RU2394941C1 - Procedure for production of corrosion inhibitors - Google Patents

Abstract

FIELD: machine building. ^ SUBSTANCE: active base in form of mixture of modified imidazoline (MI) with aldimines, or Schiff bases at weight ratio 5090:1050 is used in procedure. Also MI is produced at interaction of poly-ethylene-polyamines or polypropylene-polyamines with oleic acid or a-branched monocarbonic acids at mole ratio 1:1 first at temperature 150-170C during 3-6 h, and then at 250-260C during 1.5-2 h. Produced imidazolines are cyanethylated with nitrile of acrylic acid or oxyl-alkylated with ethylene or propylene oxide at mole ratio 1:12 at temperature 30-60C during 3-4 h. Aldimines are produced with condensation of oil or isobutyric, or 2-ethylhexene aldehydes with water solution of ammonia at temperature 90-130C, pressure 0.150.8 MPa and mole ratio 1:12.0 during 3-4 hours. Schiff bases are produced with condensation of oil or isobutyric, or 2-ethylhexene aldehydes with light fractions of polyamines at temperature 60-100C, and at mole ratio 12:1 during 5-6 h. Also surface active substance and organic solvent are added into produced active base which is mixed at temperature 20-50C during 0,5-2 h. ^ EFFECT: upgraded protection from corrosion, expanded raw materials base and assortment of corrosion inhibitors, also replacement of expensive solvents-aromatic hydrocarbons. ^ 3 cl, 1 tbl, 23 ex

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, class ЕВВ 43/00, 1979].

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

Known corrosion inhibitor in hydrogen sulfide-containing environments, 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 interaction 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 Solvent  rest.

[A.S. No. 2061091, class ⁶ 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 should be noted that the raw material base is limited and the authors do not indicate that it is an active basis for a 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, continuing to distill the reaction water under a current of rtnogo 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 alcohols.

The disadvantage 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 - modified imidazolines from polyethylene polyamines (PEPA), polypropylene polyamines (PPA), oleic acid (OLA) and α-branched monocarboxylic acids (VIC), acrylic acid nitrile (NAC), ethylene oxide (OE) or propylene oxide (OP), butyric aldehyde (MA) or isobutyric aldehyde (IMA) or 2-ethylhexene aldehyde (EA), ammonia and light fractions of polyamines (LFPA), which allows to increase the protection efficiency, enshit number of active base, expand resource base and reduce the cost of production of corrosion inhibitors.

The above result of obtaining corrosion inhibitors is achieved by the fact that the active base, which is a mixture of modified imidazolines (MI) and aldimines or Schiff bases, is obtained as follows.

MI is obtained by the interaction of PEPA or PPPA with OLK or VIK in the molar ratio of PEPA or PPPA: VIK or OLK = 1: 1 at a temperature of 150-170 ° C for 3-6 hours, then at a temperature of 250-260 ° C for 1, 5-2 hours, then the obtained imidazolines cyanethylate NAC or oxyalkylate OE or OD in the molar ratio of imidosaline: NAC or OE or OD = 1: 1 ÷ 2 at a temperature of 30-60 ° C for 3-4 hours.

Aldimines are obtained by condensation of oil (MA) or isobutyric (IMA) or 2-ethylhexene aldehydes (EA) with aqueous ammonia or gaseous ammonia at a temperature of 90-130 ° C and a pressure of 0.15 ÷ 0.8 MPa in a molar ratio of MA or IMA or EA: ammonia 1: 1 ÷ 2.0 for 3-4 hours.

Schiff bases are obtained by condensation of MA or IMA or EA with LFPA at 60-100 ° С, at atmospheric pressure in a molar ratio of MA or IMA or EA: LFPA 1 ÷ 2: 1 for 5-6 hours.

The active base is obtained by mixing MI with aldimines or Schiff bases in a mass ratio of 50 ÷ 90: 10 ÷ 50, add a surfactant, an organic solvent, mix at a temperature of 20-50 ° C for 0.5-2 hours and the components of corrosion inhibitors take in the following proportions, wt.%:

Active foundation 10-20 Surface-active substance 2-5 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. Ethylene or propylene oxide is taken as alkylene oxide, and 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 2431-200203312-2000 "Acids α-branched monocarboxylic" VIK-N.

As solvents, bottoms from the production of butyl alcohols according to TU 2421-101-05766575-2001, nefras coal, solvent, bottoms from the production of benzene according to TU 2415-004-05766801-2003, toluene oil according to GOST 14710-78, Nefras Volgosintez are used. bottoms of rectification of propylene hydroforming products or mixtures thereof.

As surface-active substances (surfactants) use neonol grades AF-9-9, AF-9-10, B-1020-3.

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, 29.5 g (0.2 mol) of PEPA (average molecular weight 147.5, average fraction of PEPA) are loaded, 56.4 (0.2 mole) of oleic acid (OLA) is heated under a stream of nitrogen at a temperature of 150-160 ° C for 4 hours, then at 250 ° C for 2 hours. The reaction mixture is cooled, after which 10.6 g (0.2 mol ) NAC and heated at a temperature of 30-40 ° C for 4 hours. The molar ratio of PEPA: OLK is 1: 1. Received 87.6 g (98.2%) of modified imidazoline (MI).

Example 2. Under the conditions of Example 1, 29.5 g (0.2 mol) of PEPA (average molecular weight of 147.5, average fraction of PEPA), 50.4 g (0.2 mol) of VIC (average molecular weight) were charged to the reactor. mass 252), heated at a temperature of 150-160 ° C for 3 hours, maintained at 260 ° C for 1.5 hours, after cooling the reaction mixture, 17.6 g (0.4 mol) of ethylene oxide was added, heated at a temperature of 30 -40 ° C for 3 hours. The molar ratio of imidazoline: OE is 1: 2. Received 88.3 g (97.8%) of MI.

Example 3. Under the conditions of example 1, 38.0 g (0.2 mol) of PEPA (average molecular weight 190, heavy fraction of PEPA), 56.4 g (0.2 mol) of oleic acid are charged to the reactor, heated at a temperature of 150 ° C for 6 hours, then stirred at 250 ° C for 2 hours, cooled to 40 ° C and added 23.2 g (0.4 mol) of propylene oxide, heated at a temperature of 50-60 ° C for 4 hours. The molar ratio of amine: acid is 1: 1. The molar ratio of imidazoline: OD is 1: 2. Received 107.5 g (98.3%) of MI.

Example 4. Under the conditions of example 1, 19.5 g (0.1 mol) of PPPA (average molecular weight 195, average fraction of PPPA), 28.2 g (0.1 mol) of oleic acid are charged into the reactor, heated at a temperature of 170 ° C for 3 hours, kept at a temperature of 250 ° C for 1.5 hours. After cooling the reaction mixture, 10.6 g (0.2 mol) of NAC are added and stirred at a temperature of 50-60 ° C for 3 hours. The molar ratio of imidazoline: NAC is 1: 2. Received 53.7 g (98.3%) of MI.

Example 5. Under the conditions of example 1, 24.0 g (0.1 mol) of PPPA, (average molecular weight 240, heavy fraction of PPPA) are loaded into the reactor, 28.2 g (0.1 mol) of oleic acid, heated at a temperature of 160 -170 ° C for 4 hours, incubated at a temperature of 250-260 ° C for 2 hours. Received 47.0 (96.8%) of imidazoline.

Example 6. Under the conditions of example 1, 30.6 g (0.2 mol) of PEPA (TU on PEPA 2413-214-00203312-2002, average molecular weight 153), 56.4 g (0.2 mol) are loaded into the reactor oleic acid, heated at a temperature of 150 ° C for 4 hours, kept at a temperature of 250 ° C for 2 hours. Received 78.6 g (98.5%) of imidazoline.

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 liquid ammonia are loaded into the reactor. The reaction mixture is heated at a temperature of 100-120 ° C and a pressure of 0.5-0.6 MPa for 3 hours. The molar ratio of IMA: NH ₃ is 1: 2. Received 34.7 g (97.6%) of aldimine.

Example 8. 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. The mixture is heated at a temperature of 90-100 ° C and a pressure of 0.15-0.4 MPa for 4 hours. The molar ratio of MA: NH ₃ is 1: 1.2. Received 34.5 g (97.1%) of aldimine.

Example 9. Under the conditions of example 1, 63.0 g (0.5 mol) of 2-ethylhexene aldehyde (EGA), 11 g (0.65 mol) of a 36% aqueous solution of NH ₃ are charged into the reactor. The reaction mixture is heated at a temperature of 120-130 ° C and a pressure of 0.3-0.8 MPa for 3. The molar ratio of EGA: NH ₃ is 1: 1.3. Received 69.78 g (97.6%) of aldimine.

Example 10. Under the conditions of example 1, 14.4 g (0.2 mol) of butyric aldehyde, 29.5 g (0.2 mol) of PEPA (middle fraction of PEPA) are charged to the reactor, heated at a temperature of 65-70 ° C for 4 hours. 39.89 g (99.0%) of aldimine obtained.

Example 11. Under the conditions of example 1, 28.8 g (0.4 mol) of butyric aldehyde (MA), 49.0 g (0.4 mol) of PEPA (light PEPA, average molecular weight of 122.5) are charged to the reactor . The reaction mixture is heated at a temperature of 60-70 ° C for 5 hours. The molar ratio of MA: PEPA is 1: 1. Received 70.1 g (99.3%) of Schiff's base.

Example 12. Under the conditions of Example 1, 14.4 g (0.2 mol) of isobutyric aldehyde, 19.5 g (0.1 mol) of PPPA (middle PPPA fraction) were charged to the reactor, heated at a temperature of 70-80 ° С for 5 hours. The molar ratio of aldehyde: amine is 2: 1. Received 29.9 g (98.8%) of Schiff base.

Example 13. Under the conditions of example 1, 25.2 g (0.2 mol) of 2-ethylhexene aldehyde (EGA), 19.0 g (0.1 mol) of PEPA (average molecular weight 190, heavy fraction of PEPA) are loaded into the reactor , heated at a temperature of 90-100 ° C for 6 hours. The molar ratio of EGA: PEPA is 2: 1. Received 39.1 g (96.4%) of Schiff base.

The IR spectra of all modified imidazolines have absorption bands in the region of 1629-1637 cm ^-1 , typical for the (C = N) group in imidazolines 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 14

a) The modified imidazoline (MI) according to example 1 is mixed with aldimine described in example 8 in a mass ratio of MI: aldimine = 60: 40 at a temperature of 20-30 ° C for 0.5-1 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 12 g of active base, 5 g of neonol AF-9-9, 83 g of solvent (VAT bottoms from benzene production) is stirred at room temperature for 0.5 h (product 1).

Example 15

a) MI according to example 2 is mixed with aldimine described in example 9 in a mass ratio of 70:30 at a temperature of 30-40 ° C for 1.5 hours (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 10 g of the active base, 5 g of neonol AF-9-10, 85 g of solvent (bottoms from the production of butyl alcohols) is stirred at a temperature of 20-30 ° C for 1 h (product 2) .

Example 16

a) MI according to example 3 is mixed with aldemin, described in example 10 in a mass ratio of 50:50 at 50 ° C for 2 hours (active base).

b) A corrosion inhibitor is prepared as follows: 20 g of an active base, 2 g of neonol grade AF-9-9, 78 g of solvent (a 1: 1 mixture of bottoms of benzene production and bottoms of rectification of propylene hydroformylation products) are mixed at a temperature of 25-30 ° C for 1 h (product 3).

Example 17

a) the MI of example 4 is mixed with the Schiff base of example 11 in a mass ratio of 60:40 at a temperature of 50 ° C for 1 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 20 g of the active base, 3 g of neonol grade AF-9-10, 77 g of solvent (bottoms from benzene production) are mixed at a temperature of 25-30 ° C for 45 minutes (product 4).

Example 18

a) MI according to example 3 is mixed with the Schiff base according to example 10 in a mass ratio of 70:30 at a temperature of 20-25 ° C for 2 hours (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 15 g of the active base, 5 g of neonol AF-9-10, 80 g of solvent (nefras) are mixed at a temperature of 25-30 ° C in a mass ratio of 65:35 for 40 minutes (product 5).

Example 19

a) MI according to example 1 is mixed with aldimine according to example 10 at a temperature of 30-40 ° C in a mass ratio of 70:30 for 1 h (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 18 g of active base, 3 g of neonol grade B-1020-3, 79 g of solvent (Nefras Volgosynthesis) is mixed at a temperature of 20-25 ° C in a mass ratio of 50:50 for 50 minutes (product 6).

Example 20

a) The imidazoline of example 5 is mixed with the Schiff base of example 11 at a temperature of 25-30 ° C in a mass ratio of 80:20 for 30 minutes (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 20 g of active base. 5 g of neonol grade B-1020-3, 75 g of solvent (toluene: still bottoms from benzene production = 1: 1) are stirred at a temperature of 40 ° C for 45 minutes (product 7).

Example 21

a) The imidazoline of example 6 is mixed with the Schiff base of example 12 at a temperature of 45-50 ° C in a mass ratio of 90:10 for 45 minutes (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 10 g of the active form, 5 g of neonol grade AF-9-9 and 85 g of solvent (bottoms of butyl alcohols) is stirred at a temperature of 30 ° C for 30 minutes (product 8).

Example 22

a) MI according to example 2 is mixed with a Schiff base according to example 13 at a temperature of 40-45 ° C in a mass ratio of 70:30 for 50 minutes (active base).

b) A corrosion inhibitor is prepared as follows: a mixture of 20 g of active base, 4 g of neonol grade AF-9-10, 76 g of solvent (bottoms from benzene production) are stirred at 45 ° C for 1 h (product 9).

Example 23

a) MI according to example 4 is mixed with a Schiff base according to example 7 at a temperature of 30-35 ° C in a mass ratio of 80:20 for 40 minutes.

b) A corrosion inhibitor is prepared as follows: a mixture of 12 g of active base, 5 g of neonol grade B-1020-3 and 83 g of solvent (solvent-xylene mixture) is stirred at a temperature of 30-35 ° C for 50 minutes (product 10).

Table 1 Corrosion inhibitor test (product 1-10) for protective activity No. p / p Corrosion Inhibitors (Product 1-10) Hcl concentration,% Inhibitor Dosage, mg / L Degree of protection, % one Product 1 (Example 14) 23 thirty 98.7 2 Product 2 (example 15) twenty thirty 99.0 3 Product 3 (Example 16) 23 fifty 98.9 four Product 4 (Example 17) 23 thirty 99.6 5 Product 5 (Example 18) fifteen fifty 97.6 6 Product 6 (Example 19) 23 thirty 99,4 7 Product 7 (Example 20) 23 fifty 97.8 8 Product 8 (Example 21) 23 fifty 97.4 9 Product 9 (Example 22) twenty fifty 99.1 10 Product 10 (Example 23) 23 thirty 99.5

Claims (3)

1. A method of obtaining a corrosion inhibitor for the protection of gas and oilfield equipment and pipelines operating in highly mineralized hydrogen sulfide-containing media containing an active base, a surfactant and a solvent, which consists in using the active base in the form of a mixture of modified imidazolines ( MI) with aldimines or Schiff bases in a mass ratio of 50 ÷ 90: 10 ÷ 50, and MI is obtained by the interaction of polyethylene polyamines or polypropylene polyamines with oleic acid or α-dec monocarboxylic acids in molar ratio of polyethylene polyamines or polypropylene polyamines: oleic acid or α-branched monocarboxylic acid 1: 1 at a temperature of 150-170 ° C for 3-6 hours, and then at a temperature of 250-260 ° C for 1.5- 2 hours, and the resulting imidazolines are cyanethylated with acrylic acid nitrile or oxyalkylated with ethylene oxide or propylene oxide in a molar ratio of imidazoline: acrylic acid nitride or ethylene oxide or propylene oxide 1: 1 ÷ 2 at a temperature of 30-60 ° C for 3-4 hours, aldimines get con by sensing oil or isobutyric or 2-ethylhexene aldehydes with aqueous ammonia or gaseous ammonia at a temperature of 90-130 ° C and a pressure of 0.15 ÷ 0.8 MPa in a molar ratio of aldehyde: ammonia of 1: 1 ÷ 2.0 for 3- 4 hours, and Schiff bases are obtained by condensation of oil or isobutyric or 2-ethylhexene aldehydes with light polyamine fractions at a temperature of 60-100 ° С and atmospheric pressure in a molar ratio of oil or isobutyric or 2-ethylhexene aldehyde: light fractions of polyamines 1 ÷ 2: 1 for 5-6 hours, while in the floor surfactant, an organic solvent is added to the active base and stirred at a temperature of 20-50 ° C for 0.5-2 hours, and the components of the corrosion inhibitor are taken in the following proportions, wt.%:
active foundation 10-20 Surfactant 2-5 solvent rest 2. The method according to claim 1, characterized in that as a surfactant use neonol grade AF-9-9, grade AF-9-10, grade B-1020-3. 3. The method according to claim 1, characterized in that the solvent used is bottoms of butyl alcohol production, nephras coal, bottoms of benzene production, petroleum toluene, Volgosintez nefras and bottoms of rectification of propylene hydroforming products.