ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIRO..CY..TRBGCZEEHUPLSK....IS..............................*JDIM360 Ver 2.15 (14 Jul 2008) - 2100000/01814965EUROPEAN PATENT SPECIFICATIONB120101229EP05820782.02005102520070604enenen97991320041102US20101229201052200708082007322010122920105220100803C10G 7/10 20060101AFI20070606BHEP C10G 9/16 20060101ALI20070606BHEP C10L 1/26 20060101ALI20070606BHEP C10L 10/04 20060101ALI20070606BHEP deHOCHTEMPERATURKORROSIONSINHIBITORenHIGH TEMPERATURE CORROSION INHIBITORfrINHIBITEUR DE CORROSION A HAUTE TEMPERATUREEP-A- 0 375 614EP-A- 0 607 640EP-A- 0 672 744LEHRER, Scott, E.143 North Piney Plains CircleThe Woodlands, TX 77382USPRUETT, S. Blake3034 North FM 1486Montgomery, TX 77356USMINEVSKI, Liliana, V.27 Sunny Oaks PlaceThe Woodlands, TX 77385USEDMONDSON, James, G.1114 Pinsonfork DriveSpring, TX 77379USGOLIASZEWSKI, Alan, E.22 Feather Branch CourtThe Woodlands, TX 77381USSHAO, Feng310 Queen StreetPhiladelphia, PA 19147USGENERAL ELECTRIC COMPANY100129092150981/123811 River RoadSchenectady, NY 12345USSzary, Anne Catherineet al100036774London Patent Operation GE International Inc. 15 John Adam StreetLondon WC2N 6LUGBATBEBGCHCYCZDEDKEEESFIFRGBGRHUIEISITLILTLULVMCNLPLPTROSESISKTRUS200503852220051025enWO200604998020060511200619 FIELD OF INVENTION

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.

BACKGROUND OF THE INVENTION

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 180°C (350°F) and 420°C (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).

In the distillation refining of crude oils, the crude oil is passed successively through a furnace and one or more fractionators such as an atmospheric tower and a vacuum tower. In most operations, naphthenic acid corrosion is not a problem at temperatures below about 180°C (350°F). Traditional nitrogen-based filming corrosion inhibitors are not effective at temperatures above 180°C (350°F), and the other approaches for preventing naphthenic acid corrosion such as neutralization present operational problems or are not effective.

It should be observed that the term "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.

Many variations of this structure and molecular weight are possible. Some practitioners include 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.

Efforts to minimize or prevent the naphthenic acid corrosion have included the following approaches:

  1. a) blending of higher naphthenic acid content oil with oil low in naphthenic acids;
  2. b) neutralization and removal of naphthenic acids from the oil; and
  3. c) use of corrosion inhibitors.

Because these approaches have not been entirely satisfactory, the accepted approach in the industry is to construct the distillation unit, or the portions exposed to naphthenic acid corrosion, with the resistant metals such as high quality stainless steel or alloys containing higher amounts of chromium and molybdenum. However, in units not so constructed, there is a need to provide inhibition treatment against this type of corrosion. The prior art corrosion inhibitors for naphthenic acid environments include nitrogen-based filming corrosion inhibitors. However, these corrosion inhibitors are relatively ineffective in the high temperature environment of naphthenic acid oils.

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. In the case of 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.

DETAILED DESCRIPTION

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 COOR1, with the proviso that vicinal pairs of W, X, Y, Z can be i.e., anhydride function. R1 in the formula is an alkyl moiety having from about 1 to about 16 carbon atoms; Ar is an aromatic moiety.

The esters or anhydrides of trimellitic acid (II) are represented by the formula (II) wherein R2 and R3 are with the proviso that when one of R2 or R3 is then the other is either or sufficient to form an anhydride group i.e., linking the 1 and 2 position on the aromatic moiety; R2 and R3 may also be COOR5 wherein each R5 is independently selected from alkyl groups of from about 1 to about 16 carbon atoms. R4 is COOR6 wherein R6 is a C1-C16 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 is presently preferred.

With regard to compounds encompassed by formula (II) above, 1,2,4 benzenetricarboxylic anhydride and trioctyltrimellitate may be mentioned.

In accordance with one aspect of the present invention, the treatment i.e., compounds I and/or II above may be fed directly to the crude change, e.g., and provide protection in the lower crude tower and vacuum column. Conversely, 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. Thus, 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. Generally, where the operating temperatures and/or the acid concentrations are higher, a proportionately higher amount of the corrosion inhibitor will be required. It has been found that the concentration of the corrosion inhibitor added to the crude oil may range from about 1 ppm to 5000 ppm, by volume. It has also been found that 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.

EXAMPLES

The invention will now be further described in conjunction with the following examples, which are provided for illustration purposes and are not intended to act as a limitation thereof.

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. In some experiments, 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 316°C (600°F) or 260°C (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.

Example 1

Inhibitor Dosage % Corrosion Inhibition MS 5Cr Gallic Acid 100 -32 40 Gallic Acid 1000 92 93 1,2,4,5-Benzenetetracarboxylic Acid 100 95 99 1,2,4,5-Benzenetetracarboxylic Acid 1000 98 99 Propyl Gallate 100 30 97 Propyl Gallate 1000 96 99

Example 2

Inhibitor Dosage % Corrosion Inhibition MS Gallic Acid 100 25 Gallic Acid 1000 78 1,2,4,5-Benzenetetracarboxylic Acid 100 78

Example 3

Inhibitor Dosage % Corrosion Inhibition MS 5Cr Gallic Acid 100 32 91 Gallic Acid 1000 98 84

Example 4

Test Compound Dosage % Corrosion ppm    Inhibition 1,2,4,5-benzenetetracarboxylic acid 25 84 1,2,4,5-benzenetetracarboxylic acid 100 82 1,2,4,5-benzenetetracarboxylic acid 250 93 1,2,4,5-benzenetetracarboxylic dianhydride 25 31 1,2,4,5-benzenetetracarboxylic dianhydride 100 84 1,2,4,5-benzenetetracarboxylic dianhydride 250 93 Octyl Gallate 25 -21 Octyl Gallate 100 -12 Octyl Gallate 250 -15 Propyl gallate 25 27 Propyl gallate 100 9 Propyl Gallate 250 41 Tetra-octyl pyromellitate 25 -30 Tetra-octyl pyromellitate 100 50 Tetra-octyl pyromellitate 250 60 Tri-octyl trimellitate 25 -9 Tri-octyl trimellitate 100 34 Tri-octyl trimellitate 250 23 1,2,4-benzenetricarboxylic anhydride 100 35 1,2,4-benzenetricarboxylic anhydride 250 58

Example 5

Test Compound Dosage % Corrosion ppm    Inhibition 1,2,4,5-benzenetetracarboxylic acid 100 35 1,2,4,5-benzenetetracarboxylic acid 250 43 1,2,4,5-benzenetetracarboxylic acid 1000 52 1,2,4,5-benzenetetracarboxylic anhydride 100 22 1,2,4,5-benzenetetracarboxylic anhydride 250 34 1,2,4,5-benzenetetracarboxylic anhydride 1000 57 Gallic acid 250 40 Gallic acid 1000 82 Octyl Gallate 250 57 Octyl Gallate 1000 72 Propyl Gallate 250 38 Propyl Gallate 1000 54 Tetra-octyl pyromellitate 250 45 Tetra-octyl pyromellitate 1000 21 Tri-octyl trimellitate 250 0 Tri-octyl trimellitate 1000 0 1,2,4-benezenetricarboxylic anhydride 250 14 1,2,4-benezenetricarboxylic anhydride 1000 58

Example 6

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 316°C (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 Dosage ppm Corrosion mpy Blank 14.2 Phenyl didecylphosphite C-1 50 13.4 Phenyl didecylphosphite C-1 ammonium salt of dinonyl phenyl 100 7.2 sulfonic acid C-2 100 11.8 gallic acid 100 9.8 gallic acid 200 10.7 pyrogallol C-3 100 11.9 catechol C-4 100 11.5 salicylic acid C-5 100 12.2 benzoic acid C-6 100 15.2 phthalic acid C-7 100 11.2

Test compound identification above having a C letter prefix designates a comparative example. As shown above in the examples, 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.

It is also noted that 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. As is known in the art, naphthenic acid corrosion appears to be exceptionally serious in the presence of sulfur compounds, especially hydrogen sulfide.

 A method for inhibiting corrosion of the internal metallic surfaces of equipment used in the processing of crude oil or high temperature distillates heated to temperatures of between about 180°C (350°F) and about 420°C (790°F) comprising adding to the crude oil or high temperature petroleum distillate a corrosion inhibiting amount of a corrosion inhibitor selected from the groups (I) and (II) and mixtures thereof, wherein said corrosion inhibitor (I) has the formula: wherein W, X, Y, and Z are all present and are the same or different and are individually selected from the groups consisting of OH; COOH; and COOR1, with the
proviso that vicinal pairs of W, X, Y, and Z may be selected from R1 is an alkyl moiety having from about 1 to 16 carbon atoms and Ar is an aromatic compound;
said corrosion inhibitor (II) having the formula wherein R2 and R3 are COOR5, with the proviso
that when one of R2 or R3 is then the other is either sufficient to form an anhydride group linking the R2 and R3 functions, each R5 is individually selected from alkyl groups having from about 1 to about 16 carbon atoms; R4 is COOR6 wherein R6 is an alkyl group having from about 1 to about 16 carbon atoms. The method as recited in claim 1 wherein Ar is substituted benzene. The method as recited in claim 2 wherein said corrosion inhibitor (I) is selected from the group consisting of gallic acid, pyromellitic acid, propyl gallate, octyl gallate, tetra octyl pyromellitate, and 1,2,4,5-benzenetetracarboxylic dianhydride. The method as recited in claim 3 wherein said corrosion inhibitor (I) is pyromellitic acid. The method as recited in claim 2 wherein the corrosion inhibitor (II) is selected from 1,2,4-benzenetricarboxylic anhydride and trioctyltrimellitate. The method as recited in claim 3 wherein said crude oil or petroleum distillate comprises naphthenic acid and said corrosion inhibitor is naphthenic acid induced corrosion. The method as recited in claim 6 wherein said crude oil or petroleum distillate further comprises a sulfur containing compound. The method as recited in claim 1 wherein the amount of corrosion inhibitor (I) and/or (II) added to the crude oil or distillate is an amount sufficient to generate a concentration of from about 1-5,000 ppm by volume. The method as recited in claim 8 wherein the concentration is from about 100 to about 1500 ppm. The method as recited in claim 3 wherein said corrosion inhibitor is 1,2,4,5-benzenetetracarboxylic dianhydride. Verfahren zum Hemmen der Korrosion der internen metallischen Oberflächen von Ausrüstung, die beim Verarbeiten von Rohöl oder Hochtemperatur-Destillaten eingesetzt wird, die auf Temperaturen zwischen 180°C (350°F) und 420°C (790°F) erhitzt werden, umfassend Hinzufügen zu dem Rohöl oder Hochtemperatur-Petroleumdestillat einer Korrosion hemmenden Menge eines Korrosionsinhibitors ausgewählt aus den Gruppen (I) und (II) und Mischungen davon,
wobei der Korrosionsinhibitor (I) die Formel hat: worin W, X, Y und Z alle vorhanden sind und gleich oder verschieden sind und einzeln ausgewählt sind aus den Gruppen bestehend aus OH, COOH und COOR1, unter der Bedingung, dass vicinale Paare von W, X, Y und Z ausgewählt sein können aus R1 eine Alkylgruppierung ist, die von etwa 1 bis 16 Kohlenstoffatome aufweist und Ar eine aromatische Verbindung ist,
der Korrosionsinhibitor (II) die Formel hat: worin R2 und R3 COOR5, ist, unter der Bedingung, dass, wenn eines von R2 oder R3 oder ist, dann ist das andere genügend oder um eine Anhydridgruppe zu bilden, die die R2- und R3-Funktionen verbindet, worin jedes R5 einzeln ausgewählt ist aus Alkylgruppen, die von etwa 1 bis etwa 16 Kohlenstoffatome aufweisen, R4 CCOR6 ist, worin R6 eine Alkylgruppe ist, die von etwa 1 bis etwa 16 Kohlenstoffatome aufweist. Verfahren nach Anspruch 1, worin Ar substituiertes Benzol ist. Verfahren nach Anspruch 2, worin der Korrosionsinhibitor (I) ausgewählt ist aus der Gruppe bestehend aus Gallussäure, Pyromellitsäure, Propylgallat, Octylgallat, Tetraoctylpyromellitat und 1,2,4,5-Benzoltetracarbonsäuredianhydrid. Verfahren nach Anspruch 3, worin der Korrosionsinhibitor (I) Pyromellitsäure ist. Verfahren nach Anspruch 2, worin der Korrosionsinhibitor (II) ausgewählt ist aus 1,2,4-Benzoltricarbonsäureanhydrid und Trioctyltrimellitat. Verfahren nach Anspruch 3, worin das Rohöl oder Petroleumdestillat Naphthensäure umfasst und der Korrosionsihibitor Naphthensäure-induzierte Korrosion ist. Verfahren nach Anspruch 6, worin das Rohöl oder Petroleumdestillat weiter eine Schwefel enthaltende Verbindung umfasst. Verfahren nach Anspruch 1, worin die zu dem Rohöl oder Destillat hinzugegebene Menge von Korrosionsinhibitor (I) und/oder (II) eine Menge ist, die genügt, um eine Konzentration von etwa 1-5000 ppm, bezogen auf das Volumen, zu erzeugen. Verfahren nach Anspruch 8, worin die Konzentration von etwa 100 bis etwa 1500 ppm beträgt. Verfahren nach Anspruch 3, worin der Korrosionsinhibitor 1,2,4,5-Benzoltetracarbonsäuredianhydrid ist Procédé permettant d'inhiber la corrosion des surfaces métalliques internes d'un équipement utilisé dans le traitement d'une huile brute ou de distillats haute température, chauffés à des températures d'environ 180 °C (350 °F) à environ 420 °C (790 °F), lequel procédé comporte le fait d'ajouter à l'huile brute ou au distillat de pétrole haute température, en une quantité appropriée pour inhiber la corrosion, un inhibiteur de corrosion choisi parmi les composés (I) et (II) et leurs mélanges ;
lequel inhibiteur de corrosion (I) présente la formule suivante : dans laquelle W, X, Y et Z représentent des entités qui sont toutes présentes, identiques ou différentes, et choisies chacune parmi les groupes symbolisés par OH, COOH ou COOR1, étant entendu que toute paire d'entités voisines, parmi les entités représentées par W, X, Y et Z, peut être symbolisée par et que R1 représente un groupe alkyle comportant à peu près 1 à 16 atomes de carbone,
et Ar représente un reste de composé aromatique ;
et lequel inhibiteur de corrosion (II) présente la formule suivante : dans laquelle R2 et R3 représentent des entités symbolisées par COOR5, -C(=O)- ou -C(=O)-O-, sous réserve que si l'un des symboles R2 et R3 représente -C(=O)- ou -C(=O)-O-, l'autre représente -C(=O)- ou -C(=O)-O-, de telle sorte que les deux symboles R2 et R3 représentent ensemble un groupe anhydride, et étant entendu que chaque symbole R5 représente une entité choisie parmi les groupes alkyle comportant d'environ 1 à environ 16 atomes de carbone,
et R4 représente une entité symbolisée par COOR6 où R6 représente un groupe alkyle comportant d'environ 1 à environ 16 atomes de carbone. Procédé conforme à la revendication 1, dans lequel Ar représente un reste de benzène à substituant(s). Procédé conforme à la revendication 2, dans lequel ledit inhibiteur de corrosion (I) est choisi dans l'ensemble formé par l'acide gallique, l'acide pyromellitique, le gallate de propyle, le gallate d'octyle, le pyromellitate de tétraoctyle, et le dianhydride d'acide benzène-1,2,4,5-tétracarboxylique. Procédé conforme à la revendication 3, dans lequel ledit inhibiteur de corrosion (I) est l'acide pyromellitique. Procédé conforme à la revendication 2, dans lequel l'inhibiteur de corrosion (II) est choisi parmi l'anhydride d'acide benzène-1,2,4-tricarboxylique et le trimellitate de trioctyle. Procédé conforme à la revendication 3, dans lequel ladite huile brute ou ledit distillat de pétrole contient des acides naphténiques et ledit inhibiteur de corrosion sert à inhiber la corrosion induite par les acides naphténiques. Procédé conforme à la revendication 6, dans lequel ladite huile brute ou ledit distillat de pétrole contient en outre un composé soufré. Procédé conforme à la revendication 1, dans lequel la quantité d'inhibiteur(s) de corrosion (I) et/ou (II) ajoutée à l'huile brute ou au distillat est une quantité suffisante pour donner une concentration d'à peu près 1 à 5000 ppm en volume. Procédé conforme à la revendication 8, dans lequel la concentration vaut d'environ 100 à environ 1500 ppm. Procédé conforme à la revendication 3, dans lequel ledit inhibiteur de corrosion est le dianhydride d'acide benzène-1,2,4,5-tétracarboxylique.