FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patent Rules, 2003
Provisional Specification
(See section 10 and rule 13)
A new additive for inhibiting acid corrosion and method of using the new additive.
Dorf Ketal Chemicals (I) Pvt. Ltd
Dorf Ketal Tower, D'monte Street, Orlem, Malad (W), Mumbai, 400064 Maharashtra
State, India
An Indian company registered under the Companies Act, 1956

The following specification describes the invention:


AN NEW ADDITIVE FOR INHIBITING ACID CORROSION AND METHOD OF USING THE NEW ADDITIVE
FIELD OF THE INVENTION
The present invention relates to the inhibition of metal corrosion in acidic hot hydrocarbons and particularly to he inhibition of corrosion of iron - containing metals in hot acidic hydrocarbons, especially when the acidity is derived from the presence of naphthenic acid and more particularly to an effective polymeric additive to effect corrosion inhibition and a method of using the same.
DISCUSSION OF PRIOR ART
It is widely known in the art that the processing of crude oil and its various fractions has led to damage to piping and other associated equipment due to naphthenic acid corrosion. These are corrosive to the equipment used to distill, extract, transport and process the crudes. Generally speaking, naphthenic acid corrosion occurs when the crude being processed has a neutralization number or total acid number (TAN), expressed as the milligrams of potassium hydroxide required to neutralize the acids in a one gram sample, above 0.2. It is also known that naphthenic acid-containing hydrocarbon is at a temperature between about 200°C and 400°C (approximately 400°F -750°F), and also when fluid velocities are high or liquid impinges on process surfaces e.g. in transfer lines, return bends and restricted flow areas.
Corrosion problems in petroleum refining operations associated with naphthenic acid constituents and sulfur compounds in crude oils have been recognized for many years. Such corrosion is particularly severe in atmospheric and vacuum distillation units at temperatures between 400°F and 790°F. Other factors that contribute to the corrosivity of crudes containing naphthenic acids include the
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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).
As commonly used, naphthenic acid is a collective term for certain organic acids present in various crude oils. Although there may be present minor amounts of other organic acids, it is understood that the majority of the acids in naphthenic based crude are naphthenic in character, i.e., with a saturated ring structure as follows:

The molecular weight of naphthenic acid can extend over a large range. However, the majority of the naphthenic acid from crude oils is found in gas oil and light lubricating oil. When hydrocarbons containing such naphthenic acid contact iron-containing metals, especially at elevated temperatures, severe corrosion problems arise.
Naphthenic acid corrosion has plagued the refining industry for many years. This corroding material consists of predominantly monocyclic or bicyciic carboxylic acids with a boiling range between 350° and 650°F. These acids tend to concentrate in the heavier fractions during crude distillation. Thus, locations such as the furnace tubing, transfer lines, fractionating tower internals, feed and reflux sections of columns, heat exchangers, tray bottoms and condensers are primary sites of attack for naphthenic acid. Additionally, when crude stocks high in naphthenic acids are processed, severe corrosion can occur in the carbon steel or ferritic steel furnace tubes and tower bottoms. Recently interest has grown in the control of this type of corrosion in hydrocarbon processing units due to the


presence of naphthenic acid in crudes from locations such as China, India, Africa and Europe.
Crude oils are hydrocarbon mixtures which have a range of molecular structures and consequent range of physical properties. The physical properties of naphthenic acids which may be contained in the hydrocarbon mixtures also vary with the changes in molecular weight, as well as the source of oil containing the acid. Therefore, characterization and behavior of these acids are not well understood. A well known method used to "quantify" the acid concentration in crude oil has been a KOH titration of the oil. The oil is titrated with KOH, a strong base, to an end point which assures that all acids in the sample have been neutralized. The unit of this titration is mg. of KOH/gram of sample and is referred to as the "Total Acid Number" (TAN) or Neutralization Number. Both terms are used interchangeably in the application.
The unit of TAN is commonly used since it is not possible to calculate the acidity of the oil in terms of moles of acid, or any other of the usual analytical terms for acid content. Refiners have used TAN as a general guideline for predicting naphthenic acid corrosion. For example, many refineries blend their crude to a TAN^O.5 assuming that at these concentrations naphthenic acid corrosion will not occur. However, this measure has been unsuccessful in preventing corrosion by naphthenic acid.
Naphthenic acid corrosion is very temperature dependent. The generally accepted temperature range for this corrosion is between 205°C and 400°C (400°F and 750°F). Corrosion attack by these acids below 205°C has not yet been reported in the published literature. As to the upper boundary, data suggests that corrosion rates reach a maximum at about 600°-700°F and then begin to diminish.
The concentration and velocity of the acid/oil mixture are also important factors
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which influence naphthenic acid corrosion. This is evidenced by the appearance of the surfaces affected by naphthenic acid corrosion. The manner of corrosion can be deduced from the patterns and color variations in the corroded surfaces. Under some conditions, the metal surface is uniformly thinned. Thinned areas also occur when condensed acid runs down the wall of a vessel. Alternatively, in the presence of naphthenic acid pitting occurs, often in piping or at welds. Usually the metal outside the pit is covered with a heavy, black sulfide film, while the surface of the pit is bright metal or has only a thin, grey to black film covering it. Moreover, another pattern of corrosion is erosion-corrosion, which has a characteristic pattern of gouges with sharp edges. The surface appears clean, with no visible by-products. The pattern of metal corrosion is indicative of the fluid flow within the system, since increased contact with surfaces allows for a greater amount of corrosion to take place. Therefore, corrosion patterns provide information as to the method of corrosion which has taken place. Also, the more complex the corrosion, i.e., in increasing complexity from uniform to pitting to erosion-corrosion, the lower is the TAN value which triggers the behavior.
The information provided by corrosion patterns indicates whether naphthenic acid is the corroding agent, or rather if the process of corrosion occurs as a result of attack by sulfur. Most crude contain hydrogen sulfide, and therefore readily form iron sulfide films on carbon steel. In all cases that have been observed in the laboratory or in the field, metal surfaces have been covered with a film of some sort. In the presence of hydrogen sulfide the film formed is invariably iron sulfide, while in the few cases where tests have been run in sulfur free conditions, the metal is covered with iron oxide, as there is always enough water or oxygen present to produce a thin film on the metal coupons.
Tests utilized to determine the extent of corrosion may also serve as indicators of the type of corrosion occurring within a particular hydrocarbon treating unit. Metal coupons can be inserted into the system. As they are corroded, they lose
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material. This weight loss is recorded in units of mg/cm.sup.2. Thereafter, the corrosion rate can be determined from weight loss measurements. Then the ratio of corrosion rate to corrosion product (mpy/mg/cm.sup.2) is calculated. This is a further indicator of the type of corrosion process which has taken place, for if this ratio is less than 10, it has been found that there is little or no contribution of naphthenic acid to the corrosion process. However, if the ratio exceeds 10, then naphthenic acid is a significant contributor to the corrosion process.
Distinguishing between sulfidation attack and corrosion caused by naphthenic acid is important, since different remedies are required depending upon the corroding agent. Usually, retardation of corrosion caused by sulfur compounds at elevated temperatures is effected by increasing the amount of chromium in the alloy which is used in the hydrocarbon treating unit. A range of alloys may be employed, from 1.25% Cr to 12% Cr, or perhaps even higher. Unfortunately, these show little to no resistance to naphthenic acid. To compensate for the corroding effects of sulfur and naphthenic acid, an austenitic stainless steel which contains at least 2.5% molybdenum, must be utilized. The corrosive problem is known to be aggravated by the elevated temperatures necessary to refine and crack the oil and by the oil's acidity which is caused primarily by high levels of naphthenic acid indigenous to the crudes.Naphthenic acids is corrosive between the range of about 175°C to 420°C. At the higher temperatures the naphthenic acids are in the vapor phase and at the lower temperatures the corrosion rate is not serious. The corrosivity of naphthenic acids appears to be exceptionally serious in 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.
6
y

Sulfur in the crudes, which produces hydrogen sulfide at higher temperatures, also aggravates the problem. The temperature range of primary interest for this type of corrosion is in the range of about 175°C to about 400°C, especially about 205°C to about 400°C.
Various approaches to controlling naphthenic acid corrosion have included neutralization and/or removal of naphthenic acids from the crude being processed; blending low acid number oils with corrosive high acid number oils to reduce the overall neutralization number; and the use of relatively expensive corrosion-resistant alloys in the construction of the piping and associated equipment. These attempts are generally disadvantageous in that they require additional processing and/or add substantial costs to treatment of the crude oil. Alternatively, various amine and amide based corrosion inhibitors are commercially available, but these are generally ineffective in the high temperature environment of naphthenic acid corrosion. Naphthenic acid corrosion is readily distinguished from conventional fouling problems such as coking and polymer deposition which can occur in ethylene cracking and other hydrocarbon processing reactions using petroleum based feedstocks. Naphthenic acid corrosion produces a characteristic grooving of the metal in contact with the corrosive stream. In contrast, coke deposits generally have corrosive effects due to carburization, erosion and metal dusting.
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/sulfur corrosion, with the resistant metals such as high quality stainless steel or alloys containing higher amounts of chromium and molybdenum. The installation of corrosion - resistant alloys is capital intensive, as alloys such as 304 and 316 stainless steels are several times the cost of carbon steel. 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.
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*

However, these corrosion inhibitors are relatively ineffective in the high temperature environment of naphthenic acid oils.
While various corrosion inhibitors are known in various arts, the efficacy and usefulness of any particular corrosion inhibitor is dependent on the particular circumstances in which it is applied. Thus, efficacy or usefulness under one set of circumstances often does not imply the same for another set of circumstances. As a result, a large number of corrosion inhibitors have been developed and are in use for application to various systems depending on the medium treated, the type of surface that is susceptible to the corrosion, the type of corrosion encountered, and the conditions to which the medium is exposed. For example, U.S. Pat. No. 3,909,447 describes certain corrosion inhibitors as useful against corrosion in relatively low temperature oxygenated aqueous systems such as water floods, cooling towers, drilling muds, air drilling and auto radiator systems. That patent also notes that many corrosion inhibitors capable of performing in non-aqueous systems and/or non-oxygenated systems perform poorly in aqueous and/or oxygenated systems. The reverse is true as well. The mere fact that an inhibitor that has shown efficacy in oxygenated aqueous systems does not suggest that it would show efficacy in a hydrocarbon. Moreover, the mere fact that an inhibitor has been efficacious at relatively low temperatures does not indicate that it would be efficacious at elevated temperatures. In fact, it is common for inhibitors that are very effective at relatively low temperatures to become ineffective at temperatures such as the 175°C to 400°C. encountered in oil refining. At such temperatures, corrosion is notoriously troublesome and difficult to alleviate. Thus, U.S. Pat. No. 3,909,447 contains no teaching or suggestion that it would be effective in non¬aqueous systems such as hydrocarbon fluids, especially hot hydrocarbon fluids. Nor is there any indication in U.S. Pat. No. 3,909,447 that the compounds disclosed therein would be effective against naphthenic acid corrosion under such conditions.
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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, this is thought to lead to a metal phosphate surface film. The film 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 problems caused by naphthenic acid corrosion in refineries and the prior art solutions to that problem have been described at length in the literature, the following of which are representative:
U.S. Pat. No. 3,531,394 to Koszman described the use of phosphorus and/or bismuth compounds in the cracking zone of petroleum steam furnaces to inhibit coke formation on the furnace tube walls.
U.S. Pat. No. 3,531,394 to Koszman described the use of phosphorus and/or bismuth compounds in the cracking zone of petroleum steam furnaces to inhibit coke formation on the furnace tube walls.
U.S. Pat. No. 4,024,049 to Shell et al discloses compounds substantially as described and claimed herein for use as refinery antifoulants. While effective as antifoulant materials, materials of this type have not heretofore been used as corrosion inhibitors in the manner set forth herein. While this reference teaches the addition of thiophosphate esters such as those used in the subject invention to the incoming feed, due to the non-volatile nature of the ester materials they do not distill into the column to protect the column, the pumparound piping, or further process steps. I have found that by injecting the thiophosphate esters as taught
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herein, surprising activity is obtained in preventing the occurrence of naphthenic acid corrosion in distillation columns, pumparound piping, and associated equipment.
U.S. Pat. No. 4,105,540 to Weinland describes phosphorus containing compounds as antifoulant additives in ethylene cracking furnaces. The phosphorus compounds employed are mono- and di-ester phosphate and phosphite compounds having at least one hydrogen moiety complexed with an amine.
U.S. Pat. No. 4,443,609 discloses certain tetrahydrothiazole phosphonic acids and esters as being useful as acid corrosion inhibitors. Such inhibitors can be prepared by reacting certain 2,5-dihydrothiazoles with a dialkyl phosphite. While these tetrahydrothiazole phosphonic acids or esters have good corrosion and inhibition properties, they tend to break down during high temperature applications thereof with possible emission of obnoxious and toxic substances.
It is also known that phosphorus-containing compounds impair the function of various catalysts used to treat crude oil, e.g., in fixed-bed hydrotreaters and hydrocracking units. Crude oil processors are often in a quandary since if the phosphite stabilizer is not used, then iron can accumulate in the hydrocarbon up to 10 to 20 ppm and impair the catalyst. Although nonphosphorus-containing inhibitors are commercially available, they are generally less effective than the phosphorus-containing compounds.
U.S. Pat. No. 4,542,253 to Kaplan et al, described an improved method of reducing fouling and corrosion in ethylene cracking furnaces using petroleum feedstocks including at least 10 ppm of a water soluble mine complexed phosphate, phosphite, thiophosphate or thiophosphite ester compound, wherein the amine has a partition coefficient greater than 1.0 (equal solubility in both aqueous and hydrocarbon solvents).
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U.S. Pat. No. 4.842,716 to Kaplan et al describes an improved method for reducing fouling and corrosion at least 10 ppm.of a combination of a phosphorus antifoulant compound and a filming inhibitor. The phosphorus compound is a phosphate, phosphite, thiophosphate or thiophosphite ester compound. The filming inhibitor is an imidazoline compound.
U.S. Pat. No. 4,941,994 Zetmeis et al discloses a naphthenic acid corrosion inhibitor comprising a dialkyl or trialkylphosphite in combination with an optional thiazoline.
A significant advancement in phosphorus-containing naphthenic acid corrosion inhibitors was reported in U.S. Pat. No. 4,941,994. Therein it is disclosed that metal corrosion in hot acidic liquid hydrocarbons is inhibited by the presence of a corrosion inhibiting amount of a dialkyl and/or trialkyl phosphite with an optional thiazoline.
While the method described in U.S. Pat. No. 4,941,994 provides significant improvements over the prior art techniques, nevertheless, there is always a desire to enhance the ability of corrosion inhibitors while reducing the amount of phosphorus-containing compounds which may impair the function of various catalysts used to treat crude oil, as well as a desire for such inhibitors that may be produced from lower cost or more available starting materials.
Another approach to the prevention of naphthenic acid corrosion is the use of a chemical agent to form a barrier between the crude and the equipment of the hydrocarbon processing unit. This barrier or film prevents corrosive agents from reaching the metal surface, and is generally a hydrophobic material. Gustavsen et al. NACE Corrosion 89 meeting, paper no. 449, Apr. 17-21, 1989 details the requirements for a good filming agent. U.S. Pat. No. 5,252,254 discloses one such
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film forming agent, sulfonated alkyl-substituted phenol, and effective against naphthenic acid corrosion.
U.S. Pat. No. 5,182,013 issued to Petersen et al. on Jan. 26, 1993 describes another method of inhibiting naphthenic acid corrosion of crude oil, comprising introducing into the oil an effective amount of an organic polysulfide. The disclosure of U.S. Pat. No. 5,182,013 is incorporated herein by reference. This is another example of a corrosion-inhibiting sulfur species. Sulfidation as a source of corrosion was detailed above. Though the process is not well understood, it has been determined that while sulfur can be an effective anti-corrosive agent in small quantities, at sufficiently high concentrations, it becomes a corrosion agent.
Phosphorus can form an effective barrier against corrosion without sulfur, but the addition of sulfiding agents to the process stream containing phosphorus yields a film composed of both sulfides and phosphates. This results in improved performance as well as a decreased phosphorus requirement. This invention pertains to the deliberate addition of sulfiding agents to the process stream when phosphorus-based materials are used for corrosion control to accentuate this interaction.
Organic polysulfides (Babaian-Kibala, U.S. Pat. No. 5,552,085), organic phosphites (Zetlmeisl, U.S. Pat. No. 4,941,994), and phosphate/phosphite esters (Babaian-Kibala, U.S. Pat. No. 5,630,964), have been claimed to be effective in hydrocarbon-rich phase against naphthenic acid corrosion. However, their high oil solubility incurs the risk of distillate side stream contamination by phosphorus.
Phosphoric acid has been used primarily in aqueous phase for the formation of a phosphate/iron complex film on steel surfaces for corrosion inhibition or other applications (Coslett, British patent 8,667, U.S. Pat. Nos. 3,132,975, 3,460,989 and 1,872,091). Phosphoric acid use in high temperature non-aqueous
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environments (petroleum) has also been reported for purposes of fouling mitigation (U.S. Pat. No. 3,145,886).
There remains a continuing need to develop additional options for mitigating the corrosivity of acidic crudes at lower cost. This is especially true at times of low refining margins and a high availability of corrosive crudes from sources such as Europe, China, or Africa, and India. The present invention addresses this need.
In view of above, there is a need to provide alternative composition to provide effective high temperature naphthenic acid corrosion inhibition, which will overcome the disadvantages of the prior - art compositions.
DESCRIPTION OF THE INVENTION
The present invention uses the following reacted compound to be used as corrosion inhibitor for inhibiting high temperature naphthenic acid corrosion. This reacted compound is obtained by reaction of hydroxy - terminated polyisobutylene (PIB) compound and phosphorous pentasulfide..
Conventional PIBs and so-called "high-reactivity" PIBs (see for example EP-B-0565285) are suitable for use in this invention. High reactivity in this context is defined as a PIB wherein at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type, for example the GLISSOPAL compounds available from BASF.
The ratio ofP2S5to PIB is preferably 0.01 to 4moleof P2S5to 1 moleofPIB.
It has been surprisingly discovered by the inventor of the present invention, that a polymer based phosphate ester, having low phosphorus content, low acidity and high thermal stability, and non - fouling nature gives very effective control of napthenic acid corrosion.
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The novel additive is made in four basic steps.
1. High reactive PIB (Polyisobutylene) is reacted with Maleic Anhydride to make Poluisobutylene succinic anhydride (PIBSA)
2. The resultant reaction - compound of step No. 1 is further reacted with ethylene glycol to give an ester having hydroxyl end termed as PIB ester, which is polyisobutenyl succinate ester.
( 3. The resultant reaction - compound of step no. 2 is then reacted with
phosphorus pentsulfide. (The resulting reaction compound is also effective in inhibition of napthenic acid corrosion). The reaction can be carried out by using various mole ratios of PIB ester and phosphorus pentasulfide. The resultant reaction compound obtained after completing step no. 3 is Thiophosphate ester of polyisobutenyl succinate ester.
It should be noted that the above mentioned steps can be understood better by referring to the corresponding examples.
The present invention is directed to a method for inhibiting corrosion on the metal surfaces of the processing units which process hydrocarbons such as crude oil and its fractions containing naphthenic acid. The invention is explained in details in its simplest form wherein the following method steps are carried out, when it is used to process crude oil in process units such as distillation unit. Similar steps can be used in different processing units such as, pumparound piping, heat exchangers and such other processing units.
These method steps are explained below:
a) heating the hydrocarbon containing naphthenic acid to vaporize a portion of the hydrocarbon:
b) allowing the hydrocarbon vapors to rise in a distillation column;
c) condensing a portion of the hydrocarbon vapours passing through the distillation column to produce a distillate;


d) adding to the distillate, from 1 to 2000 ppm of Thiophosphate ester of polyisobutenyl succinate ester or combination thereof, which is the required additive of present inventions;
e) allowing the distillate containing compound of step (d) to contact substantially the entire metal surfaces of the distillation unit to form protective film on such surface, whereby such surface is inhibited against corrosion.
It is advantageous to treat distillation column, trays, pumparound piping and related equipment to prevent naphthenic acid conosion, when condensed vapours from distilled hydrocarbon fluids contact metallic equipment at temperatures greater than 200 °C, and preferably 400 °C. The additive is generally added to the condensed distillate and the condensed distillate is allowed to contact the metallic surfaces of the distillation column, packing, trays, pump around piping and related equipment as the condensed distillate passes down the column and into the distillation vessel. The distillate may also be collected as product. The corrosion inhibitors of the instant invention remain in the resultant collected product.
In commercial practice, the additives of this invention may be added to a distillate return to control corrosion in a draw tray and in the column packing while a second injection may be added to a spray oil return immediately below the draw trays to protect the tower packing and trays below the distillate draw tray. It is not so critical where the additive of the invention is added as long as it is added to distillate that is later returned to the distillation vessel, or which contact the metal interior surfaces of the distillation column, trays, pump around piping and related equipments.
The method of using the of the present invention for achieving inhibition of high temperature naphthenic acid corrosion is explained below with the help of examples and tables.
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Thus it is seen that the additive compound of present invention used for corrosion - inhibition has the following important distinguishing features, as compared to the prior art.
1) The inventor of the present invention, after extensive
experimentation, has surprisingly found that the additive
compound used by the inventor, is the only POLYMERIC
ADDITIVE, which is highly effective in high temperature
corrosion inhibition, as shown by the experimental results given in
Tables.
The prior - art does not teach or suggest use of a polymeric additive in naphthenic acid corrosion inhibition or sulphur corrosion inhibition or any corrosion inhibition, in general.
2) Another distinguishing feature of the additive compound of present invention is that it has more thermal stability as compared to the additive compounds taught by the prior - art, due to the polymeric nature of the additive compound of present invention. Due to its high thermal stability the additive compound of present invention is very effective in high temperature naphthenic corrosion inhibition or high temperature sulphur corrosion.
3) Yet another distinguishing feature of the additive compound of present invention is that, it has very low acidity as compared to the additive compounds of prior art, for example, the phosphate esters of prior art has very high acidity. The phosphate esters of prior art are known to have a tendency to decompose, even at lower temperatures, to form phosphoric acids, which travel farther along the hydrocarbon stream and react with metal surfaces of equipments such as packing of distillation column, to form solid
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iron phosphate. These solids plug the holes of equipments and
thereby lead to fouling of distillation column.
The additive compound of the present invention does not have this
deficiency.
EXAMPLE 1
Step I: Polyisobutenyl succinic anhydride

Product name %wt
1 HRPIB (OLOA 16500) 89.48
2 Maleic anhydride 10.52
Total size 100.00
Procedure
1. Charge HRPIB (High Reactive Polyisobutylene) into a clean and dry four
necked flask equipped with nitrogen inlet, stirrer and thermometer.
2. Raise temperature to 125°C.
3. Start N2 gas bubbling and continue for 10 minutes.
4. Stop / reduce rate of N2 gas bubbling, sample for moisture content
5. Add maleic anhydride at 125°C.
6. After addition of maleic anhydride raise temperature to 170°C and maintain it for 2 hours with nitrogen bubbling.
7. After completion of maintaining period, further temperature raise to 205°C, heat such a rate it should reach 170° C - 205°C in 3 hours (5°C/25min).
8. At 205°C maintain for 6 hours
9. After completion of 6 hours (at 205°C) and coo) the reaction mixture to 170"C.
10. Apply vacuum slowly then raise temperature to 205°C .
11. At 205°C continue vacuum (below 10 mm). After 2 hours sample online -1 for argon and free maleic acid and after 3 hours sample online - II for argon and free maleic aid.
The desired acid value of the product is between 70 to 120 mg / KOH
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Step II: PIB Ester

Product name %wt Remarks
1 Ist step 79.899 Sample diluted on Toluene to 85% strength Sic-85.714%
2 Mono ethylene glycol 20.101
Total size 100.00
Procedure
1. Charge 1st step and mono ethylene glycol.
2. Raise temperature to 190° C (remove Toluene and water from dean stark to reach the temperature) with nitrogen gas bubbling.
3. Maintain at 190" C up to required acid value.
It should be noted that, the desired acid value should be less than 5 mg / KOH
EXAMPLE 2
Reaction of PIB Ester with Phosphorus pentasulfide ( Theoratical Phosphorous content in the final 100 % active product P - 3.156 %)

Product name %wt Remarks
1 PIB Ester (IInd step product) 88.701 EXAMPLE 1 STEP 2
2 phosphorus pentasulfide 11.299 SD Fine'
100.00
Procedure
1. Change PIB Ester, Raise temperature to 90° C with nitrogen gas bubbling
2. Add phosphorus pentasulfide at 90° C slowly in one lot
3. After addition of phosphorus pentasulfide raise temperature to 120°C
4. At 120° C maintain it for 1 hour
5. After 1 hour at 120° C slowly raise temperature to 140° C and maintain it for 1 hour. Then cool to 90° C
6. acid value of the as auch sample is (45.61 mg/KOH)
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7. Dilute with 1:1 Toluene
8. Raise temperature to reflux, start nitrogen gas bubbling and continue for 6 hours.
9. Cool and filter through byflow 60° C.
10. Adjust solid content to 50%.
( Theoratical Phosphorous content in the final 100 % active product
P-4.47%)

Product name %wt Remarks
1 PIB Ester 83.981 EXAMPLE 1 STEP 2
2 phosphorus pentasulfide 16.019 SD fine
100.00
Acid value (as such) - is between 64 and 73 mg/KOH
( Theoratical Phosphorous content in the final 100 % active product P- 7.715)

Product name %wt Remarks
1 PIB Ester 72.374 EXAMPLE 1 STEP 2
2 phosphorus pentasulfide 27.626 SD Fine
100.00
Acid value (assuch)- 109.65 mg/KOH
EXAMPLE 3
High Temperature Naphthenic Acid Corrosion Test
In this example, various amounts of a 50 % formulation of the composition prepared in accordance, with Examples 1 to 3, were tested for corrosion inhibition efficiency on steel coupons in hot oil containing naphthenic acid. A weight loss coupon, immersion test was used to evaluate the invention compound for its effectiveness in inhibition of naphthenic acid corrosion at 290°C temperature.
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Different dosage such as 300, 400 and 600 ppm of invention compound were used, as 50% active solution.
A static test on steel coupon was conducted without using any additive. This test provided a blank test reading.
The reaction apparatus consisted of a one - litre four necked round bottom flask equipped with water condenser, N2 purger tube, thermometer pocket with thermometer and stirrer rod. 600 gm (about 750 ml) paraffin hydrocarbon oil (D -130) was taken in the flask. N2 gas purging was started with flow rate of 100 cc / minute and the temperature was raised to 100°C, which temperature was maintained for 30 minutes.
An additive compound of examples 2 and 3. The reaction mixture was stirred for 15 minutes at 100°C temperature. After removing the stirrer, the temperature of the reaction mixture was raised to 290°C. A pre - weighed weight - loss carbon steel coupon CS 1010 with dimensions 76mm... times 13mm... times 1.6 mm was immersed. After maintaining this condition for l hour to 1.5 hours, 31 gm of naphthenic acid (commercial grade with acid value of 230 mg /KOH) was added to the reaction mixture. A sample of one gm weight of reaction mixture was collected for determination of acid value, which was found to be approximately 11.7. This condition was maintained for four hours. After this procedure, the metal coupon was removed, excess oil was rinsed away, the excess corrosion product was removed from the metal surface. Then the metal coupon was weighed and the corrosion rate was calculated in mils per year.
Calculation of Corrosion Inhibition Efficiency.
The method used in calculating Corrosion Inhibition Efficiency is given below. In this calculation, corrosion inhibition efficiency provided by additive compound is
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calculated by comparing weight loss due to additive with weight loss of blank coupon (without any additive).
Corrosion (Weight loss for blank (weight loss with
Inhibition = without additive) : additive) X 100
Efficiency (weight loss for blank without additive)
The calculated magnitudes are entered in the Tables in appropriate columns. The results of the experiments are presented in Table I, II and III.
Table I: Phosphrous Content P 3.145%

Experiment
No. Compound Dosage
in
Ppm Effective
Dosage
inppm Weight Loss in
mg Corrosion Rate
MPY Corrosion Inhibition efficiency
1 Blank — ~ 89 445 —
2 EXAMPLE 2 600 300 1.8 mg 9 97.97
Table II: 4.47 %P

Experiment No. Compound Dosage
in Ppm Effective
Dosage
inppm Weight Loss in mg Corrosion Rate
MPY Corrosion Inhibition efficiency
1 Blank — — 89 445 —
2 EXAMPLE
2 300 150 24.7 123 72.4
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Table III: 7.75%P

Experiment No. Compound Dosage
in
Ppm Effective Dosage in ppm Weight Loss in mg Corrosion Rate
MPY Corrosion Inhibition efficiency
1 Blank ~ — 89 445 —
2 EXAMPLE
2 400 200 0.4 2 99.6
3 EXAMPLE
2 300 150 3.7 18.5 95.84
The corrosion rate in MPY (mils per year) is calculated by the formula,
MPY = 534 x Weight loss in mg
(Density in gm/cc) x (Area in in ) x (Time of test in hours)
Dated this 25m of August, 2008