JPS6097099A - Composition preventing adhesion of inorganic salt - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for preventing the deposition of inorganic salts from aqueous solutions on metal surfaces, and is used in return water supply systems, distillation systems for mineral water, extraction, transportation and pretreatment of oil and natural gas. Can be useful in processing steps.

Compositions for preventing the deposition of inorganic salts containing aminomethylene phosphonic compounds and surfactant additives are known in the art.

U.S. Patent No. 3,467.193 C1,166-279
(z+68 years) is nitrilotrimethylenephosphonic acid of the following formula as an aminomethylene phosphonic compound, i.e., and a compound of the following formula as a surfactant, i.e., [('12 H25+2 N100H,)2) ” [0
1]-.

In addition, in this technical field, polyethylenepolyamine-N-methylenephosphonic acid of the following general formula, i.e., -f CH2-0H2-N +n OH2 PO(OH)2 (however, n = 1 to 14) and polyacrylamide are used. Compositions that prevent the adhesion of inorganic salts they contain are also known (US Pat. No. 3,483,925 cl.).

166-279.1968).

Additionally, methods are known in the art for preventing the deposition of inorganic salts through the use of aminomethylene phosphonic acid having the general formula: That is, PO(OH) PO(OH)2 (however, n = 1 to 5) (Soviet Union Inventor's Certificate No. 789
No. 434, Int, 01,5002F 5/14 J
21 B 43/12° 1980).

However, the above-mentioned methods provide only insufficient protection against the deposition of inorganic salts. Furthermore, the use of polyacrylamide in the above-mentioned compositions involves considerable difficulties in formulating the use solutions of this particular compound from gel-like commercial products.

The production of aqueous solutions of polyacrylic rhodides requires special equipment, which necessarily results in inefficient labor and power consumption.

The prior art compositions that are most similar in content and effect to the compositions of the present invention are those of the general formula 1,
Phosphonomethylated derivatives of 3-diaminopropano-2, i.e. PO(OH) PO(OH)2 (where n=1 to 5) and 1,3-diaminopropano-2
2 and/or a derivative of 1,3-diaminopropanol-2 of the general formula below, i.e. H2N-fGH
A composition that prevents the adhesion of inorganic salts containing 2-OH-OH2-NH-)nH(II)OH (where n=2 to 5), hydrochloric acid, sodium chloride, and water. The components are present in the following proportions (% by weight): That is, the phosphonomethylated derivative S, O~20.01.3-diaminopropanol-2 of general formula (1) 1,3-diaminopropanol-2 and/or 1,3-diamino of general formula (II) Propanol-2 derivative 3.0~
7.0 Hydrochloric acid 3.0-30.0 Sodium chloride 30-T, 0 Water ~100 (Soviet Union Inventor's Certificate No. 834334, Int.

However, the composition with C1,5 Crown 21 B 43100.1981 has only an insufficient protective effect against the deposition of inorganic salts, and the minimum freezing temperature of the composition is -35°C. Therefore, it is difficult to handle it under winter weather conditions. The latter condition severely limits the possibilities of using this composition in areas with an arctic climate or requires the use of expensive antifreeze components.

The aim of the invention is to overcome the above-mentioned drawbacks.

The present invention aims to provide a composition which has an increased protective effect and which prevents the deposition of inorganic salts having a low freezing point.

The purpose is to phosphonomethylate 1,3-diaminopropanol-2 of the following general formula! 1! conductor, t & PC(OH) PO(OH)2 (F41. n = 1 to 20), and 1,3-diaminopropanol-2 and (or) 1,3-diamino of the following general formula This is achieved by providing a composition that prevents the adhesion of inorganic salts containing derivatives of propano-2, i.e. OH (where n=2-20), hydrochloric acid, alkali metal chlorides and water. .

The composition according to the invention further comprises a mixture of benzyl chloride, chlorobenzyl chloride or benzylidene chloride or a mixture of these chlorinated compounds and hexamethylenetetramine.
: products of interaction in a molar ratio of 0.25 to 0.450,
and a water-soluble organic solvent, and these components are present in the following proportions (% by weight). That is, phosphonomethylated derivatives of 1,3-diaminopropanol-2 of general formula (1) 50-50.0 1.3-diaminopropanol-2 and (t) 1.3 of general formula (2) -S) Aminopropanol-2 derivative 5.0-10.0 hydrochloric acid
・3.0-30.0 Alkali metal chloride 3.0-7.0 Product of the interaction of benzyl chloride, benzylidene chloride, chlorbenzyl chloride, or a mixture of these chlorinated compounds with hexamethylenetetramine 05 ~2.5 Water-soluble organic solvent 0.5-4.0 Water Residual As the water-soluble organic solvent, it is preferable to use diacetone alcohol, methanol, ethanol, methyl ethyl ketone, dimethylformamide, and triethylamine.

Due to the introduction of the product of the interaction of hexamethylenetetramine with the above-mentioned benzyl halide, the composition according to the invention has a protective effect against the deposition of inorganic salts in equipment using water compared to the compositions of the prior art. This makes it possible to increase the amount considerably.

Therefore, at the lower concentration limit of the components of the known composition according to Soviet Union Inventor's Certificate No. 834334, the protective effect against calcium sulfate deposition is only 46.6%, whereas the protective effect of the composition according to the invention is Maximum 63.8
%Met.

Similar results were obtained at the upper limit concentrations of the components of both groups of acids.

That is, the protective effect of the Soviet Union Inventor's Certificate No. 834334 was 86.5%, while that of the present invention was 99.6%.

The freezing point of the composition according to the present invention is bottom -100°C,
This makes it possible to use the composition under arctic climatic conditions without introducing expensive antifreeze agents.

It is inappropriate to reduce the lower concentration limits of the components of the compositions according to the invention. This is because this reduces the protective effect and deprives the composition of its advantage over prior art compositions.

It is also inappropriate to increase the upper concentration limits of the components of the compositions according to the invention. This is because already at the above concentrations of the components the protective effect is equal to 100%.

The composition for preventing the deposition of inorganic salts on buttons of the present invention is prepared in a conventional manner by dissolving the starting components in an aqueous solution of hydrochloric acid.

The components used in the composition according to the invention, namely the general formula (
The phosphonomethylated derivative of 1,3-diaminopropanol-2 in 1) is prepared by preparing 1,3-diaminopropanol-2 and (t) the general formula (II) with formaldehyde and phosphorus trichloride at a temperature of 45°C. The desired product is prepared by precipitating the desired product from the reactants with methanol after modification of the derivative of 1,3-diaminopurpanol-2.

The product is a white crystalline compound that is highly soluble in water and insoluble in alcohol and acetone, and is strongly acidic.

1. The procedure for preparing the phosphonomethylated derivative of 3-diaminopropanol-2 is based on the Federal Inventor's Certificate No. 8766.
No. 66, Int, C1, '008 G 79104.
Described in ODa J 5/20.

Components of the composition according to the invention, namely 1,3-diaminopropanol-2 and/or 1 of general formula (If)
,3-diaminopropanol-2 derivatives are prepared by reacting shrimp chlorohydrin with a considerable excess of ammonia in the form of an aqueous solution and then reacting at a temperature of 10 to 30°C for a period of 1/4 to 6 hours. The ammonia solution is prepared by heating the body, neutralizing the hydrochloric acid formed with an alkali metal hydroxide such as sodium hydroxide, and distilling off the excess aqueous solution of ammonia.

A method for preparing 1,3-diaminopropanol-2 and/or derivatives of 1,3-diaminopropanol-2 of general formula () is described in U.S. Pat. No. 4,432,553 01.26.
0 to 585.

Products further included in the composition according to the invention are:
benzyl chloride, chlorobenzyl chloride or benzylidene chloride or mixtures of these chlorinated compounds, respectively at t:
o, zs ~ 0.45: 100 at a molar ratio of 2.2 to 3.6
It is prepared by reaction with hexamethylenetetramine in the presence of caustic at a temperature in the range of -125°C.

The product consists of a clear yellow-brown liquid.

The procedure for preparing the product of the interaction of hexamethylenetetramine with the benzyl halide described above is described in Sogieto Inventor's Certificate No. 469771, Xnt, G1. '023
F 11/1 OK is listed.

Compositions according to the invention may be useful in return water supply systems, mineral water distillation systems, and oil and natural gas extraction, transportation and pretreatment processes.

For example, in oil field extraction, several embodiments are possible for introducing the composition according to the invention (antiscaling agent) into the extraction valve. 1. Continuous dosing of the composition into the annular space of the oil well by means of a metering device.

2. Continuous dosing of the composition through pump wells to the device that maintains reservoir pressure.

3. Periodic bombing of compositions into production formations via extraction wells. This mode uses compositions that prevent the deposition of inorganic salts, which are adsorbed onto the porous surfaces of the critical wells and are slowly flushed by mineral water during well sampling by known methods, thus leaving the well and the surface for several months. It is based on the composition's ability to prevent inorganic salt deposition in well appurtenances.

4. Continuous dosing of the composition by means of a metering device to the inlet of the heat exchange device of the device for thermochemical pretreatment of crude oil.

The evaluation of the protective effect of the compositions according to the invention and of the compositions according to Soviet Union Inventor's Certificate No. 834334 against calcium sulfate deposits is carried out according to the following procedure.

A supersaturated calcium sulfate solution is prepared by mixing equal amounts of sodium sulfate and calcium chloride. The reaction occurs according to the equation below. That is, Ca0t2+Na2804-+Ca804↓+2NaO
The initial concentration of calcium sulfate in the supersaturated solution is 10 g/
It is l.

The amount of composition added to the supersaturated solution of calcium sulfate in the entire series of experiments was 20.0 mg/L, whereas only a few composition components were changed.

The solution was kept constant at a temperature of 25°C. The protective effect against calcium sulfate deposition was determined by sampling and analyzing samples for 240 hours of ridge calcium ion. The protective effect was calculated according to the formula below. i.e. co -ak where E is the protective effect (%), CO is the initial concentration of calcium ions in the supersaturated solution (g/L) and Ck is the concentration in the solution at a given moment without addition of the composition of the invention The concentration of calcium ions (g/l), C11d is the concentration of calcium ion (g/l') in the solution at a given moment after the introduction of the composition according to the invention.

Table 1 shows the compositions according to the present invention and the inventor's certificate No. 834.
334, and the values of the protective effect against calcium sulfate deposition.

The phosphonomethylated derivatives of 1,3-diaminopropanol-2 of general formula (1) have different degrees of polymerization, that is, n=1. n=5. A mixture of products with n=20 is used. The ingredients are used in the following proportions (% by weight). That is, n = 1, 80 n = 5 1 5 n = 20 5 Furthermore, 1,3-diaminopropanol-2 (n = 1)
and a mixture of derivatives of 1,3-diaminopropanol-2 of the general formula a) with n=s and n=20 in the same proportion of products in the mixture.

Sodium chloride is used according to the invention as alkali metal chloride.

As can be seen from the data given in Table 1 above, the composition according to the invention is superior in its efficiency to the known composition according to Soviet Union Inventor's Certificate No. 834334. Therefore, the protective effect of the composition according to the invention is 638%, while the protective effect of the composition according to the Soviet Union inventor's certificate at the lower limit concentration of the components is only 446%.

Similar results were found regarding the protective effects at the upper concentration limits of both acid classes. Therefore, the protective effect for the known composition is 865% and for the composition according to the invention it is 965%.
It is 96%.

Furthermore, data showing the protective effect of the composition according to the invention against calcium sulfate deposition are shown below in Cloth 2 (test procedure described above). Table 2 shows specific formulations of the compositions according to the invention and the corresponding values of the protective effect obtained. General formula f
The phosphonomethylated derivative of 1,3-diaminopropanol-2 in fl and the derivative of 1,3-diaminopropanol-2 in general formula (11) are shown as individual compounds. Sodium chloride was used as alkali metal chloride according to the invention.

From the data given in Table 2 above, it can be seen that the compositions according to the invention reliably provide a high protective effect against scaling deposits of inorganic salts.

! 23 shows the specific formulation of the composition according to the invention and the corresponding values of the protective effect against calcium sulfate deposition. Further products included in the compositions according to the invention are the products of the interaction of various mixtures of hexamethylenetetramine and benzyl halides. Sodium chloride is used as alkali metal chloride.

Table 4 shows the specific formulations of the compositions according to the invention and the corresponding values of the protective effect on the formation of scaling of A.sium sulfate. The products further contained in the compositions according to the invention are the products of the reaction between hexamethylenetetramine and the respective benzyl halides, and potassium chloride is used as the alkali metal chloride.

Composition according to the invention against calcium carbonate scaling deposits and Soviet Union Inventor's Certificate No. 834334
The protective effect of the composition of No. 1 was evaluated according to the following procedure.

Prepare a supersaturated solution of calcium carbonate by mixing equivalent amounts of sodium carbonate and the salt ``hycalcium.''

The reaction proceeds according to the formula below. That is, 0aOt2
+Na200. −+ (jaCO, ↓+2aacz The initial concentration of calcium carbonate in the supersaturated solution is 7.0 g/l
It is. All experiments are carried out at a temperature of 40 ± 1 °C with stirring at a speed of 500 r, p, m). The feed rate of the composition is υ20. Omg.

The protective effect was evaluated by sampling and analyzing samples for calcium ions after 240 hours. The value of protective effect was calculated by the above formula.

Table 5 shows specific formulations of the compositions according to the invention and the corresponding values of the protective effect against calcium carbonate deposition.

As phosphonomethylated derivatives of 1,3-diaminopropanol-2 of general formula (■), different degrees of polymerization, i.
A mixture of products with =1, n=s and n=20 is used. These products are used in the following proportions (% by weight). That is, when n=1, 80 n-515 n=20 5 Furthermore, 1,3-diaminopropanol-2 (n=1)
oh! 1.3- of the general formula ('Il) of n-5 and 20
A mixture of derivatives of diaminopurpanol-2 is used in the same proportion of products in the mixture.

Sodium chloride is used as alkali metal chloride.

For comparison, Table 5 shows the Soviet Union inventor's certificate No. 8343.
Also shown is the evaluation of the protective effect against calcium carbonate scaling deposits obtained from the prior art composition according to No. 34.

Comparative evaluation of the data given in Table 5 shows that the composition according to the invention is effective in the prevention of calcium carbonate scaling according to Soviet Union Inventor's Certificate No. 8343.
The conclusion is that it is substantially superior to the prior art composition according to No. 34. Therefore, the protective effect reliably provided by the composition according to the invention at the lower concentration limit is 63.1%, whereas the protective effect of the prior art composition is only 52.3%.

Similar results are obtained for the upper limit concentrations of the components of both groups of acids. Therefore, the protective effect of the prior art composition is 93.0
%, whereas for the composition according to the invention 1
Equal to 00%.

Claims (2)

[Claims] (1) A phosphonomethylated derivative of 1,3-diaminopropanol-2 of the following general formula, namely PO(OH)P
O(OH)22 (where n=1 to 20) and 1,3-cyaξnolobanol-2 and (t) derivatives of 1,3-diaminopropanol-2 of the following general formula, i.e. H2N (-OH2-OH-OH2-NH+nH@■OH (however, n=2 to 20), in a composition for preventing the adhesion of an inorganic salt containing hydrochloric acid, an alkali metal chloride, and water, the above composition furthermore, the product of the interaction of benzyl chloride, chlorobenzyl chloride or benzylidene chloride, or a mixture of the above chlorinated compounds, with hexamethylenetetramine in a molar ratio of 1:0.25 to 0.45, respectively, and a water soluble The above components are contained in the following proportions (mI amount %), i.e., the phosphonomethylated rust conductor of the general formula (11, 1,3-diaminopropanol-2) 5.0 to 50,0 1. 3-diaminopropanol-2 and (or) a derivative of 1,3-diaminopropanol-2 of general formula (1) 5.0-10.0 Hydrochloric acid 3.0-3G, 0 Alkali metal chloride 3.0 ~7.0 Product of the interaction of hexamethylenetetramine with hensyl chloride, chlorobenzyl chloride or benzylidene chloride or a mixture of the above chlorinated compounds 0.5-2.5 Water-soluble organic solvent 0.5-4.0 Water Balance A composition for preventing the adhesion of the above-mentioned inorganic salt, characterized in that it is used in. (2) The composition according to claim 1, which contains diacetone alcohol, methanol, ethanol, methyl ethyl ketone, dimethylformamide, or triethylamine as the water-soluble organic solvent.