Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G7/00—Distillation of hydrocarbon oils
  • C10G7/10—Inhibiting corrosion during distillation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
  • C10G9/16—Preventing or removing incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
  • C10L1/1895—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom polycarboxylic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1033—Oil well production fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
  • C10G2300/203—Naphthenic acids, TAN
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4075—Limiting deterioration of equipment

Definitions

• This invention relates generally to a process for inhibiting corrosion in refining operations. It is specifically directed toward the inhibition of corrosion caused by naphthenic acids which are present in the crude oil.
• Corrosion problems in petroleum refining operations associated with naphthenic acid constituents in crude oils have been recognized for many years. Such corrosion is particularly severe in atmospheric and vacuum distillation units at temperatures of between about 350° F. and 790° F.
• Other factors that contribute to the corrosivity of crudes containing naphthenic acids include the amount of naphthenic acid present, the concentration of sulfur compounds, the velocity and turbulence of the flow stream in the units, and the location in the unit (e.g., liquid/vapor interface).
• the crude oil is passed successively through a furnace and one or more fractionators such as an atmospheric tower and a vacuum tower.
• one or more fractionators such as an atmospheric tower and a vacuum tower.
• naphthenic acid corrosion is not a problem at temperatures below about 350° F.
• Traditional nitrogen-based filming corrosion inhibitors are not effective at temperatures above 350° F., and the other approaches for preventing naphthenic acid corrosion such as neutralization present operational problems or are not effective.
• naphthenic acid includes mono- and di-basic carboxylic acids and generally constitutes about 50% by weight of the total acidic components in crude oil. Many of the naphthenic acids may be represented by the following formula: where R is an alkyl or cycloalkyl group and n ranges generally from 2 to 10.
• alkyl organic acids within the class of naphthenic acids.
• Naphthenic acids are corrosive between the range of about 350° F. (180° C.) to about 790° F. (420° C.). At the higher temperatures, the naphthenic acids are in the vapor phase and the rate of decarboxylation increases. At the lower temperatures, the corrosion rate is not serious.
• the corrosivity of crude oils and distillates is also affected by the presence of sulfide compounds, such as hydrogen sulfide, mercaptans, elemental sulfur, sulfides, disulfides, polysulfides and thiophenols. Corrosion due to sulfur compounds becomes significant at temperatures as low as 450° F.
• the catalytic generation of hydrogen sulfide by thermal decomposition of mercaptans has been identified as a cause of sulfidic corrosion.
• Atmospheric and vacuum distillation systems are subject to naphthenic acid corrosion when processing certain crude oils.
• Currently used treatments are thermally reactive at use temperatures.
• phosphorus-based inhibitors these are thought to lead to a metal phosphate surface film that is more resistant to naphthenic acid corrosion than the base steel.
• These inhibitors are relatively volatile and exhibit fairly narrow distillation ranges. They are fed into a column above or below the point of corrosion depending on the temperature range.
• Polysulfide inhibitors decompose into complex mixtures of higher and lower polysulfides and perhaps, elemental sulfur and mercaptans. Thus, the volatility and protection offered is not predictable.
• the present invention provides a method for inhibiting the corrosion of the internal metallic surfaces of the equipment used in processing crude oil or the high temperature petroleum distillates derived therefrom. It comprises adding to the crude oil or distillate an effective amount, sufficient to inhibit corrosion, of a tetra functional substituted aromatic compound (I) and/or a trimellitic acid ester or trimellitic anhydride (II).
• the tetra functional substituted aromatic compounds (I) as defined above may be represented by the general formula: wherein W, X, Y, and Z are all present and may be the same or different and are individually selected from the groups consisting of (OH); (COOH); and COOR 1 , with the proviso that vicinal pairs of W, X, Y, Z can be i.e., anhydride function.
• R 1 in the formula is an alkyl moiety having from about 1 to about 16 carbon atoms;
• Ar is an aromatic moiety.
• esters or anhydrides of trimellitic acid (II) are represented by the formula (II) wherein R 2 and R 3 are with the proviso that when one of R 2 or R 3 is then the other is either sufficient to form an anhydride group i.e., linking the 1 and 2 position on the aromatic moiety; R 2 and R 3 may also be COOR 5 wherein each R 5 is independently selected from alkyl groups of from about 1 to about 16 carbon atoms.
• R 4 is COOR 6 wherein R 6 is a C 1 -C 16 alkyl group.
• Representative compounds falling within formula I above include propyl gallate, gallic acid, pyromellitic acid (i.e., 1,2,4,5-benzenetetracarboxylic acid); 1,2,4,5-benezenetetracarboxylic dianhydride; octyl gallate;, and tetra octyl pyromellitate.
• pyromellitic acid i.e., 1,2,4,5-benzenetetracarboxylic acid
• 1,2,4,5-benezenetetracarboxylic dianhydride 1,2,4,5-benezenetetracarboxylic dianhydride
• octyl gallate etra octyl pyromellitate.
• Pyromellitic acid is presently preferred.
• the treatment i.e., compounds I and/or II above may be fed directly to the crude charge, e.g., and provide protection in the lower crude tower and vacuum column.
• the inhibition treatment can be fed anywhere to the process stream wherein it will be brought into contact with the process medium, e.g., crude or distillate fraction thereof.
• the most effective amount of the corrosion inhibitor to be used in accordance with this invention can vary, depending on the local operating conditions and the particular hydrocarbon being processed.
• the temperature and other characteristics of the acid corrosion system can have a bearing on the amount of the inhibitor or mixture of inhibitors to be used.
• the concentration of the corrosion inhibitor added to the crude oil may range from about 1 ppm to 5000 ppm, by volume.
• the inhibitor it is preferred to add the inhibitor at a relatively high initial dosage rate of 2000-3000 ppm and to maintain this level for a relatively short period of time until the presence of the inhibitor induces the build-up of a corrosion protective coating on the metal surfaces.
• the corrosion inhibitor may be added either neat or diluted. Once the protective surface is established, the dosage rate needed to maintain the protection maybe reduced to a normal operational range of about 100-1500 ppm without substantial sacrifice of protection.
• a weight loss coupon autoclave test was used to evaluate compounds for naphthenic acid corrosion. Test specimens were cleaned, preweighed, mild steel or 5Cr corrosion coupons that were provided with a glass bead surface finish. A paraffinic hydrocarbon oil was dosed with naphthenic acids to give a Total Acid Number of 6.0 and placed into the test autoclave. Candidate treatments, which were solids at room temperature, were added to the autoclaves and mixed. The oil was deareated with argon.
• the effect of sulfide on corrosion and inhibition was determined by the addition of a sulfur containing compound, namely n-dodecylmethylsulfide in Example 2 and dibutylsulfide in Example 5, which resulted in 0.5% sulfide in those experiments.
• the autoclaves were heated to the desired test temperature of either 600° F. or 500° F. After 20 hours exposure, the coupons were removed, cleaned, and reweighed. Test results are shown below. In the experiments with n-dodecylmethylsulfide, corrosion inhibition was only determined with the mild steel coupons since corrosion rates were quite low, ⁇ 10 mpy, with the 5Cr coupons.
• a high temperature autoclave was used to evaluate a number of comparative and prospective corrosion inhibitors in a dearated HVG0 derived from a Venezuelan crude oil.
• One static carbon steel coupon was hung in the vapor space.
• Two carbon steel coupons were rotated at about 2 fps in the liquid phase.
• Liquid phase temperature was controlled at 600° F. for approximately 20 hours.
• the weight loss, surface area, and exposure time were used to calculate the general corrosion rate in mpy for untreated and treated coupons. Results are shown below.
• Test compound identification above having a C letter prefix designates a comparative example.
• the tetra acidic aromatic compounds (I) and trimellitic acid esters and anhydrides II are effective in reducing corrosion of metallic surfaces in contact with high temperature crudes, particularly naphthenic acid containing crudes.
• the treatments of the invention also do not contain phosphorous or sulfide moieties which have proven problematic with regard to possible catalyst poisoning and thermal instability respectively.
• the treatments of the invention are effective corrosion inhibitors in those crude oil and petroleum distillate containing systems in which both naphthenic acids and sulfur compounds are present.
• naphthenic acid corrosion appears to be exceptionally serious in the presence of sulfur compounds, especially hydrogen sulfide.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Combustion & Propulsion (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2004
  • 2004-11-02 US US10/979,913 patent/US20060091044A1/en not_active Abandoned
• 2005
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  • 2005-10-25 DE DE602005025679T patent/DE602005025679D1/de active Active
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