RU2394817C1 - Method of producing corrosion inhibitors - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of corrosion inhibitors, specifically to a method of producing an active base for corrosion inhibitors - a mixture of modified acid amide, aldimines and Schiff bases. According to the method, the active base component - modified acid amides are obtained by reacting polyethylene polyamine or polypropylene polyamine (A) with oleic acid or α-branched monocarboxylic acids (B) in molar ratio of polyethylene polyamine or polypropylene polyamine A:B = 1-1.4:1, temperature of 160-180°C for 4-8 hours. The obtained acid amides are cyanoethylated with acrylonitrile or oxyalkylated with ethylene oxide or propylene oxide in molar ratio acid amide:acrylonitrile or ethylene oxide or propylene oxide = 1:2-4 at 40-60°C for 4-6 hours. The obtained modified acid amides are mixed with aldimines or Schiff bases in mass ratio of 50-80:20-50, solvents and surfactants at 20-80°C for 0.5-2 hours and components of corrosion inhibitors are taken in the following ratios in wt %: active base 15-25, surfactant 2-8, solvent - the rest.

EFFECT: disclosed method enables to obtain more effective corrosion inhibitors.

3 cl, 12 ex, 1 tbl

Description

The invention relates to the field of corrosion protection of gas and oilfield equipment and pipelines for transporting oil and gas operating in highly mineralized hydrogen sulfide-containing environments.

A known inhibitor of hydrogen sulfide corrosion, consisting of a mixture of hydrochlorides of aminoparaffins [A.S. No. 652315, K1 E21B 43/00, 1979].

A disadvantage of the known inhibitor is the low protective effect at a dosage of up to 100 mg / L.

A known corrosion inhibitor in hydrogen sulfide-containing media, which contains the product of the interaction of 1 mol of fatty acid with the number of carbon atoms C ₁₀ -C ₂₀ , and (0.1-1) mol of aminoparaffin with the number of carbon atoms C ₈ -C ₂₀ in the following ratio of components, wt .%:

The reaction product of 1 mol of fatty acid with the number of carbon atoms C ₁₀ -C ₂₀ and (0.1-1) mol of aminoparaffin with the number of carbon atoms C ₈ -C ₂₀ - 10 ÷ 50;

Nonionic surfactant - 10 ÷ 30;

The solvent is the rest [A.S. No. 2061091, K6 C23F 11/00, 1996].

The disadvantage of using a known inhibitor is the relatively low protective effect (87-94%) at a dosage of 50 mg / L. Another disadvantage is the use of poison - methyl alcohol, the latter has a low boiling point and is used in an amount of 80 ml per 10 g of active base. In addition, it is necessary to note the limited raw material base and the authors do not indicate that it is the active basis of the corrosion inhibitor and it is impossible to establish the conditions for the interaction of fatty acid and aminoparaffin from the description.

Closest to the proposed technical essence and the achieved results is a corrosion inhibitor described in a method for producing corrosion inhibitors and hydrogen pickling metals [US Pat. RF 2135483, 1999, bull. No. 24]. In the proposed method, a corrosion and hydrogenation inhibitor of metals in acidic and aqueous-salt hydrogen sulfide-containing media is prepared by reacting amines with carboxylic acids, distilling off reaction water, mixing the residue with a composite solvent and a sparingly soluble dispersant selected from alkyl phenol adducts with ethylene oxide. As amines, polyethylene and polypropyleneamines are used, as well as mixed polyethylene and polypropyleneamines, which are the reaction products of polyethylene and polypropyleneamines with dichloroethane and dichloropropane, isomeric α-branched carboxylic acids of fractions C ₅ -C ₂₈ are used as carboxylic acids, and the reaction is carried out first at a temperature of 120-140 ° C for 6-8 hours with simultaneous distillation of water and subsequent heating of the reaction mixture to 250-280 ° C for 3-4 hours, while continuing to distill the reaction water under inert current -gas, followed by alkylation, or oxyalkylation tsianetilirovaniem resulting product at 40-80 ° C. An inhibitor is a mixture of imidazolines and amides of higher isomeric α-branched monocarboxylic acids (VIC) and polyethylene polyamines (PEPA) with aromatic hydrocarbons, surfactants and surfactants.

The disadvantages of the above method of obtaining a corrosion inhibitor are:

1) insufficiently high efficiency of corrosion inhibitors in the late and final stages of development of oil and gas fields;

2) increased foaming ability;

3) limited raw material base.

The objective of the invention is the development of a method for producing corrosion inhibitors, increasing the efficiency of protecting gas and oilfield equipment and pipelines for transporting oil and gas from corrosion, expanding the raw material base and assortment of corrosion inhibitors, replacing expensive solvents - aromatic hydrocarbons.

The technical result when using the invention is expressed in obtaining an active base of corrosion inhibitors - a mixture of modified amides, aldimines and Schiff bases from polyethylene polyamines (PEPA), polypropylene polyamines (PPA), oleic acid (OLA), α-branched monocarboxylic acids (VIC), acrylic acid nitrile (NAC), ethylene oxide (OE), propylene oxide (OP), butyric aldehyde (MA), isobutyric aldehyde (IMA), 2-ethylhexene aldehyde (EGA), salicylic aldehyde (CA), benzaldehyde (BA), acetone (A) ), cyclohexanone ( CH), ammonia and light fraction of polyamines (LFPA), which allows to increase the efficiency of protection of gas and oilfield equipment and pipelines for oil and gas transportation from corrosion, to expand the raw material base and range of corrosion inhibitors and to reduce the cost of production of corrosion inhibitors.

The above result of obtaining corrosion inhibitors is achieved in that the active base, which is a mixture of modified acid amides (MAAs) and aldimines or Schiff bases, is obtained as follows:

MAK is obtained by the interaction of PEPA or PPPA with OLK or VIK at a molar ratio of PEPA or PPPA: VIK or OLK = 1 ÷ 1.4: 1, temperature 160-180 ° C for 4-8 hours, the obtained amides of acids (AA) cyanate NAC or hydroxyalkylate OE or OD in a molar ratio of AK: NAC or OE or OD = 1: 2 ÷ 4 at 40-60 ° C for 4-6 hours.

Aldimines are obtained by condensation of MA or IMA or EGA with aqueous ammonia or gaseous ammonia at a temperature of 100-140 ° C and a pressure of 0.5-1.0 MPa in a molar ratio of MA or IMA or EGA: ammonia = 1: 1 ÷ 2.0 within 4-6 hours

Schiff bases are obtained by condensation of SA or BA, or A or CG with LFPA at a temperature of 50-90 ° C, at atmospheric pressure in a molar ratio of MA, or IMA, or EGA, or CA, or BA, or A, or TsG: LFPA = 1 ÷ 2.0: 1 for 5-6 hours.

The obtained MAA is mixed with aldimines or Schiff bases in a mass ratio of 50 ÷ 80: 20 ÷ 50, organic solvents and surface-active substances (surfactants) at a temperature of 20-80 ° C for 0.5-2 hours and the components of corrosion inhibitors are taken in the following ratios, wt.%:

Active foundation 15-25 Surface-active substance 2-8 Solvent Rest

Used polyethylene polyamines (PEPA) according to TU 2413-214-00203312-2002 "Technical polyethylene polyamines." Polypropylene polyamines (PPPA) are obtained under the conditions of patent RU 2290396, Bull. No. 36, 12/27/06. The dispersed PEPA TU 2413-214-00203312-2002 is used as the light fraction of polyamines.

Used α-branched monocarboxylic acids (VIC) according to TU No. 2431-200203312-2000 "Acids α-branched monocarboxylic" VIK-N.

As solvents, bottoms of butyl alcohol production are used in accordance with TU 2421-101-05766575-2001, coal nephras, bottoms of benzene production are in accordance with TU 2415-004-05766801-2003, petroleum toluene is in accordance with GOST 14710-78, solvent, volgosynthesis nefras bottoms of rectification of propylene hydroforming products or mixtures thereof.

As surfactants use neonol grades AF-9-9, AF-9-10, B-1020-3, monoalkylphenol, ethoxylated based on α-olefins - α-12 or α-14 according to TU 2483-004-05766801 -93, OP-10.

The invention is illustrated by the following examples.

Example 1. In a reactor equipped with a mechanical stirrer, a thermometer, a refrigerator and a dropping funnel, 30.6 g (0.2 mol) of PEPA (average molecular weight 153), 56.4 g (0.2 mol) of oleic acid ( OLK), the molar ratio of PEPA: OLK = 1: 1, is heated under a stream of nitrogen at a temperature of 160-170 ° C for 4 hours. The reaction mixture is cooled, then 21.2 g (0.4 mol) of NAC are added, the molar ratio of AK : NAC = 1: 2, heated at a temperature of 50-60 ° C for 4 hours. 103.1 g (98.6%) of MAA were obtained.

Example 2. Under the conditions of example 1, 40.6 g (0.28 mol) of PEPA (average molecular weight 145), 50.4 g (0.2 mol) VIC (average molecular weight VIC 252), molar are charged to the reactor the ratio of PEPA: VIC = 1.4: 1, heated at a temperature of 170-180 ° C for 8 hours, the mixture was cooled, 35.2 g (0.8 mol) of ethylene oxide was added, the molar ratio of AK: OE = 1: 4 , heated at a temperature of 40 ° C for 4 hours. Received 121.5 g (99.1%) of MAC.

Example 3. Under the conditions of example 1, 33.6 g (0.24 mol) of PEPA (average molecular weight 140), 56.4 g (0.2 mol) of oleic acid, molar ratio of PEPA: OLA = 1, are loaded into the reactor 2: 1, heated at 170 ° C for 6 hours, the reaction mixture was cooled, 23.2 g (0.4 mol) of propylene oxide was added, the molar ratio AK: OD = 1: 2, heated at a temperature of 50 ° C within 6 hours. 108.2 g (98.8%) of MAA were obtained.

Example 4. Under the conditions of example 1, 23.4 g (0.12 mol) of PPPA (average molecular weight 195), 28.2 g (0.1 mol) of oleic acid, the molar ratio of PPA: OLA = 1, are loaded into the reactor 2: 1, heated at a temperature of 160-170 ° C for 6 hours, and after cooling the reaction mixture, 10.6 g (0.2 mol) of NAC are added, the molar ratio of AK: NAC = 1: 2, stirred at a temperature of 50-55 ° C for 4 hours. 55.6 g (98.5%) of MAA were obtained.

Example 5. Under the conditions of example 1, 24.0 g (0.1 mol) of PPPA (average molecular weight of PPPA 240), 25.2 g (0.1 mol) of VIC are charged to the reactor, heated at a temperature of 165-170 ° C for 5 hours. The mixture is cooled, 11.6 g (0.2 mol) of propylene oxide (OD) are added, heated at a temperature of 55-60 ° C for 4 hours. 57.8 (98.0%) of MAA is obtained.

Example 6. Under the conditions of example 1, 28.8 g (0.4 mol) of butyric aldehyde (MA), 8.16 g (0.48 mol) of a 36% aqueous ammonia solution are charged to the reactor, molar ratio MA: NH ₃ = 1: 1.2, the mixture is heated at a temperature of 100-120 ° C for 6 hours. 34.5 g (97.0%) of aldimine are obtained.

Example 7. Under the conditions of example 1, 28.8 g (0.4 mol) of isobutyric aldehyde (IMA), 13.6 g (0.8 mol) of gaseous ammonia, a molar ratio of IMA: NH ₃ = 1: 2 are charged to the reactor. the contents of the reactor are heated at a temperature of 100-115 ° C and a pressure of 0.5-0.6 MPa for 4 hours. 34.6 g (97.2%) of aldimine are obtained.

Example 8. Under the conditions of example 1, 63.0 g (0.5 mol) of 2-ethylhexene aldehyde, 9.35 g (0.55 mol) of ammonia in the form of a 36% aqueous solution are charged into the reactor, molar ratio of EGA: NH ₃ = 1: 1.1, heated at a temperature of 120-140 ° C and a pressure of 0.6-1 MPa for 4. Received 69.3 g (97.0%) of aldimine.

Example 9. Under the conditions of example 1, 29.0 g (0.2 mol) of PEPA (average molecular weight 145), 48.8 g (0.4 mol) of salicylic aldehyde (CA), molar ratio of PEPA: CA = 1: 2, heated at a temperature of 70-80 ° C for 5 hours. Received 69.6 g (98.7%) of Schiff base.

Example 10. Under the conditions of example 1, 30.6 g (0.2 mol) of PEPA (average molecular weight 153), 42.4 g (0.4 mol) of benzaldehyde (BA), the molar ratio of PEPA: BA = 1 are loaded into the reactor : 2, the mixture is heated at a temperature of 80-85 ° C for 6 hours. 64.1 g (97.5%) of Schiff base are obtained.

Example 11. Under the conditions of example 1, 28.0 g (0.2 mol) of PEPA (average molecular weight 140), 23.2 g (0.4 mol) of acetone (A) are loaded into the reactor, the molar ratio of PEPA: A = 1 : 2, the reaction mixture is heated at a temperature of 50-60 ° C for 6 hours. 42.1 g (95.8%) of Schiff base are obtained.

Example 12. Under the conditions of example 1, 31 g (0.2 mol) of PEPA (average molecular weight 155), 18.6 g (0.2 mol) of cyclohexanol (CH), the molar ratio of PEPA: CH = 1: 1 are loaded into the reactor , the mixture is heated at 90 ° C for 6 hours. 44.3 g (96.4%) of Schiff base are obtained.

The IR spectra of all modified acid amides have absorption bands in the region of 1675-1690 cm ^-1 , characteristic of the (-CONH-) group in acid amides, and at 2230-2234 cm ^-1 for the (C≡N) group in cyanethylation products, 1065-1075 cm ^-1 for the (OH) group in oxyalkylated imidazolines. Aldimines and Schiff bases have absorption bands at 1665-1774 cm ^-1 for the (R-CH = NR) group.

Example 13

a) the modified acid amide (MAA) of Example 1 is mixed with the aldimine described in Example 6 in a mass ratio of MAA: aldimine = 80: 20 at a temperature of 20-30 ° C for 0.5 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 25 g of the active base, 4 g of neonol AF-9-9, 71 g of solvent (bottoms from the production of butyl alcohols) is stirred at a temperature of 20-30 ° C for 0.5 h (product one).

Example 14

a) MAK according to example 2 is mixed with aldimine according to example 7 in a mass ratio of MAK: aldimine = 60: 40 at a temperature of 40-50 ° C for 1 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 15 g of the active base, 6 g of neonol AF-9-10, 79 g of solvent (solvents are a mixture of xylenes) are stirred at a temperature of 50-60 ° C for 1 h (product 2).

Example 15

a) MAK according to example 3 is mixed with aldimine according to example 8 in a mass ratio of MAK: aldimine = 50: 50 at a temperature of 70-80 ° C for 1 h (active bases).

b) A corrosion inhibitor is prepared as follows: a mixture of 20 g of active base, 8 g of neonol grade B-1020-3, 72 g of solvent (VAT bottoms of benzene) is stirred at a temperature of 70 ° C for 1.5 hours (product 3).

Example 16

a) MAK in example 2 is mixed with the Schiff base in example 9 at a temperature of 40 ° C for 1 h in a mass ratio of 60:40 (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 15 g of active base, 7 g of OP-10, 78 g of solvent (Nefras Volgosynthesis is stirred at 45 ° C for 1 h (product 4).

Example 17

a) MAK in example 1 is mixed with the Schiff base in example 10 in a mass ratio of 80:20 at a temperature of 60 ° C for 1 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 20 g of active base, 4 g of monoalkylphenol, ethoxylated on the basis of α-olefins - α-14, 76 g of solvent (distillation bottoms of rectification of propylene hydroforming products) are mixed at a temperature of 30-40 ° C for 2 hours (product 5).

Example 18

a) MAK according to example 3 is mixed with the Schiff base of the reaction according to example 11 in a mass ratio of 60:40 at a temperature of 40-50 ° C for 2 hours (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 25 g of the active base, 6 g of monoalkylphenol, ethoxylated based on α-olefins - α-12, 69 g of solvent (a mixture of bottoms from the production of benzene and butyl alcohols in a volume ratio of 50:50) is stirred at temperature 50-60 ° C for 1 h (product 6).

Example 19

a) MP according to example 1 is mixed with the reaction product of example 12 in a mass ratio of 50:50 at a temperature of 50 ° C for 0.5 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 15 g of the active base, 8 g of neonol grade AF-9-9 and 77 g of solvent (VAT bottoms of benzene) is stirred at 35-45 ° C for 1 h (product 7).

Table 1 Corrosion inhibitor test (product 1-7) for protective activity No. p / p Corrosion Inhibitors (Product 1-7) Hcl concentration,% Inhibitor Dosage, mg / L Degree of protection, % one Product 1 (Example 13) 23 fifty 99,2 2 Product 1 (Example 13) twenty thirty 98.6 3 Product 2 (Example 14) 23 fifty 99.0 four Product 2 (Example 14) 23 thirty 98.8 5 Product 3 (example 15) fifteen thirty 98.6 6 Product 4 (Example 16) 23 thirty 98.9 7 Product 4 (Example 16) 23 fifty 99,2 8 Product 5 (example 17) 23 thirty 99,2 9 Product 6 (example 18) twenty fifty 98.9 10 Product 6 (example 18) 23 thirty 98.6 eleven Product 7 (Example 19) twenty fifty 99.1 12 Product 7 (Example 19) 23 thirty 98.5

Claims (3)

1. The method of obtaining corrosion inhibitors for the protection of gas and oilfield equipment and pipelines operating in highly mineralized hydrogen sulfide-containing environments, which consists in the fact that the active base, which is a mixture of modified acid amides with aldimines or Schiff bases in a mass ratio of 50 ÷ 80: 20 ÷ 50 are obtained by reacting polyethylene polyamines or polypropylene polyamines with oleic acid or α-branched monocarboxylic acids in a molar ratio of polyethylene polyamines or polyprop ilenpolyamines: oleic acid or α-branched monocarboxylic acid 1 ÷ 1.4: 1 at a temperature of 160-180 ° C for 4-8 hours and the resulting acid amides are cyanethylated with acrylic acid nitrile or hydroxyalkylated with ethylene oxide or propylene oxide in a molar ratio of amide acid : nitrile of acrylic acid, or ethylene oxide, or propylene oxide 1: 2 ÷ 4 at a temperature of 40-60 ° C for 4-6 hours, the obtained modified acid amides are mixed with aldimines obtained by condensation of butyric aldehyde, or isobutyric aldehyde, or 2 ethylhex new aldehyde with aqueous ammonia or gaseous ammonia at a temperature of 100-140 ° C and a pressure of 0.5-1 MPa, in a molar ratio of aldehyde: ammonia 1: 1.1 ÷ 2.0 for 4-6 hours, or Schiff bases obtained by condensation of salicylic aldehyde, or benzaldehyde, or acetone, or cyclohexanone with light fractions of polyamines at a temperature of 50-90 ° С, at atmospheric pressure in a molar ratio of aldehyde or ketone: light fractions of polyamines 1: 1 ÷ 2.0 for 5- 6 hours, a surfactant is added to the obtained active base, sol the agent, is stirred at a temperature of 20-80 ° C for 0.5-2 hours, the components of corrosion inhibitors are taken in the following proportions, wt.%:
Active base 15-25
Surface active agent 2-8
Solvent rest 2. The method of obtaining corrosion inhibitors according to claim 1, characterized in that as a surfactant use OP-10, neonol grades AF-9-9, AF-9-10, B-1020-3, monoalkylphenol, ethoxylated on the basis of α-olefins - α-12 or α-14. 3. The method of producing corrosion inhibitors according to claim 1, characterized in that the solvents are bottoms of butyl alcohol production, nephras coal, bottoms of benzene production, solvent, petroleum toluene, Volgosintez nefras, bottoms of rectification of propylene hydroformation products.