SU865851A1 - Method of producing inhibitor of mineral salt deposits - Google Patents

Description

one

The invention relates to the field of obtaining substances that prevent the formation of salt crystals and are added to the circulating water supply systems, as well as in the extraction of oil and associated water to prevent salt deposition in pipelines, valves, equipment and downhole equipment.

Known methods for producing scale inhibitors include the usual mixing of substances with inhibitory properties and substances that enhance their inhibitory ability U J.

The closest in technical essence and the achieved result, by inhibiting calcium sulphate and carbonate deposits, is a method of producing an inhibitor, consisting of mixing polyethylene enpolyamine, myoethanolamine, carbamide and ammonium chloride, then subjected to phosphorylation in the presence of form and dehydrated ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho ortho sphyte, and further orthospheric dehydrogenation, and then subjected to phosphorylation in the presence of phosphorus in the presence of phosphate and ammonium chloride. medium followed by neutralization and cooling of the obtained inhibitor solution 2.

The ratio of the components is chosen so that for each hydrogen atom of the ammonium or amide group there are 1 mol of formaldehyde and 1 mol of phosphorous acid. The resulting inhibitor is an aqueous solution that does not freeze at minus 30 ° C.

The disadvantages of the known β-method are: 1. The increased residual formaldehyde content in the finished product is 0.8-2.0%. which gives the inhibitor an unpleasant smell and increases its toxicity in the water of water bodies

(MPC formaldehyde 0.05 mg / l).

2. High inhibition efficiency at optimal inhibitor concentration (3 mg / l), strong and nonex15

vivasit decreases with decreasing concentration.

The purpose of the invention is to reduce the residual content of free form 20 aldehyde in the resulting product and to increase the effectiveness of the inhibitor.

The goal is achieved by the fact that two-stage phosphorylation is carried out.

25 stage of phosphorylation of the component containing nitrogen, which is the most active with respect to the formaldegnd, and then introducing into the neutralized and cooled solution of the peroxide compound inhibitor (hydrogen peroxide

yes or sodium percarbonate) e amount 0.3-0.5% by weight of the inhibitor solution S

The amount of formaldehyde injected should be equimolar to the amount of phosphorous lobe and the number of hydrogen atoms in the amino groups. If this violation is violated, i.e. in the presence of hydrogens of the amino group not substituted by methylphosphonic groups, the effectiveness of the inhibitor decreases markedly, the same happens with an excess of unreacted phosphorous acid and formaldehyde. However, even if the exact ratios are observed, the phosphorylation reaction is difficult to complete, since the reaction rate decreases with a decrease in the concentration of the reactive substances and with the disappearance of the most actively reacting amino groups. Experiments not with a synergistic mixture of aminovir with individual components showed that with equimolar loads and the same reaction conditions, the highest content of free formaldehyde is obtained using polyethylene polyamine (1.942, 0%), and the lowest for ammonium chloride (0.3-0.4 %), urea and monoethanolamine occupy an intermediate position (O, 79-1.1%). In the amino mixture, the most active groups react first and the less active remain and, due to their low reactivity, cannot reduce the formald content. The guid is lower than 0.70, 8%. Therefore, the phosphorylation reaction must be carried out in Stage 2, first with less active amines, and at the end with more active components. The addition of peroxide compounds (30% hydrogen peroxide solution or persalt salt powder — sodium percarbonate) further reduces the content of free formaldehyde by a factor of magnitude and, moreover, increases the effectiveness of the inhibitor at low concentrations. The amount of hydrogen peroxide added is calculated to bring the residual formaldehyde content to 0.1-0.15%; such a small amount of formaldehyde does not adversely affect the smell, nor the toxicological properties, nor the effectiveness of inhibition.

The method for producing the inhibitor is carried out in a manner that is as follows.

Polyethylene polyamine, carbamide, and monoethanolamine (amines play an additional role as inhibitors of acid corrosion), then water, hydrochloric acid, phosphorous acid, and formaldehyde are loaded into the enamelled reactor. The temperature of the mixture due to the neutralization of the amines increases to 50 ° C ° C, the heating is turned on, the temperature is brought to 100 ° C and the mixture is kept for 2.5 hours with the stirrer at 98 ° C and then ammonium chloride is added and left for another 1 hour. with the same temperature. Then the contents of the reactor are cooled and a 40-45% sodium hydroxide solution is added while cooling, bringing the pH of the mixture to 3.6-3.9. After that, a peroxide compound (or technical hydrogen peroxide of 30% concentration, or a dry sodium percarbonate (persol) composition of Na, CO2-HjO- with hydrogen peroxide content of 24.3%) is introduced into the inhibitor solution. The role of peroxide is to oxidize most of the mass of free formaldehyde, thus reducing the toxicity of the product and increasing the efficiency of inhibition at low concentrations of inhibitor. When the peroxide is introduced into the hot inhibitor solution, it is completely consumed within 1 hour, and at 20 ° C, its action lasts for a day, in the latter case, the data on the effectiveness of inhibition are higher. When the content of the inhibitor is 1 mg / l while reducing the residual formaldehyde in it from 0.78% to 0.1%, the efficiency of inhibition with calcium carbonate increases 1.5 times, and with calcium sulfate 2.3 times. Such a decline. the amount of formaldehyde is achieved (depending on the initial content) with the addition of 0.3-0.7% peroxide (calculated per 100%). A further increase in the amount of peroxide, while bringing the content of free formaldehyde to hundredths or thousandths of a percent, but has little effect on the effectiveness of inhibition.

Claims (3)

Example 1. In a reactor with an acid-resistant coating, equipped with an ample cooler, devices for mixing, temperature measurement, heating and cooling, 37 l of water, 11 kg of polyethylene polyamine (with a nitrogen content of 31% and an average molecular weight of 189), 9 kg of monoethanolamine counting on 100%, 4.9 kg of urea, 77 kg of 28% hydrochloric acid or equivalent amount of acid of another concentration, 82 kg of technical orthophosphorous acid, and 83 kg of 37% formalin. After enticing to obtain a homogeneous reaction mass, it is heated to 98-100 G and kept at this temperature and stirring for 2.5 hours. Then, 1.7 kg of ammonium chloride are charged and kept at 98-100 ° C for another 1 h, then cooling is turned on. and at 60-70 ° C, a 42% sodium hydroxide solution is gradually supplied in an amount of 130 g, while the pH of the reaction mass is set in the range 3.6-3.9. After cooling the reaction mass to 20–25 ° C, 7.3 kg of a 30% hydrogen peroxide solution or the equivalent amount (0.5% by weight) of a peroxide solution of a different concentration is added to it. 440 kg of an inhibitor solution are obtained with an inhibitor content of 32%. Example 2. The process of obtaining the number of input components, order of loading, temperature and time parameters of all stages of the process are the same as in Example 1. The difference in the amount of hydrogen peroxide administered. 4.4 kg of 30% hydrogen peroxide (0.3% by weight of the solution, calculated on 100% peroxide) are introduced. Example 3. The number of input components, loading order, temperature and time parameters of all stages of the production process are the same as in Example 1. The difference in the amount of hydrogen peroxide added. 10 kg of 30% hydrogen peroxide (0.68% by weight of the solution, calculated as 100% peroxide) are introduced. Example 4. The number of input components, loading order, temperature and time parameters of all stages of the production process are the same as in Example 1. The difference in replacing hydrogen peroxide with sodium percarbonate (persol). 7.2 kg of sodium percarbonate (0.4% by weight of the solution, per 100% peroxide) are added. Get 438 kg of the solution with the content of the inhibitor 32%. It is possible to carry out the method of obtaining the inhibitor without using phosphorous acid, instead it can be taken phosphorus trichloride or dimethyl phosphite. Froze Into a reactor with an acid-resistant coating, devices for mixing, intensive cooling and heating, a tube with a bubbler at the very bottom of the reactor and a HFc i back is followed by a cooler, followed by a ns1 absorption column, 83 kg of 37% formalin is loaded, 51 kg of water, 11 kg of polyethylene polyamine, 9 kg of monoethanolamine and 4.2 kg of urea. By lowering the temperature in the reactor, 137.5 kg of phosphorus trichloride are gradually supplied through a pipe with a sparger, over a period of 1 hour, cooled, without allowing the temperature to rise higher. In this case, 75% of the formed HC1 goes through the reflux condenser to the absorption column, and 25% remains in the reaction zone. After the end of the supply, the temperature is raised to EV-SOO C, the ature is maintained at this rate {) for 2.5 hours, 1.7 kg of ammonium chloride is added and the aging is continued for another 1 hour. Then cooling is switched on and at 60-70 ° C 142 kg of a 42% sodium hydroxide solution are fed in, obtaining a pH in the range 3.6-3.9. After cooling to 20–25 ° C, 7 kg of 30% hydrogen peroxide (0.5% by weight of the solution, calculated as 100% peroxide) are added, and 410 kg of the solution with a content of 34% of an inhibitor is obtained. Example 6. A reactor with an acid-resistant coating, devices for stirring, heating, cooling and measuring the temperature, equipped with a direct cooler, is charged with 15 liters of water, 11 kg of polyethylene polyamine, 9 kg of monoethanolamine, 4.2 kg of urea, 110 kg of dimethylphosphite (1 mol) , 165 kg of 37% formalin (2 mol) and 77 kg of 28% hydrochloric acid. The contents of the reactor are heated, gradually stripping 80 kg of methylalarite. After termination of the mixture, with stirring and 98-100 seconds, the mixture is kept for 2.5 hours, 1.7 kg of ammonium chloride is added and the mixture is kept at the same temperature for another 1 hour, after which cooling is started. And at 60-70 ° C 130 kg of a 42% aqueous solution of sodium hydroxide, the pH of the mass is adjusted to 3.6-3.9. After cooling, 8.5 kg of 30% hydrogen peroxide (0.6% of the mass of the solution, calculated as 150% peroxide) are added to 20-25 ° C and 442 kg of solution are obtained with an inhibitor content of 32%. The obtained and comparative data on the effectiveness and content of formaldehyde in the resulting inhibitors are given in the table. All samples of inhibitors, including those known, when left for 48 h at minus, remained liquid. The technical and economic advantages of the proposed method in comparison with the known one are as follows: 1. EFFECT: inhibiting the effectiveness of deposits of mineral salts from solutions containing 1 mg / l of inhibitor for calcium sulfate and calcium carbonate more than 2 times. 2. Reducing the residual content of free formaldehyde to 0.1Q, 15% r i.e. more than 5 times, which improves the toxicological properties of the inhibitor and improves its smell, beside him with it (reducing odor). 3. The preparation of the inhibitor is based on raw materials, the industrial output of which has been mastered by the domestic industry on a large scale; the production process has no production wastes other than hydrochloric acid using phosphorus trichloride and methylal using dimethylphosphite. The method of obtaining the inhibitor of deposits of mineral salts by phosphorating a mixture of polyethylenepolyamine, monoethanolamine, carbigundum and ammonium chloride in the presence of formaldehyde and orthophosphoric forkstoy acid at 98-100 ° C with aqueous phosphorolation in an aqueous salt and ammonium chloride with 98% to 100 ° C, followed by the neutralization and cooling of the acid with a mixture of polyethylene polyamine and ammonium chloride. the effectiveness of the inhibitor and the decrease in its residual formaldehyde content, first 18,8 43.3 36.9 43.0 40.8 42.0 43.8 phosphorylated a mixture of polyethylphenolamine, monoethanolamine and urea, then ammonium chloride, and after cooling, hydrogen peroxide or sodium percarbonate was added in an amount of 0.30, 5% of the total mass of the inhibitor solution. Sources of information taken into account in the examination 1. The author's certificate of the USSR 610852, cl. From 09 K 7/02, 1976. 2. USSR author's certificate No. 719970, „cl. C 02 C 5/00, 1978.