US3766053A - Corrosion inhibitors for refining & petrochemical processing equipment - Google Patents

Corrosion inhibitors for refining & petrochemical processing equipment Download PDF

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Publication number
US3766053A
US3766053A US00267333A US3766053DA US3766053A US 3766053 A US3766053 A US 3766053A US 00267333 A US00267333 A US 00267333A US 3766053D A US3766053D A US 3766053DA US 3766053 A US3766053 A US 3766053A
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United States
Prior art keywords
corrosion
refinery
percent
naphthenic acid
imidazoline
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Expired - Lifetime
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US00267333A
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English (en)
Inventor
W Seffens
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ChampionX LLC
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Nalco Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • This invention relates to a process for the prevention of corrosion in refinery systems by injecting an imidazoline compound into the overhead vapor line. More specifically, this invention relates to the addition of an imidazoline compound having corrosion inhibition properties to the refinery system, the imidazoline being capable of preventing corrosion inside the refinery system.
  • the preferred imidazolines are formed by the reaction of dipropylene triamine and naphthenic acid.
  • the imidazoline surfactant is known to the art as a corrosion inhibitor.
  • the composition and its use as a corrosion inhibitor in motor fuel and on metal surfaces is disclosed in U. S. Pat. No. 2,466,517 and U. S. Pat. No. 3,510,282, the specifications of which are to be incorporated by reference in its entirety.
  • the imidazoline surfactant formed by the reaction of dipropylene triamine and a naphthenic acid is disclosed as a corrosion inhibitor.
  • OBJECTS lt is an object of this invention to provide a process for the prevention of corrosion in refinery systems by injecting into the overhead vapor line an imidazoline compound.
  • This invention relates to a process for the prevention of corrosion in refinery systems comprising the step of injecting into the refinery system a composition consisting of:
  • composition consists of:
  • the organic solvent of the composition acts merely as a solvent or carrier for the imidazoline surfactant.
  • the organic solvent may be aliphatic or non-aliphatic liquid.
  • the organic solvent is a hydrocarbon liquid having from 3 to 22 carbon atoms.
  • high boiling aromatic organics are used in the practice of this invention.
  • kerosene is a preferred organic solvent.
  • Other solvents which may be used are propane, butane, and heptane.
  • the organic solvents used in this invention are not limited to those mentioned above but include a large type and variety of organic solvents in which the imidazoline surfactant is soluble.
  • the imidazoline surfactant of this invention is formed by the reaction of dipropylene triamine and a naphthenic acid in a ratio of 1:2 to 2:1.
  • the preferred ratio of dipropylene triamine to naphthenic acid is 1:2. It has been found that when ratios of the dipropylene triamine to naphthenic acid outside the above mentioned range are used, an inferior imidazoline surfactant is obtained which is not as efficient in preventing the formation of an emulsion between water and the fuel.
  • the naphthenic acid used in this invention is defined in US. Pat. No. 3,510,282 as being a petroleum refining by-product obtained when the alkali liquor from the caustic treatment of gas oil is acidified with sulfuric acid. This treatment produces a dark brown about 12 on the Gardner color scale (when out 1 to 9 with mineral spirits) oily liquid which separates to the top of the aqueous liquor.
  • the mixed acids can be divided roughly into three groups having the general formulas: C,,H ,,O C H O and C l-I ,O The first group occurs largely in the lower boiling fraction of the mixture. They usually contain 6 or 7 carbon atoms and are colorless.
  • the second group usually the largest, contains acids of 8 to 12 carbon atoms having the structure:
  • the third group contains the heaviest molecules which are polycyclic and have from 12 to 23 carbon atoms.
  • Grade 2 has a somewhat higher molecular weight, for instance 320-330 and contains about 8 percent of nonsaponifiable matter.
  • Grade 3 which finds considerable utility, has a molecular weight range of 410-420 and contains about l0 percent nonsaponifiable matter.
  • naphthenic acid may be used but preference is to use the commercial grades above described, or in some instances, mixtures of two different grades so as to give, for example, an average molecular weight of 360 to 370 in some instance, and in others, a molecular weight of about 3 l0, or thereabouts.
  • the most preferred naphthenic acid those known as Sunaptic acids which are high-molecular-weight naphthenic acids prepared by the caustic extraction of selected base stocks. They range in acid number from TABLE I.SPECIFICATIONB Sunaptic Acids A Sunaptic Acids B Sunaptic Acids C Speclfi- Typical Specifi- Typical Specifi- Typical cation analysis cation analysis cation analysis Acid number, mg. KOH/g 170-180 172 150-160 157 120-130 12 Unsaponiflables, percent by wt. 4 7 6. 3 4 7 5.0 4 11 Density, 20/4 Specific gravity at F. API gravity at 60 F..
  • the amine that reacts with the naphthenic acid to form the imidazoline surfactant of this invention is dipropylene triamine.
  • Qne molecule of dipropylene triamine reacts with two molecules of naphthenic acid to form two isomers:
  • imidazoline surfactant isomers which may be formed from the reaction of dipropylene triamine and naphthenic acid.
  • water is usually present in the refinery system. Water is present with the crude petroleum when extracted from the ground and, in addition,
  • the imidazoline surfactant is injected into the refinery system.
  • the imidazoline surfactant is generally diluted by an organic solvent.
  • the preferred concentration of the imidazoline surfactant is percent by weight.
  • the diluted imidazoline surfactant can be injected at numerous stages of the refinery system.
  • the preferred points of injection are at the overhead vapor line and at the reflux line.
  • the composition is injected as a spray.
  • the imidazoline surfactant will distribute throughout the system preventing formation of an emulsion as well as preventing corrosion on the metal surfaces inside the refinery unit. Generally from 2-5ppm of the composition is injected.
  • EXAMPLE 1 At a petroleum refinery in Southern California, an imidazoline surfactant dissolved in kerosene was injected into the overhead vapor line as a fine spray. The
  • the imidazoline surfactant was prepared by the reaction of dipropylene triamine and a commerical naphthenic acid in a molar ratio of 1:2.
  • the naphthenic acid used in the Examples is derived from petroleum and is an organic acid containing a substituted naphthenic ring structure.
  • the naphthenic acid has the following properties:
  • the reactants were charged to reactor and heated to 170C. for 30 minutes at which time a vacuum of about 28 inches was applied for an additional 4 hours.
  • the product was cooled and dissolved in the heptane.
  • the composition was injected in a concentration of l2ppm. Samples of the fuel were removed from the refinery system and the amount of water emulsified was measured by using the test procedure ASTM D 2550. This is a measure of transmittance with the WlSM values ranging from 0-100 with the higher WlSM value indicating lower amounts of water present. The WlSM value obtained was 97.
  • EXAMPLE Ill The corrosion rate of the imidazoline surfactant as prepared in Example I was measured as compared to the corrosion rates of the surfactants listed in Table lll. The resulting corrosion rates are tabulated in Table IV.
  • the refinery stream water is deionized water containing 1000 ppm hydrochloric acid and 500 ppm acetic acid.
  • the pH of the water is adjusted to 7.5 with ammonium hydroxide.
  • the surfactant is also added at this point.
  • the gas tube holder is inserted into the flask neck and the flow of gas started.
  • the gas consists of 93 percent prepurified nitrogen, 5 percent air and 3 percent hydrogen sulfide and is fed at a rate of 40 cc/min./test through calibrated capillary tubings.
  • the cone drive motor is turned on as is the heating mantle.
  • the test is allowed to run for an hour before the coupon is inserted to attain equilibrium.
  • the coupon is positioned such that the gas dispersion tube is on the downstream side of the coupon, the gas makes a complete circuit of the flask before it hits the coupon.
  • the corrosion coupon is a 0.9525 cm (55; inch) X 3.81 cm (lfz inches X 0.317 cm (1% inch) S.A.E. 1020 mild steel coupon.
  • a 0.317 cm diameter hold is drilled or punched through one end of the coupon not less than 0.317 cm from the edge.
  • This coupon Prior to use, this coupon is sandblasted and weighed. Contact with skin is avoided.
  • the coupon remains in the system overnight at which time it is removed from the flask, cleaned with cleansing powder to remove loose corrosion products, dipped with agitation in an inhibited acid bath for 30 seconds, in a saturated soda ash bath for seconds, washed in tap water to remove remaining salts, dipped with agitation in an acetone bath and spun dry.
  • the coupon is then dried in a 100C. oven for 30 minutes and reweighed. The corrosion rate is calculated on the basis of weight loss and test duration.
  • the corrosion rate ofthe product formed in Example 1 was 12 mpy at a dosage of 12 ppm and 14 mpy at a dosage of 6 ppm.
  • a process for the prevention of corrosion in refinery systems comprising the step of injecting into the overhead vapor line of the refinery system a composition consisting of:
  • a process for the prevention of corrosion in refinery systems in refinery processing comprising the step of injecting into the overhead vapor line of the refinery system a composition consisting of:
  • Bi percent by weight of an imidazoline surfactant having corrosion inhibition properties said surfactant formed by the reaction of dipropylene triamine and a naphthenic acid in the ratio of 1:2.
  • a process for the prevention of corrosion in refinery systems as in claim 1 wherein from 2-5 ppm of the composition is injected into the overhead vapor line.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US00267333A 1972-06-29 1972-06-29 Corrosion inhibitors for refining & petrochemical processing equipment Expired - Lifetime US3766053A (en)

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US26733372A 1972-06-29 1972-06-29

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US3766053A true US3766053A (en) 1973-10-16

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US (1) US3766053A (enrdf_load_stackoverflow)
JP (1) JPS5322532B2 (enrdf_load_stackoverflow)
CA (1) CA997132A (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB336129I5 (enrdf_load_stackoverflow) * 1973-02-26 1975-01-28
US5300235A (en) * 1991-02-08 1994-04-05 Exxon Chemical Patents Inc. Corrosion inhibitors
US5322630A (en) * 1992-05-14 1994-06-21 Exxon Chemical Patents Inc. Amine derivatives as corrosion inhibitors
US5576140A (en) * 1995-03-07 1996-11-19 Fuji Photo Film Co., Ltd. Image-receiving sheet material, method for forming transfer image and laminate
US5683626A (en) * 1995-08-25 1997-11-04 Exxon Research And Engineering Company Process for neutralization of petroleum acids
WO2000000668A1 (en) * 1998-06-30 2000-01-06 Betzdearborn Inc. Inhibition of silica and silicate deposition
US6063288A (en) * 1998-06-30 2000-05-16 Betzdearborn Inc. Inhibition of silica and silicate deposition using imidazolines
US6258258B1 (en) 1998-10-06 2001-07-10 Exxon Research And Engineering Company Process for treatment of petroleum acids with ammonia
US11649393B1 (en) 2022-03-22 2023-05-16 Saudi Arabian Oil Company Corrosion inhibition compositions and methods of use
US11667829B1 (en) 2022-03-22 2023-06-06 Saudi Arabian Oil Company Corrosion inhibition compositions and methods of use
US12291785B2 (en) 2022-11-22 2025-05-06 Saudi Arabian Oil Company Ethoxylated fatty diamine as a corrosion inhibitor for pipelines and storage tanks

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4176059A (en) 1978-06-08 1979-11-27 Quatic Chemicals Limited Anti-corrosion composition for use in aqueous systems
BE871408A (fr) * 1978-10-20 1979-04-20 Gordon Roy G Procede pour produire des pellicules transparentes d'oxyde stannique sur un substrat chauffe.
JPS57162327A (en) * 1981-03-30 1982-10-06 Nec Home Electronics Ltd Manufacture of semiconductor device
JPS61169186U (enrdf_load_stackoverflow) * 1985-04-05 1986-10-20
JPS6219731U (enrdf_load_stackoverflow) * 1985-07-20 1987-02-05
US6800594B2 (en) * 2003-01-24 2004-10-05 Cortec Corporation Corrosion inhibitor barrier for ferrous and non-ferrous metals
US20110031165A1 (en) * 2009-08-04 2011-02-10 Karas Larry John Processes for removing hydrogen sulfide from refined hydrocarbon streams
JP7692572B2 (ja) * 2021-04-22 2025-06-16 株式会社片山化学工業研究所 石油プロセスにおける薬剤供給方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466517A (en) * 1948-01-10 1949-04-05 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2908640A (en) * 1956-02-27 1959-10-13 Sun Oil Co Inhibiting corrosion in distillation processes
US2938851A (en) * 1956-02-10 1960-05-31 Universal Oil Prod Co Preventing corrosion of plant equipment
US3510282A (en) * 1967-08-11 1970-05-05 Petrolite Corp Naphthenyl-acylated polyamines and uses

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466517A (en) * 1948-01-10 1949-04-05 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2938851A (en) * 1956-02-10 1960-05-31 Universal Oil Prod Co Preventing corrosion of plant equipment
US2908640A (en) * 1956-02-27 1959-10-13 Sun Oil Co Inhibiting corrosion in distillation processes
US3510282A (en) * 1967-08-11 1970-05-05 Petrolite Corp Naphthenyl-acylated polyamines and uses

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB336129I5 (enrdf_load_stackoverflow) * 1973-02-26 1975-01-28
US3923606A (en) * 1973-02-26 1975-12-02 Universal Oil Prod Co Prevention of corrosion
US5300235A (en) * 1991-02-08 1994-04-05 Exxon Chemical Patents Inc. Corrosion inhibitors
US5322630A (en) * 1992-05-14 1994-06-21 Exxon Chemical Patents Inc. Amine derivatives as corrosion inhibitors
US5576140A (en) * 1995-03-07 1996-11-19 Fuji Photo Film Co., Ltd. Image-receiving sheet material, method for forming transfer image and laminate
US5683626A (en) * 1995-08-25 1997-11-04 Exxon Research And Engineering Company Process for neutralization of petroleum acids
WO2000000668A1 (en) * 1998-06-30 2000-01-06 Betzdearborn Inc. Inhibition of silica and silicate deposition
US6063288A (en) * 1998-06-30 2000-05-16 Betzdearborn Inc. Inhibition of silica and silicate deposition using imidazolines
US6077440A (en) * 1998-06-30 2000-06-20 Betzdearborn Inc. Inhibition of silica and silicate deposition
US6258258B1 (en) 1998-10-06 2001-07-10 Exxon Research And Engineering Company Process for treatment of petroleum acids with ammonia
US11649393B1 (en) 2022-03-22 2023-05-16 Saudi Arabian Oil Company Corrosion inhibition compositions and methods of use
US11667829B1 (en) 2022-03-22 2023-06-06 Saudi Arabian Oil Company Corrosion inhibition compositions and methods of use
US12291785B2 (en) 2022-11-22 2025-05-06 Saudi Arabian Oil Company Ethoxylated fatty diamine as a corrosion inhibitor for pipelines and storage tanks

Also Published As

Publication number Publication date
JPS5322532B2 (enrdf_load_stackoverflow) 1978-07-10
JPS4936551A (enrdf_load_stackoverflow) 1974-04-04
CA997132A (en) 1976-09-21

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