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
  • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
  • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
• • 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
  • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
• • 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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
• • 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
  • C10G2300/80—Additives

Definitions

• the present invention relates to an additive and method for removal of calcium from crude oils containing calcium naphthenate, wherein the additive is effective to remove the calcium not only at low pH but also at high pH of the wash water for the desalter used in the crude oil processing system.
• the present invention relates to an additive and method for removal of calcium from crude oils containing calcium naphthenate, wherein the additive is effective to remove the calcium under basic or alkaline conditions and having a pH varying from about 5 to 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 of the wash water for the desalter used in the crude oil processing system.
• the DOBA is a high acid crude oil originating from the Chad region of West Africa.
• the DOBA is known to contain calcium naphthenate and the amount of calcium naphthenate varies over a range from about 150 to about 700 ppm. In a typically supplied DOBA crude oil, the amount of calcium naphthenate may vary from about 250 - about 300 ppm.
• the DOBA is a heavy high acid crude oil with Total Acid Number [TAN] ranging upwards of 4.0 mg KOH/gm of sample and the API gravity is about 19.
• TAN Total Acid Number
• the sulfur content in DOBA is very low to nil.
• the DOBA is typically a crude oil with a lot of residue in it and for proper blending, typically internationally, refiners blend it with very light crude oil or condensates to increase the API of the resulted blend to more than 30.
• Such blending with light crude oil or condensates helps to create sufficient light ends to help achieve product yields for the crude distillation unit.
• the most of light crude oil or condensates thus selected generally have very little to nil sulfur contents, which means the overall sulfur content still remains very low. Further, the H 2 S being oil soluble is not present in relatively higher quantities in these types of blends.
• the inventor of present invention has observed that if solution of calcium naphthenate in an organic solvent, for example toluene having concentration of Ca of about 2247 ppm is treated with equal weight of water by heating to about 130 degree C, that is, being equal to a crude oil having very little to nil sulfur contents or say in absence of sulfur compound in a Parr autoclave under autogenous pressure, and separated into organic and aqueous layers in a separating funnel, no black layer is formed at the interface in presence of water or say in presence of very little to nil sulfur contents, being less than 0.2%.
• organic layer, as separated was dried by evaporating toluene, its acid value was found to be very low - about 48.36 (mg OH per gm). The low Acid Value indicates that calcium naphthenate does not hydrolyze appreciably merely in presence of water or say in presence of very little to nil sulfur contents, being less than 0.2%.
• the inventor of present invention has observed that when DOBA or its blend containing calcium naphthenate with no sulfur or sulfur contents being very little [less than 0.2%] is treated with additives as known in the art, for example with glycolic acid it does not hamper removal of metals including calcium from such DOBA crude oil or its blend.
• the inventor has experimentally found that even with very little to nil sulfur contents, the efficiency of glycolic acid to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases to about 6 or to about 11 due to presence of ammonium hydroxide or ammonia or other nitrogen compounds in wash water for desalter.
• the inventor of present invention has also observed that when DOBA or its blend containing calcium naphthenate with no sulfur or sulfur contents being very little [less than 0.2%] is treated with additives as known in the art, for example with malic acid, it does not hamper removal of metals including calcium from such DOBA crude oil or its blend.
• the inventor has experimentally also found that even with very little to nil sulfur contents, the efficiency of malic acid to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases to about 6 or to about 9 or to about 11 due to presence of ammonium hydroxide or ammonia or other nitrogen compounds in wash water for desalter.
• the inventor has also found that efficiency of prior art additives - maleic anhydride, citric acid, D-gluconic acid to remove calcium from DOBA crude oil is very low particularly when pH of the crude oil or wash water increase to about 6 or preferably to about 9 or to about 11.
• the problem to be solved by present invention is to provide an additive and method for removal of calcium from crude oils or its blends containing calcium naphthenate, which should be effective to remove the calcium from crude oil or its blends not only at low pH but also at high pH, particularly under basic or alkaline conditions of the wash water for the desalter used in the crude oil processing system.
• the inventor has tried to solve the above described industrial problem with known additives - glycolic acid (the mono basic hydroxyl acid) and malic acid (the dibasic hydroxyl acid), and maleic anhydride, D-gluconic acid, and found that when solution of calcium naphthenate in toluene was treated with equal weight of water containing the additive - glycolic acid or malic acid or maleic anhydride, or or D- gluconic acid, the efficiency of these acids to remove calcium from the crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil (of the wash water for desalter) increases to about 6 or to about 9 or to about 11.
• the mechanism of reduced efficiency of glycolic acid, malic acid, maleic anhydride, and D-gluconic acid to remove calcium from crude oil containing calcium naphthenate particularly of further reduced efficiency of glycolic acid, malic acid, maleic anhydride, and D-gluconic acid to remove calcium from crude oil containing calcium naphthenate under basic or alkaline conditions of wash water for desalter and at pH varying from about 5 to about 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 could not be visualized at present.
• the problem to remove calcium from crude oil or its blends containing calcium naohthenate under basic or alkaline conditions of the wash water of desalter still remains unresolved.
• the main object of the present invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends containing calcium naphthenate not only at low pH but also at high pH of the wash water for the desalter used in the crude oil processing system.
• the main object of the present invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends containing calcium naphthenate under basic or alkaline conditions of wash water for desalter and at a pH varying from about 5 to about 11.
• the object of the present invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends containing calcium naphthenate under basic or alkaline conditions of wash water for desalter, which may be due to presence of a compound selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds and at a pH varying from about 5 to about 1 1, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11.
• the inventor of present invention has fdund that when glyoxylic acid is employed as an additive in processing of crude oils or its blends containing calcium naphthenate in presence of water, it not only removes the calcium from the crude oil or its blends at low pH, but, surprisingly and effectively, it also removes calcium from the crude oil or its blends at high pH of about 6 to about 11, particularly of pH of about 7 to about 11, more particularly of pH of about 9 to about 11 of the wash water for the desalter used in the crude oil processing system, and that's too without causing any problem.
• the present invention relates to an additive for removing calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH, wherein the additive is glyoxylic acid.
• the present invention relates to a method for removing calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH, wherein the additive added to crude oil or its blend or the wash water for the desalter is glyoxylic acid.
• the present invention relates to use of glyoxylic acid for removal of calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH.
• the glyoxylic acid may be added to or mixed with crude oil or its blend or the wash water for the desalter.
• the inventor has particularly found that even with very little to nil sulfur contents, the efficiency of additives known in the prior art to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases upto about 7 or upto about 9 or upto about 11 due to basic or alkaline conditions, which may be due to the presence of a compound selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter.
• the inventor of present invention has found that when glyoxylic acid is employed as an additive in processing of crude oils or its blends containing calcium naphthenate in presence of water and under basic or alkaline conditions, which may be due to the presence of a compound selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter, it, surprisingly and unexpectedly, removes the calcium from the crude oil or its blends even if the pH of the crude oil processing mixture has increased upto about 7 or upto about 9 or upto about 11 under basic or alkaline conditions, which may be due to the presence of ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter, and that's too without causing any problem.
• the present invention relates to an additive for removing calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11, wherein the additive is glyoxylic acid.
• the basic or alkaline conditions of crude processing system are due to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
• the pH varies from about 6 to about 11.
• the pH more particularly varies from about 7 to about 11.
• the pH even more particularly varies from about 9 to about 11.
• the pH referred is of wash water for desalter used in the crude oil processing system.
• the present invention also relates to a method for removing calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11, wherein the additive added to crude oil or its blend or wash water for the desalter is glyoxylic acid.
• the basic or alkaline conditions of crude processing system are due to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
• the pH varies from about 6 to about 11.
• the pH more particularly varies from about 7 to about 11.
• the pH even more particularly varies from about 9 to about 11.
• the pH referred is of wash water for desalter used in the crude oil processmg system.
• the additive is added in the crude oil phase or wash water for the desalter.
• the present invention also relates to use of glyoxylic acid for removal of calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11.
• the basic or alkaline conditions of crude processing system are due to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
• the pH varies from about 6 to about 11.
• the pH more particularly varies from about 7 to about 11.
• the pH even more particularly varies from about 9 to about 11.
• the pH referred is of wash water for desalter used in the crude oil processing system.
• the additive is added in the crude oil phase or wash water for the desalter.
• the glyoxylic acid is identifiable by cas no. 298-12-4.
• the glyoxylic acid is taken in an amount varying from about 1:1 to 1:3 mole ratio of calcium to glyoxylic acid. In accordance with one of the preferred embodiments of the present invention, the glyoxylic acid is taken in an amount varying from about about 1 to about 2000 ppm in the crude oil or its blends or wash water for desalter.
• the inventor has found that even small amount of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds varying upto about 500 ppm inactivates other acids, but, surprisingly and unexpectedly, does not in-activate (deactivate) effects of glyoxylic acid (present additive).
• the present invention is more particularly applicable under following conditions:- a) basic or alkaline conditions of wash water;
• wash water which is preferably 6 or more, more preferably 9 or more;
• pH of mixture in desalter which is 6 or more, preferably between about
• wash water or desalter system which may vary from about 6 to about 11 due to basic or alkaline conditions.
• basic or alkaline conditions may be achieved by one or more of the compounds selected from a group comprising ammonia, ammonium hydroxide, nitrogen compounds, amine compounds, basic compounds and alkaline compounds.
• treatment of crude oil or wash water for removal of calcium can be carried out by any known method.
• the treatment is carried out as described in the following examples a reference to which is drawn herein for the purpose of describing and claiming the method for removal of calcium from the crude oil containing calcium naphthenate under basic or alkaline conditions.
• the treatment for the purpose of describing and claiming the method for removal of calcium from the crude oil containing calcium naphthenate is carried out by heating the reacting mixture to about 130°C.
• the solution of Ca-Napthenate was prepared in toluene followed by addition of selected additive and ultra pure water [demineralized (DM) water] without pH adjustment (for present additive, and prior art additives - glycolic acid, malic acid) and with pH adjustment (for present additive, and prior art additives - glycolic acid, malic acid, maleic anhydride, and D-gluconic acid).
• the individual resulted solutions were heated to 130°C for 10, 20 and 30 mins followed by cooling to room temperature.
• the individual resulted reacted solution was poured into a separating funnel and shaken. The two separated layers were formed with top layer being the hydro carbonaceous layer and the bottom layer being the aqueous layer.
• the top layer was analyzed for Ca content using Inductive Coupled Plasma [ICP], and the dried sample from top layer was also analyzed for its Acid Value.
• ICP Inductive Coupled Plasma
• pH of water used for extraction after adding selected additive without pH adjustment was found to be as follows:- pH of Glyoxylic Acid was found to be 2.17;
• pH of Malic Acid was found to be 2.3.
• the Acid Value of the dried sample obtained from the top layer after treatment with additive of present invention is higher than that of the dried samples obtained from the top layers after treatment with additives of prior art.
• the mixture was then poured into the EDDA tubes (Electro static Desalting Dehydration Apparatus, supplied by Inter AV, USA) to just about 100 ml mark, and a calcium removing agent - glycolic acid and dl malic acid (prior art additives), glyoxylic acid (present invention additive), demulsifier (about 30 ppm) were was added individually in a tube. With every test, a blank test without the calcium removing agent was conducted for comparison purposes. The tubes with respective calcium removing agent were placed in the EDDA heating block at the desired test temperature of 130° C. The tubes were then capped with electrode caps and placed in the heating block for approximately ten minutes.
• EDDA tubes Electro static Desalting Dehydration Apparatus, supplied by Inter AV, USA
• the tubes were shaken for 2 minutes and placed back in the heating block to reheat for ten minutes.
• the electrode cover was then placed over the tubes and locked into place.
• the 3000 volts voltage was applied for eight minutes.
• the tubes were taken out for measuring the amount of water, which is the percent water drop.
• the calcium content of the crude phase was measured after 10 minutes using ICP (Inductive coupled plasma) in each tube, and results are given in Table V.
• the calcium content of the crude phase of the blank run was 274 ppm.
• glyoxylic acid of present invention is far better additive than prior art additives for calcium removing even at high pH of about 10.4 and under alkaline conditions, as can be seen from the calcium content of the top layer, which is surprisingly and unexpectedly, as low as 5 ppm as compared to 51 ppm and 45 ppm for glycolic and malic acid respectively. Therefore, it can also be concluded from Table V that Glyoxylic acid removes calcium from the crude phase at much faster rate and more effectively than prior art additives at high pH and under alkaline conditions.
• glyoxylic acid of present invention is far better additive than prior art additives, as the calcium removing efficiency of glyoxylic acid, surprisingly and unexpectedly, even at pH of 6 and under alkaline conditions, after 10 minutes of treatment, is about 67.9% as compared to 46% and 44.1% for glycolic and malic acid respectively [re Table - VI];
• glyoxylic acid is, surprisingly and unexpectedly, useful for removal of calcium from crude oil or its blends containing the calcium naphthernate even in presence of ammonia or other alkaline or basic compounds at a pH varying from about 5 to about 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 with ease and economically, and therefore, the present invention provides a solution to long awaited industrial problems in processing mixture of crude oils or its blends containing calcium naphthenate under alkaline or basic conditions.

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