RU2350689C2 - Method for making acid corrosion inhibitors - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention refers to protect metals against corrosion in acid, aqua-saline mediums and can be used in chemical, gas-and-oil producing industries, as well as in metallurgy and power engineering. Method covers reaction of polyethylene polyamine PEPA or polypropylene polyamine PPPA and benzyl chloride BC and application of reaction product as an active base of inhibitor. Herewith PEPA or PPPA and BC react with desalted water at first at temperature 45-50°C within 0.5 h, then at temperature 65-70°C at mole ratio (PEPA or PPPA):BC equal to 1:(1-3) within 2-5 h. Then it is exposed while mixed within 1-3 h at 80-85°C with or without following dispensing of isopropyl alcohol at temperature 70-75°C and aqueous solution of urotropine and neonol, prepared by dissolution urotropine and neonol in desalted water at ambient temperature within 0.5-1.0 h. Reaction mass is exposed while mixed at temperature 65-70°C within 1 h thus producing inhibitor containing, wt %: active base 12-22, isopropyl alcohol 0-30, urotropin 5-12, neonol 3-7, water - the rest.

EFFECT: improved inhibiting properties, reduction in price of yield products and extended raw materials sources of inhibitors.

1 tbl, 5 ex

Description

The invention relates to the field of protection of metals from corrosion in acidic, water-salt environments, namely, to obtain an inhibitory composition based on polyethylene polyamines (PEPA), polypropylene polyamines (PPPA) and benzyl chloride (CB), which can be used in the chemical, oil and gas mining industries as well as in metallurgy and energy for various types of acid treatment of products, equipment and transportation of acids.

It is known to use a wide range of compositions of complex composition — Neftekhim-3, SNPKh-6301, SNPKh-6302, SNPKh-6011, SNPKh-6014, Vikor, as well as a mixture of aminoparaffins obtained by amination of the chlorination product of liquid paraffins with liquid chlorine, to prevent corrosion of oilfield equipment of a wide range of compositions From _10-26 with a boiling range of 220-345 ° C [RF Patent No. 2074170, Bull. No. 6, 1997]. The disadvantage of using these corrosion inhibitors is the low degree of protection of the metal from corrosion, poor solubility of the inhibitor in the above environments.

Known corrosion inhibitor obtained by amination of benzenesulfonyl chloride with an aqueous solution of ammonia [RF Patent No. 2096523, 1997].

The disadvantage of this inhibitor is the low degree of metal protection, its poor solubility in the above environments, the multi-stage process of its synthesis.

Closest to the claimed technical essence and the achieved result is an acid corrosion inhibitor based on polyamines and benzyl chloride. The method is carried out by the interaction of acyclic, cyclic di and polyamines with alternating nitrogen atoms between ethylene, propylene or mixed ethylene or propylene groups with benzyl chloride at a temperature of 50-70 ° C in an alcoholic medium in the presence of a 20-23% hydrochloric acid solution for 4-6 hours. The inhibitor may additionally contain 5-30% urotropine. [RF patent No. 2237110, 2004]

A disadvantage of the known acid corrosion inhibitor is the use of polyamines obtained by the synthesis of individual amines (currently not produced in the Russian Federation) and dichloralkanes, with subsequent stages of neutralization, salt separation, distillation of water and distillation of polyamines.

The objective of the invention is the development of a one-stage method for producing an acid corrosion inhibitor, which provide effective protection of metal gas and oilfield equipment, pipelines against corrosion, increase the efficiency of metal protection against corrosion.

The technical result when using the invention is expressed in the cheapening of the finished product, the expansion of the raw material base and the range of corrosion inhibitors.

The above result of obtaining an acid corrosion inhibitor operating in acidic and aqueous-salt environments is achieved by the feature that polyethylene polyamines (PEPA) or polypropylene polyamines (PPPA) are reacted with benzyl chloride in the presence of demineralized water at first at 45-50 ° C in for 0.5 h, then at 65-70 ° C in a molar ratio (PEPA or PPPA): CB, equal to 1: (1-3), for 1.5-5 hours and holding with stirring for 1-3 h at 80-85 ° C followed by dosage at a temperature of 70-75 ° C of isopropyl alcohol and and without it, and an aqueous solution of urotropine and neonol, previously prepared by dissolving urotropin and neonol in demineralized water at ambient temperature for 0.5-1.0 hours, by holding the reaction mass with vigorous stirring at a temperature of 65-70 ° C for 1 h to obtain an acid corrosion inhibitor containing components in the following ratio, wt.%:

Active foundation 12-22 Isopropyl alcohol 0-30 Urotropin 5-12 Neonol 3-7 Water rest

As PEPA, technical mixtures of PEPA with a molecular weight of 132.5-159.5 (average PEPA) are used. As PPPA, technical mixtures of PPPA with a molecular weight of 131-188 (average PPPA).

The technical mixture of PEPA is synthesized at Sterlitamak OJSC “Caustic”, and the technical mixture of PPAA is see “Chemical. prom. ”, 2003, T.80, No. 4, p. 3-7; RF patent No. 2226199; Bull. No 9, 2004

The method of obtaining an acid corrosion inhibitor is confirmed by the following examples.

Example 1. In a reactor equipped with a mixing device, a metering device, a heat transfer jacket, a contact thermometer, a reflux condenser, 13.25 g of PEPA (0.1 mol) (average molecular weight 132.5, composition, wt.%: H ₂ O 0.15; ethylenediamine (EDA) 10.2; diethylenetriamine (DETA) 28.3; N, β-aminoethylpiperazine (N, β-AED) 2.8; triethylenetetramine (THETA) 26.8); tetraethylene pentamine (TEPA) 19.9; pentaethylene hexamine (PEGA) 9.6) and 3 g demineralized water. The reaction mass is stirred at a temperature of 45-50 ° C for 0.5 h. Next, 25.3 g (0.2 mol) of CB are dosed in a molar ratio of PEPA: CB equal to 1: 2, at a temperature of 70 ° C for 1 ,5 o'clock. Maintain the reaction mass at 80-85 ° C for 1.5 hours with vigorous stirring. Then, isopropyl alcohol and a pre-prepared aqueous solution of urotropine and neonol, obtained by dissolving at room temperature in 40.1 g of demineralized water 12.0 g of urotropine and 7.0 g of neonol, are metered into the reactor at a temperature of 70 ° C. The reaction mixture was stirred at 70 ° C for 1 hour. The test results are shown in the table.

Example 2. Under the conditions of example 1, 13.1 g of PPPA (0.1 mol) (average molecular weight 131, composition, wt.%: Н ₂ О 0.6; 1,2-propylene diamine (1,2- DAP) 10.6; dipropylene triamine (DPTA) 25.8; N, β-aminopropyl-2,5-dimethylpiperazine (N, β-APP) 2.0; tripropylenetetramine (TPTA) 22.0; tetrapropylene pentamine (TPPA) 10, 2; pentapropylenehexamine (PPHA) 6.3) and 3 g of demineralized water. The reaction mass is stirred at a temperature of 45-50 ° C for 0.5 hours. Next, 25.3 g (0.2 mol) of CB are dosed in a molar ratio of PPPA: CB equal to 1: 2 at a temperature of 65 ° C for 3 hours followed by exposure of the reaction mixture at 80-85 ° C for 1.5 hours with vigorous stirring. Then, a previously prepared aqueous solution of urotropin and neonol is metered into the reactor at a temperature of 70 ° C. The reaction mixture was stirred at 65 ° C for 1 hour. The test results are shown in the table.

Example 3. Under the conditions of example 1, 15.95 g of PEPA (0.1 mol) was loaded into the reactor (average molecular weight 159.5 composition, wt.%: Н ₂ О 0.1; EDA 7.4; DETA 23.6 ; N, β-AED 9.8; TETA 33.9; TEPA 20.6; PEGA 12.8) and 8 g of demineralized water. The reaction mass is stirred at a temperature of 45-50 ° C for 0.5 hours. Next, 25.3 g (0.2 mol) of CB are dosed in a molar ratio of PEPA: CB equal to 1: 2, at a temperature of 67 ° C for 3 hours followed by exposure of the reaction mixture at 80-85 ° C for 2 hours with vigorous stirring. Then, isopropyl alcohol and a pre-prepared aqueous solution of urotropine and neonol are metered into the reactor at a temperature of 75 ° C. The reaction mixture was stirred at 70 ° C for 1 hour. The test results are shown in the table.

Example 4. Under the conditions of example 1, 18.8 g of PPPA (0.1 mol) were loaded into the reactor (average molecular weight 188 composition, wt.%: Н ₂ О 0.5; 1,2-DAP 12.7; DPTA 27 , 4; N, β-APP 4.5; TPTA 29.8; TPAA 18.7; PPGA 10.8) and 15 g of demineralized water. The reaction mass is stirred at a temperature of 45-50 ° C for 0.5 hours. Next, 37.97 g (0.3 mol) of CB are dosed in a molar ratio of PPPA: CB equal to 1: 3, at a temperature not exceeding 70 ° C. for 5 hours, followed by exposure of the reaction mixture at 80-85 ° C for 2 hours with vigorous stirring. Then, isopropyl alcohol and a pre-prepared aqueous solution of urotropine and neonol are metered into the reactor at a temperature of 75 ° C. The reaction mixture was stirred at 70 ° C for 1 hour. The test results are shown in the table.

Example 5. Under the conditions of example 1, 15.95 g of PPPA (0.1 mol) (average molecular weight 159.5 composition, wt.%: H ₂ O 0.7; 1,2-DAP 12.2; DPTA 29.6; N, β-APP 3.0; TPTA 20.6; TPPA 17.6; PPGA 9.2) and 3 g demineralized water. The reaction mass is stirred at a temperature of 45-50 ° C for 0.5 h. Next, 12.65 g (0.1 mol) of CB are dosed in a molar ratio of PPA: CB equal to 1: 2, at a temperature not exceeding 70 ° C for 2 hours, followed by exposure of the reaction mixture at 80-85 ° C for 3 hours with vigorous stirring. Then, a previously prepared aqueous solution of urotropin and neonol is metered into the reactor at a temperature of 75 ° C. The reaction mixture was stirred at 70 ° C for 1 hour. The test results are shown in the table.

Table - Acid Corrosion Inhibitor Test Results (The test medium is a 27% aqueous hydrochloric acid solution.) No. The composition of the acid corrosion inhibitor (wt.%) The amount of injected inhibitor, g Test duration, hour Corrosion rate, g / m ² h Protective effect,% one 2 3 four 5 6 one Active Foundation - 15 0.25 0.29 98.36 Isopropyl alcohol - 18 0.5 0.24 98.64 Urotropin - 5 1,0 24 0.20 98.87 Neonol - 4 1,2 0.16 99.09 Water - 58 1,5 0,07 99.60 2 Active Foundation - 12 0.25 0.24 98.64 Isopropyl alcohol - 0 0.22 98.75 Urotropin - 12 1,0 0.20 98.87 Neonol - 7 1,2 24 0.14 99,20 Water - 69 1,5 0.04 99.77 3 Active Foundation - 22 0.25 0.52 97.05 Isopropyl alcohol - 30 0.5 720 0.38 97.85 Urotropin - 12 1,0 022 98.75 Neonol - 3 1,2 0.26 98.53 Water - 33 1,5 0.24 98.64 four Active Foundation - 18 0.25 0.28 98.41 Isopropyl alcohol - 15 0.5 0.24 98.64 Urotropin - 8 1,0 720 0.22 98.75 Neonol - 7 1,2 0.14 99,20 Water - 52 1,5 0.04 99.77 5 Active Foundation - 20 0.25 0.24 98.63 Isopropyl alcohol -20 0.5 0.22 98.75 Urotropin - 7 1,0 24 0.20 98.86 Neonol - 6 1,2 0.14 99,20 Water - 47 1,5 0.06 99.66

Claims (1)

A method of producing an acid corrosion inhibitor, including the interaction of polyethylene polyamine (PEPA) or polypropylene polyamine (PPPA) with benzyl chloride (CB) and the use of an interaction product as the active base of the inhibitor, characterized in that the interaction of PEPA or PPPA with benzyl chloride is carried out first in the presence of demineralized water at a temperature of 45-50 ° C for 0.5 h, then at a temperature of 65-70 ° C at a molar ratio (PEPA or PPPA): CB, equal to 1: (1-3), for 1.5-5, 0 h and holding with stirring for 1- 3 hours at 80-85 ° C, followed by dosage at or between 70-75 ° C of isopropyl alcohol and an aqueous solution of urotropin and neonol, previously prepared by dissolving urotropin and neonol in demineralized water at ambient temperature for 0.5- 1.0 h, holding the reaction mass with vigorous stirring at a temperature of 65-70 ° C for 1 h to obtain an acid corrosion inhibitor containing components in the following ratio, wt.%:
active foundation 12-22 isopropyl alcohol 0-30 urotropin 5-12 neonol 3-7 water rest