of the oil well by means of a metering device. 
     2. Continuous dispensing of the composition into the system of maintaining the formation pressure through the pumping well. 
     3. Periodic pumping of the composition into the productive layer through the exploitation well. This mode of using the composition for preventing deposition of inorganic salts is based on the ability of the composition to get adsorbed on the porous surface of the critical zone of the well and to be slowly washed by mineralized waters during exploitation of the well by known methods, thus inhibiting deposition of inorganic salts in the well and well equipment for a period of several months. 
     4. Continuous dispensing of the composition by means of a metering device to the inlet of a heat-exchanging equipment of the unit for a thermochemical field preconditioning of crude oil. 
    
    
     The assessment of the protective effect of the composition according to the present invention and the composition according to the USSR Inventor&#39;s Certificate No. 834334 against deposition of calcium sulphate is effected according to the following procedure. 
     Oversaturated calcium sulphate solutions are prepared by mixing equivalent amounts of sodium sulphate and calcium chloride. The reaction occurs according to the scheme: ##STR11## 
     The initial concentration of calcium sulphate in the oversaturated solution is 10 g/l. 
     In all series of experiments the amount of the composition added to the oversaturated solution of calcium sulphate was 20.0 mg/l, whereas only proportions of the composition components were changed. The solutions were thermostatted at the temperature of 25° C. The protective effect against deposition of calcium sulphate was determined 240 hours afterwards by sampling and analysis of the sample for calcium ions. The protective effect was calculated according to the formula: ##EQU1## wherein: E is protective effect, %: 
     C o  --initial concentration of calcium ions in the oversaturated solution, g/l; 
     C k  --concentration of calcium ions in the solution at a given moment without the addition of the composition of the present invention, g/l; 
     C i  --concentration of calcium ions in the solution at a given moment after introduction of the composition according to the present invention, g/l. 
     Table 1 shows particular formulations of the composition according to the present invention and those of the known composition according to the USSR Inventor&#39;s Certificate No. 834334, as well as values of the protective effect against deposition of calcium sulphate. 
     As the phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula (I) use is made of a mixture of products with a different polymerization degree, namely with n=1, n=5, n=20. The components are employed in the following proportions, percent by weight: 
     
         ______________________________________   at n = 1          80   n = 5  15   n = 20 5.______________________________________ 
    
     Moreover, use is made of a mixture of 1,3-diaminopropanol-2 (n=1) and a derivative of 1,3-diaminopropanol-2 of the general formula (II) where n=5 and n=20 at the same proportions of the products in a mixture. 
     As the alkali metal chloride sodium chloride is used according to the present invention. 
     
         TABLE 1  Components of the composition Pro-       Product of reaction Product of reaction  tective      Product of reaction of chlorobenzyl of benzylidene   effect  Mixture of 1,3-diami-    of benzyl chloride chloride with chloride and  after Phosphonomethylated nopropanol-2 and   Water-soluble and hexamethylene hexamethylene hexamethylene  240 derivative of 1.3-di- 1,3-diaminopropanol-2 Hydrochloric Sodium organic solvent tetramine (molar tetramine (molar tetramine (molar  hours, No. Composition aminopropanol-2 derivative acid chloride Name Amount ratio 1:0.25 ratio 1:0.35) ratio 1:0.45) Water  % 1 2 3 4 5 6 7 8 9 10 11 12 13   1 Known composi- 5.0 5.0 3.0 3.0 -- -- -- -- -- to 100 44.6  tion (USSR 2. Inv. Certifica- 7.5 5.5 10.0 4.0 -- -- -- -- -- to 100 56.8  te No. 834334) 3.  10.0 6.0 18.0 5.0 -- -- -- -- -- to 100 68.7 4.  15.0 6.5 24.0 6.0 -- -- -- -- -- to 100 79.9 5.  20.0 7.0 30.0 7.0 -- -- -- -- -- to 100 86.5 6. Composition of 5.0 5.0 3.0 3.0 Diacetone 0.5 0.5 -- -- to 100 63.8  this inventionalcohol 7.  10.0 5.0 10.0 3.7 Diacetone 1.0 0.75 -- -- to 100 82.3 alcohol 8.  20.0 6.5 18.0 4.0 Diacetone 1.5 1.0 -- -- to 100 92.6  alcohol 9.  30.0 6.5 20.0 4.25  2.0 2.5 -- -- to 100 93.0 10.  40.0 10.0 24.0 7.0  3.0 2.0 -- -- to 100 98.0 11.  50.0 7.0 30.0 5.0  4.0 1.5 -- -- to 100 99.6 12.  5.0 5.0 3.0 3.0  0.5 -- 0.5 -- to 100 60.2 13.  10.0 5.0 10.0 3.7  1.0 --  0.75 -- to 100 76.9 14. 20.0 6.5 18.0 4.0  1.5 -- 1.0 -- to 100 91.8 15.  30.0 6.0 20.0 4.25 2.0 -- 2.5 -- to 100 94.1 16.  40.0 10.0 24.0 7.0  3.0 -- 2.0 -- to 100 96.1 17. Composition of 50.0 7.0 30.0 5.0  4.0 -- 1.5 -- to 100 98.6 this invention 18.  5.0 5.0 3.0 3.0  0.5 -- -- 0.5 to 100 63.1 19.  10.0 5.0 10.0 3.7  1.0 -- --  0.75 to 100 77.2 20.  20.0 6.5 18.0 4.0  1.5 -- -- 1.0 to 100 90.6 21.  30.0 6.0 20.0 4.25  2.0 -- -- 2.5 to 100 96.0 22.  40.0 10.0 24.0 7.0  3.0 -- -- 2.0 to 100 96.4 23.  50.0 7.0 30.0 5.0  4.0 -- -- 1.5 to 100 98.6 24.  5.0 5.0 3.0 3.0 Ethanol 0.5 0.5 -- -- to 100 61.8 25.  10.0 5.0 10.0 3.7  1.0  0.75 -- -- to 100 78.5 26. 20.0 6.5 18.0 4.0  1.5 1.0 -- -- to 100 90.5 27.  30.0 6.0 20.0 4.25 2.0 2.5 -- -- to 100 93.2 28.  40.0 10.0 24.0 7.0  3.0 2.0 -- -- to 100 95.4 29.  50.0 7.0 30.0 5.0  4.0 1.5 -- -- to 100 96.9 30.  5.0 5.0 3.0 3.0 Methanol 0.5 -- 0.5 -- to 100 62.7 31.  10.0 5.0 10.0 3.7  1.0 -- 0.75 -- to 100 75.5 32.  20.0 6.5 18.0 4.0  1.5 -- 1.0 -- to 100 89.9 33.  30.0 6. 20.0 4.25  2.0 -- 2.5 -- to 100 92.7 34.  40.0 10.0 24.0 7.0  3.0 -- 2.0 -- to 100 96.0 35.  50.0 7.0 30.0 5.0  4.0 -- 1.5 -- to 100 97.4 36.  5.0 5.0 3.0 3.0 Methyl- 0.5 -- -- 0.5 to 100 59.5 37. 10.0 5.0 10.0 3.7 ethyl ke- 1.0 -- --  0.75 to 100 72.9 38.  20.0 6.5 18.0 4.0 tone 1.5 -- -- 1.0 to 100 90.5 39.  30.0 6.0 20.0 4.25  2.0 -- -- 2.5 to 100 93.0 40.  40.0 10.0 24.0 7.0  3.0 -- -- 2.0 to 100 96.1 41.  50.0 7.0 30.0 5.0  4.0 -- -- 1.5 to 100 96.8 42. Composition of 5.0 5.0 3.0 3.0 Dimethyl 0.5 0.5 -- -- to 100 60.9  this invention 43.  10.0 5.0 10.0 3.7 formamide 1.0  0.75 -- -- to 100 76.2 44.  20.0 6.5 18.0 4.0  1.5 1.0 -- -- to 100 91.7 45.  30.0 6.0 20.0 4.25  2.0 2.5 -- -- to 100 94.8 46.  40.0 10.0 24.0 7.0  3.0 2.0 -- -- to 100 96.2 47.  50.0 7.0 30.0 5.0  4.0 1.5 -- -- to 100 96.8 48.  5.0 5.0 3.0 3.0 Triethyl- 0.5 0.5 -- -- to 100 63.7 49.  10.0 5.0 10.0 3.7 amine 1.0  0.75 -- -- to 100 78.9 50.  20.0 6.5 18.0 4.0  1.5 1.0 -- -- to 100 90.5 51.  30.0 6.0 20.0 4.25  2.0 2.5 -- -- to 100 92.0 52.  40.0 10.0 24.0 7.0  3.0 2.0 -- -- to 100 95.8 53.  50.0 7.0 30.0 5.0  4.0 1.5 -- -- to 100 96.7 54. Comparison 2.5 3.0 2.0 2.5 Diacetone 0.4  0.25 -- -- to 100 28.3 55. composition 2.5 3.0 2.0 2.5 alcohol 0.4 --  0.25 -- to 100 28.5 56.  2.5 3.0 2.0 2.5  0.4 -- --  0.25 to 100 29.5 
    
     As it follows from the data given in the above Table 1, the composition according to the present invention is superior to the known composition according to USSR Inventor&#39;s Certificate No. 834334 in the efficiency thereof. Thus, the protective effect at lower limits of concentrations of the components of the composition according to the USSR Inventor&#39;s Certificate referred to is only 44.6%, whereas that of the composition according to the present invention is 63.8%. 
     A similar result is observed for the protective effect at upper limits of concentrations of the components of both compositions. Thus, for the known composition the protective effect is 86.5%, for the composition according to the present invention it is equal to 99.6%. 
     Furthermore, data illustrating the protective effect of the composition according to the present invention against deposition of calcium sulphate are shown in Table 2 hereinbelow (the test procedure is described hereinabove). Table 2 also specifies particular formulations of the composition according to the present invention and corresponding values of the protective effect obtained. The phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula (I) and the derivative of 1,3-diaminopropanol-2 of the general formula (II) are presented as individual compounds. As the alkali metal chloride according to the present invention sodium chloride is used. 
     
                                           TABLE 2__________________________________________________________________________   1Components of the composition percent by weight                             Product of                                   Product of                                         Product of                             interac-                                   interaction                                         interaction                             tion of                                   of chloro-                                         of benzyli-Phospho-   1,3-Diami-                benzyl                                   benzyl                                         dene chloridenomethy-   nopropanol-               chloride                                   chloride                                         withlated de-   2 and de-                 and hexa-                                   and hexa-                                         hexamethy-rivative   rivative                  methylene                                   methylene-                                         lene tet-  Protectiveof 1,3-di-   of 1,3-di-          Hydro-              Sodium                  Water-solible                             tetramine                                   tetramine                                         ramine (mo-                                                    effect afteraminopro-   aminopro-          chloric              chlo-                  organic solvent                             (molar ra-                                   (molar ra-                                         lar ratio  240 hours,No.   panol-2   panol-2          acid              ride                  Name  Amount                             tio 1:0.25)                                   tio 1:0.35)                                         of (1:0.45)                                                Water                                                    %1  2    3      4   5   6     7    8     9     10     11  12__________________________________________________________________________   n = 1   n = 1          Diacetone                  alcohol1. 20.0 6.5    18.0              4.0 Diacetone                        1.5  1.0   --    --     to                                                    94.6                  alcohol2. 20.0 6.5    18.0              4.0 Diacetone                        1.5  --    1.0   --     to                                                    95.0                  alcohol3. 20.0 6.5    18.0              4.0 Diacetone                        1.5  --    --    1.0    to                                                    93.7                  alcohol   n = 5   n = 54. 5.0  5.0    3.0 3.0 Diacetone                        0.5  0.5   --    --     to                                                    66.7                  alcohol5. 20.0 6.5    18.0              4.0 Diacetone                        1.5  --    1.0   --     to                                                    97.8                  alcohol6. 40.0 10.0   24.0              7.0 Diacetone                        3.0  --    --    2.0    to                                                    99.5                  alcohol   n = 20   n = 207. 20.0 6.5    18.0              4.0 Diacetone                        1.5  --    1.0   --     to                                                    89.7                  alcohol8. 20.0 6.5    18.0              4.0 Ethanol                        1.5  --    1.0   --     to                                                    90.09. 20.0 6.5    18.0              4.0 Dimethyl-                        1.5  --    1.0   --     to                                                    90.2                  formamide__________________________________________________________________________ 
    
     From the data given in the above Table 2 it follows that the composition according to the present invention ensures a high protective effect against deposition of scaling of inorganic salts. 
     Table 3 gives particular formulations of the composition according to the present invention and corresponding values of the protective effect against deposition of calcium sulphate. As the product additionally contained in the composition according to the present invention use is made of a product of interaction of hexamethylene tetramine with different mixtures of benzylhalides. As the alkali metal chloride sodium chloride is used. 
     Table 4 gives particular formulations of the composition according to the present invention and corresponding values of the protective effect against the formation of scaling of calcium sulphate. As the product additionally contained in the composition according to the present invention use is made of a product of the reaction between hexamethylenetetramine with an individual benzylhalide, as the alkali metal chloride potassium chloride is used. 
     
                                           TABLE 3__________________________________________________________________________     Components of the composition                                              Product of interaction                                              ofComposition     Phosphonomethylated                1,3-diamino-       Water-soluble                                              benzyl chloride andsupply rate,     derivative of                propanol-2                       Hydrochloric                              Sodium                                   organic solvent                                              hexamethylenetetramine                                              8No.   mg/l   1,3-diaminopropanol-2                derivative                       acid   chloride                                   Name  Amount                                              (molar ratio 1:0.25)1  2      3          4      5      6    7     8    9__________________________________________________________________________1. 20.0   5.0        5.0    3.0    3.0  Diacetone                                         0.5  0.252. 20.0   20.0       6.5    18.0   4.0  alcohol                                         1.5  --3. 20.0   40.0       10.0   24.0   7.0        3.0  1.04. 20.0   5.0        5.0    3.0    3.0  Ethanol                                         0.5  0.255. 20.0   20.0       6.5    18.0   4.0        1.5  0.56. 20.0   40.0       10.5   24.0   7.0        3.0  --7. 20.0   5.0        5.0    3.0    3.0  Dimethyl                                         0.5  0.28. 20.0   20.0       6.5    18.0   4.0  formamide                                         1.5  0.259. 20.0   40.0       10.0   24.0   7.0        3.0  0.75__________________________________________________________________________                      Components of the composition                      Product of interaction of                                   Product of interaction                                                    Protective               Composition                      chlorobenzylchloride and                                   benzylidene chloride                                                    effect after               supply rate,                      hexamethylene tetramine                                   hexamethylenetetramone                                                    240 hours,            No.               mg/l   (molar ratio 1:0.35)                                   (molar ratio 1:0.45)                                                Water                                                    %            1  2      10           11           12  13__________________________________________________________________________            1. 20.0   0.25         --           to                                                    68.6            2. 20.0   0.5          0.5          to                                                    97.7            3. 20.0   --           1.0          to                                                    99.7            4. 20.0   --            0.25        to                                                    68.8            5. 20.0   0.5          --           to                                                    96.6            6. 20.0   1.0          1.0          to                                                    99.3            7. 20.0   0.2          0.1          to                                                    69.9            8. 20.0   0.25         0.5          to                                                    97.0            9. 20.0   0.75         0.5          to                                                    99.7__________________________________________________________________________ 
    
     
                                           TABLE 4__________________________________________________________________________     Components of the composition, percent by weight     PhosphonomethylatedComposition     derivative of                Derivative of           Water-solublesupply rate,     1,3-diaminopropanol-2                1,3-diaminopropanol-2                           Hydrochloric                                  Potassium                                        organic solventNo.   mg/l   n = 5      n = 5      acid   chloride                                        Name   Amount1  2      3          4          5      6     7      8__________________________________________________________________________ 1.   20.0   5.0        5.0        3.0    3.0   Diacetone                                               0.5 2.   20.0   20.0       6.5        18.0   4.0   alcohol                                               1.5 3.   20.0   40.0       10.0       24.0   7.0          3.0 4.   20.0   5.0        5.0        3.0    3.0   Ethanol                                               0.5 5.   20.0   20.0       6.5        18.0   4.0          1.5 6.   20.0   40.0       10.0       24.0   7.0          3.0 7.   20.0   5.0        5.0        3.0    3.0   Methanol                                               0.5 8.   20.0   20.0       6.5        18.0   4.0          1.5 9.   20.0   40.0       10.0       24.0   7.0          3.010.   20.0   5.0        5.0        3.0    3.0   Methylethyl-                                               0.5   20.0   20.0       6.5        18.0   4.0   ketone 1.5   20.0   40.0       10.0       24.0   7.0          3.0   20.0   5.0        5.0        3.0    3.0   Dimethyl-                                               0.5   20.0   20.0       6.5        18.0   4.0   formamide                                               1.5   20.0   40.0       10.0       24.0   7.0          3.0   20.0   5.0        5.0        3.0    3.0   Triethyl-                                               0.5   20.0   20.0       6.5        18.0   4.0   amine  1.5   20.0   40.0       10.0       24.0   7.0          3.0__________________________________________________________________________     Components of the composition, percent by weight     Product of reaction of                 Product of reaction of                              Product of reaction of                                              Protective   Composition     benzyl chloride and                 chlorobenzyl chloride and                              benzylidene chloride                                              effect after   supply rate,     hexamethylenetetramine                 hexamethylene tetramine                              hexamethylenetetramine                                              240 hours,No.   mg/l   (molar ratio 1:0.25)                 (molar ratio 1:0.35)                              (molar ratio 1:0.45)                                          Water                                              %1  2      9           10           11          12  13__________________________________________________________________________ 1.   20.0   0.5         --           --          to 100                                              64.3 2.   20.0   --          1.0          --          to 100                                              93.0 3.   20.0   --          --           2.0         to 100                                              98.3 4.   20.0   --          0.5          --          to 100                                              63.1 5.   20.0   --          --           1.0         to 100                                              90.4 6.   20.0   2.0         --           --          to 100                                              96.0 7.   20.0   --          --           0.5         to 100                                              63.0 8.   20.0   1.0         --           --          to 100                                              90.1 9.   20.0   --          2.0          --          to 100                                              96.410.   20.0   --          0.5          --          to 100                                              59.9   20.0   --          1.0          --          to 100                                              91.2   20.0   --          2.0          --          to 100                                              96.9   20.0   0.5         --           --          to 100                                              61.4   20.0   1.0         --           --          to 100                                              92.0   20.0   2.0         --           --          to 100                                              97.3   20.0   --          --           0.5         to 100                                              64.4   20.0   --          --           1.0         to 100                                              91.3   20.0   --          --           2.0         to 100                                              96.0__________________________________________________________________________ 
    
     The evaluation of the protective effect of the composition according to the present invention and that of the USSR Inventor&#39;s Certificate No. 834334 against deposition of calcium carbonate scaling was effected according to the following procedure. 
     Oversaturated solutions of calcium carbonate are prepared by mixing equivalent amounts of sodium carbonate and calcium chloride. 
     The reaction proceeds according to the scheme: ##STR12## 
     The initial concentration of calcium carbonate in the oversaturated solution is 7.0 g/l. All the experiments are conducted at the temperature of 40±1° C. under stirring at the speed of 500 r.p.m. The supply rate of the composition is 20.0 mg per liter of the oversaturated solution. 
     Assessment of the protective effect was carried out 240 hours afterwards by sampling and analysis of the sample for calcium ions. The protective effect value was calculated by the formula given hereinabove. 
     Table 5 gives particular formulations of the composition according to the present invention and corresponding values of the protective effect against deposition of calcium carbonate. 
     As the phosphonomethylated derivative of 1,3-diaminopropanol-2 of the general formula (I) a mixture of products with a different degree of polymerization, namely n=1, n=5 and n=20 is used. These products are employed in the following proportions, percent by weight: 
     
         ______________________________________   at  n = 1         80       n = 5         15       n = 20         5.______________________________________ 
    
     Moreover, use is made of a mixture of 1,3-diaminopropanol-2 (n=1) and the derivative of 1,3-diaminopropanol-2 of the general formula (II) where n=5 and 20 at the same proportions of the products in a mixture. 
     As the alkali metal chloride sodium chloride is used. 
     For the purpose of comparison, Table 5 also shows the assessment of the protection effect against deposition of calcium carbonate scaling obtained from the prior art composition according to the USSR Inventor&#39;s Certificate No. 834334. 
     
                                           TABLE 5__________________________________________________________________________        Components of the composition, percent by weight                   Mixture of        Phosphonomethylated                   1,3-diaminopropanol-2      Water-soluble        derivative of                   derivative of Hydrochloric                                        Sodium                                              organic solventNo.   Composition        1,3-diaminopropanol-2                   1,3-diaminopropanol-2 acid                                 acid   chloride                                              Name   Amount1  2         3          4             5      6     7      8__________________________________________________________________________1. Known composition        5.0        5.0           3.0    3.00  --     --2. (USSR Inventor&#39;s        7.5        5.5           10.0   4.0   --     --3. Certificate        10.0       6.0           18.0   5.0   --     --4. No. 834434)        15.0       6.5           24.0   6.0   --     --5.           20.0       7.0           30.0   7.0   --     --6. Composition of        5.0        5.0           3.00   3.0   Diacetone                                                     0.57. this invention        20.0       6.5           18.0   4.0   alcohol                                                     1.58.           40.0       10.0          24.0   7.0          3.09.           50.0       7.0           30.0   5.0          4.010.          5.0        5.0           3.0    3.0   Ethanol                                                     0.511           20.0       6.5           18.0   4.0          1.512.          40.0       10.0          24.0   7.0          3.013.          50.0       7.0           30.0   5.0          4.014.          5.0        5.0           3.0    3.0   Methanol                                                     0.515.          20.0       6.5           18.0   4.0          1.516.          40.0       10.0          24.0   7.0          3.017.          50.0       7.0           30.0   5.0          4.018.          5.0        5.0           3.0    3.0   Methylethyl-                                                     0.519.          20.0       6.5           18.0   4.0   ketone 1.520.          40.0       10.0          24.0   7.0          3.021.          50.0       7.0           30.0   5.0          4.022           5.0        5.0           3.0    3.0   Dimethyl-                                                     0.523           20.0       6.5           18.0   4.0   formamide                                                     1.524.          40.0       10.0          24.0   7.0          3.025.          50.0       7.0           30.0   5.0          4.026.          5.0        5.0           3.0    3.0   Triethylamine                                                     0.527.          20.0       6.5           18.0   4.0          1.528.          40.0       10.0          24.0   7.0          3.029.          50.0       7.0           30.0   5.0          4.030.   Comparison        2.5        3.0           2.0    2.5   Diacetone                                                     0.4   composition        2.5        3.0           2.0    2.5   alcohol                                                     0.432.          2.5        3.0           2.0    2.5          0.4__________________________________________________________________________         Components of the composition, percent by weight         Product of reaction of                     Product of reaction of                                   Product of reaction                                                    Protective         benzyl chloride and                     chlorobenzyl chloride and                                   benzylidene chloride                                                    effect after         hexamethylenetetramine                     hexamethylene tetramine                                   hexamethylene tetramine                                                    240 hours,No.   Composition         (molar ratio 1:0.25)                     (molar ratio 1:0.35)                                   (molar ratio 1:0.45)                                               Water                                                    %1  2          9           10            11          12   13__________________________________________________________________________1. Known composition         --          --            --          to 100                                                    52.32. (USSR Inventor&#39;s         --          --            --          to 100                                                    61.63. Certificate         --          --            --          to 100                                                    70.44. No. 834434 --          --            --          to 100                                                    89.25.            --          --            --          to 100                                                    43.26.            0.5         --            --          to 100                                                    66.27.            1.0         --            --          to 100                                                    90.38. this invention         2.0         --            --          to 100                                                    95.89.            1.5         --            --          to 100                                                    99.810.           --          0.5           --          to 100                                                    66.811            --          1.0           --          to 100                                                    91.212.           --          2.0           --          to 100                                                    94.813.           --          1.5           --          to 100                                                    99.914.           --          --            0.5         to 100                                                    65.715.           --          --            1.0         to 100                                                    90.716.           --          --            2.0         to 100                                                    95.017.           --          --            1.5         to 100                                                    10018.           0.5         --            --          to 100                                                    63.819.           1.0         --            --          to 100                                                    91.320.           2.0         --            --          to 100                                                    96.421.           1.5         --            --          to 100                                                    10022.           --          0.5           --          to 100                                                    62.823.           --          1.0           --          to 100                                                    90.324.           --          2.0           --          to 100                                                    94.425.           --          1.5           --          to 100                                                    10026.           --          --            0.5         to 100                                                    63.027.           --          --            1.0         to 100                                                    90.228.           --          --            2.0         to 100                                                    95.029.           --          --            1.5         to 100                                                    10030.   Comparison  0.25       --            --          to 100                                                    38.9   composition         --           0.25         --          to 100                                                    40.032.           --          --             0.25       to 100                                                    40.0__________________________________________________________________________ 
    
     The comparative evaluation of the data given in Table 5 allows a conclusion that the composition according to the present invention is substantially superior, in the efficiency thereof, over the prior art composition according to the USSR Inventor&#39;s Certificate No. 834334 upon inhibition of calcium carbonate scaling. Thus, the protective effect ensured by the composition according to the present invention at lower limits of concentrations is 63.7%, whereas that of the prior art composition is only 52.3%. 
     A similar result is obtained for upper limits of concentrations of the components of both compositions. Thus, the protective effect of the prior art composition is 93.0%, whereas for the composition according to the present invention it is equal to 100%.