Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
  • B01D17/02—Separation of non-miscible liquids
  • B01D17/04—Breaking emulsions
  • B01D17/047—Breaking emulsions with separation aids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
  • B01D17/02—Separation of non-miscible liquids
  • B01D17/04—Breaking emulsions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/28—Chemically modified polycondensates
  • C08G8/36—Chemically modified polycondensates by etherifying
• • 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
  • C10G33/00—Dewatering or demulsification of hydrocarbon oils
  • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
• • 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

• Demulsification Additive composition and method of use thereof, and method of demulsification.
• the present invention relates to demulsification additive composition for demulsification of water-in-oil emulsion.
• the present invention relates to demulsification additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil, more particularly caused by mixing of wash water and crude oil in the desalter unit of the refinery.
• the present invention relates to demulsification additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the demulsification additive composition comprises at least a combination of:
• (c) further comprises phosphoric acid.
• the present invention relates to a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery by employing the demulsification additive composition of the present invention.
• the present invention relates to a method of using the demulsification additive composition of the present invention for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
• the water-in-oil emulsions are formed in various industrial operations, and are responsible for substantial loss of various industrial ingredients including difficulties in separation of oil. Therefore, breaking of water-in-oil emulsions during the processing of oil is the requirement of the industry, particularly of the crude oil refinery industry wherein the wash water gets mixed with crude oil in the desalter unit of the refinery and forms water-in-oil emulsion.
• the water-in-oil emulsion caused by mixing of wash water and crude oil is broken by addition of demulsifier to the wash water.
• the main problem of using the demulsifiers is that these are to be used in higher amounts and required continuously through the processing of crude oil, which results in substantial increase in cost of processing of crude oil.
• demulsifiers are expensive, which also results in substantial increase in cost of processing of crude oil.
• demulsifiers are condensation product of nonyl phenols, and presently, there is a need to reduce consumption of nonyl phenols in view of their cost and environmental adverse effects.
• the present invention aims at providing a solution to above-described existing industrial problems by providing:
• the main object of the present invention is to provide:
• a demulsification additive composition for demulsification of water-in-oil emulsions particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.
• the other object of the present invention is to provide: ii) a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery by employing the demulsification additive composition of the present invention.
• Another object of the present invention is to provide:
• an object of the present invention is to provide a demulsification additive composition for demulsification of water-in-oil emulsions, which is preferably caused by mixing of wash water and crude oil, more preferably for demulsification of the water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery so as to reduce the amount of the presently used demulsifiers, which are condensation product of nonyl phenols, and hence, to reduce consumption of nonyl phenols or condensation product of nonyl phenols, and thereby to reduce cost of processing and associated environmental adverse effects.
• composition comprising:
• component (a) one or more demulsifiers (may be referred to as component (a)); and (b) a compound selected from the group comprising glyoxal, neutralized glyoxal, glyoxal derivative and a mixture thereof (may be referred to as component (b)), and
• component (c) further comprising phosphoric acid (may be referred to as component (c)), surprisingly and unexpectedly, substantially improves demulsification efficiency of the demulsifier (the component (a)), and thereby, results in substantial reduction of requirement of amount of the demulsifier, which results in substantial decrease in cost of processing of crude oil, and associated environmental adverse effects.
• composition of the present invention comprising a combination of the component (a), the component (b), and the component (c), surprisingly and unexpectedly, also substantially improves demulsification efficiency:
• composition consisting of a combination of the component (a) and the component (b), and
• composition consisting of a combination of the component (a) and the component (c).
• glyoxal and neutralized glyoxal are less expensive than the demulsifiers, it further results in substantial decrease in cost of processing of the crude oil.
• the present invention relates to a demulsification additive composition for demulsification of water-in-oil emulsion caused due to wash water in the crude oil, wherein the composition comprises:
• (b) a compound selected from the group comprising glyoxal, glyoxal derivative, neutralized glyoxal, and a mixture thereof (the component (b)), and
• (c) further comprises phosphoric acid (the component (c)).
• composition comprising a combination of the component (a) and the component (b), or comprising a combination of the component (a) and the component (b), and the component (c), wherein
• the component (b) comprises one or more of the following:
• the component (c) comprises phosphoric acid
• the present composition does not comprise one or more of the following: Glycolic acid;
• the neutralized glyoxal is glyoxal having pH neutral to basic.
• the inventor has observed that the glyoxal is very acidic, and therefore, it may cause corrosion. Accordingly, neutralizing the glyoxal till its pH is neutral to basic avoids corrosion of crude oil processing unit, and still improves demulsification efficiency of the demulsifier.
• the neutralized glyoxal is obtained by neutralizing the glyoxal with an amine or alkaline medium.
• the amine may include (or comprises) triethanol amine (TEA).
• TAA triethanol amine
• the alkaline medium may include (or comprises) sodium hydroxide aqueous solution.
• the neutralized glyoxal may also include (or comprise) neutralized derivative of glyoxal. Therefore, in the present invention, the term “neutralized glyoxal” or the term “neutralized derivative of glyoxal” have one and same meaning unless otherwise explicitly described.
• the pH neutral to basic includes a pH varying from about 7 to about 12.
• the glyoxal derivative may comprise (or include) methanol, ethanol, butanol, or ethylene glycol derivative of glyoxal, or a mixture thereof.
• the demulsifier is selected from the group comprising oxyalkylated condensation product of:
• the demulsifier is selected from the group comprising oxyalkylated condensation product of: i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;
• the demulsifier is selected from the group comprising:
• the demulsifier may be selected from a group comprising:
• the oxyalkylated product is an ethylene oxide derivative, propylene oxide derivative, butylene oxide derivative or a mixture thereof.
• the oxyalkylated product is an oxyalkylated copolymer or an oxyalkylated polymer or an oxyalkylated resin.
• the oxyalkylated product is a base catalyzed oxyalkylated copolymer or a base catalyzed oxyalkylated polymer or a base catalyzed oxyalkylated resin of one or more of the said phenolic compound (i.e. cardanol, nonyl phenol, butyl phenol, amyl phenol, alkyl phenol) and formaldehyde.
• the said phenolic compound i.e. cardanol, nonyl phenol, butyl phenol, amyl phenol, alkyl phenol
• the oxyalkylated product is the oxyalkylated phenol formaldehyde resin, oxyalkylated phenol formaldehyde polymer, or oxyalkylated phenol formaldehyde copolymer.
• the phenolic reactants includes alkyl phenols comprising alkyl group.
• the alkyl group comprises from about 1 to about 20 carbon atoms.
• the substitution may be of butyl, amyl, nonyl, hexyl, octyl, isooctyl, decyl, or dodecyl group.
• copolymer means a polymer made from two different phenols and the term “polymer” means a polymer made from one phenol, and resin is intended to include the polymers and copolymers.
• the reaction of alkyl phenol formaldehyde resin with alkylene oxide forms a high molecular weight oxyalkylated alkyl phenol formaldehyde resin.
• the alkylene oxide comprises ethylene oxide, propylene oxide, butylene oxide or a mixture thereof, preferably the alkylene oxide comprises ethylene oxide, propylene oxide, or a mixture thereof.
• the molecular weight of the demulsifier of the present invention may vary from about 1000 to about 20000 daltons, preferably from about 2000 to about 15000 daltons, more preferably from about 2000 to about 10000 daltons as measured by Gel Permeation Chromatography (GPC) using the tetrahydro furan (THF) as solvent.
• GPC Gel Permeation Chromatography
• the average molecular weight of the demulsifier of the present invention may vary from about 1000 to about 20000 daltons, preferably from about 2000 to about 15000 daltons, more preferably from about 2000 to about 10000 daltons as measured by Gel Permeation Chromatography (GPC) using the tetrahydro furan (THF) as solvent.
• GPC Gel Permeation Chromatography
• the composition comprises: a) the component (a) in an amount varying from about 99.1 % to about 0.1 % by weight of the total composition;
• the component (b) in an amount varying from about 0.1 % to about 99.1 % by weight of the total composition
• the additive composition may be added to the crude oil phase or to the desalter wherein wash water is mixed with crude oil and forms a water-in-oil emulsion.
• scope of the present invention is not limited by the crude oil or the wash water.
• the present invention relates to a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions formed by mixing of wash water and crude oil, more particularly of water-in-oil emulsions formed by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the water-in-oil emulsion formed due to mixing of wash water in the crude oil is treated with the presently provided demulsification additive composition.
• the present invention also relates to a method of using the presently provided demulsification additive composition for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions formed by mixing of wash water and crude oil, more particularly of water-in-oil emulsions formed by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the presently provided demulsification additive composition is added to the water-in-oil emulsion formed due to mixing of wash water in the crude oil.
• the scope of the present invention is not limited by amount of the additive composition of the present invention, which has to be added in an amount sufficient for demulsification of the water-in-oil emulsions.
• Component (a) is demulsifier, which is 50% active nonylphenol formaldehyde ethoxylate resin (or may be a base catalysed nonylphenol formaldehyde resin);
• Component (b) of the present invention is glyoxal or neutralized glyoxal, wherein the glyoxal has been neutralized with triethanol amine (TEA);
• Component (c) of the present invention is phosphoric acid
• Comparative component may be selected from glycolic acid, glyoxylic Acid, citric acid, and maleic anhydride. In the following experiments these have been identified as follows and are taken in 14% by weight of DM (demineralized water):
• Comparative component (bl) is glycolic acid (40%);
• Comparative component (b2) is glyoxylic acid (40%);
• Comparative component (b3) is citric acid (40%);
• Comparative component (b4) is maleic anhydride (40%).
• Comparative compositions do not comprise the combination of the component (b) and the component (c) of the present invention.
• the 'blank' is without any additive.
• Table - 1
• dosage ' 10+3' indicates that the additive comprises 10 ppm of Component (a) and 3 ppm of Comparative component (bl), and so on.
• the 'Present Composition' comprises 10 ppm of Component (a) and 3 ppm of [Component (b) + Component (c)], wherein the [Component (b) + Component (c)] comprises the Component (b) which is glyoxal (40%) and the Component (c) which is H 3 P0 4 (85%) in DM (demineralized water) water in a weight ratio of 14/0.43/85.57.
• composition of the present invention demonstrates 84% efficiency as against 56% or 74% efficiency of the comparative compositions.
• Table - II
• dosage ' 10+3 ' indicates that the additive comprise 10 ppm of Component (a) and 3 ppm of second component, i.e. Comparative component (bl), Comparative composition (B), Comparative component (b2), Comparative composition (C), Comparative component (b3), Comparative composition (D), Comparative component (b4), Comparative composition (E).
• Component (a) is 50% active nonyl phenol formaldhyde ethoxylate resin (oxyalkylated condensation product);
• Component (b) comprises glyoxal (40%) in 14% DM water;
• Component (c) comprises H 3 P0 4 (85%) in 0.43% of DM water;
• Present Composition comprises in-addition to the Component (a), the Component (b) which is glyoxal (40%) and the Component (c) which is H 3 P0 4 (85%) in DM water in a weight ratio of 14/0.43/85.57;
• Comparative component (bl) is glycolic acid (40%) in 14% DM water;
• Comparative composition (B) comprises Comparative component (bl) which is glycolic acid (40%) and the component (c) which is H 3 P0 4 (85%) in DM water in a weight ratio of 14/0.43/85.57;
• Comparative component (b2) is glyoxylic acid (40%) in 14% by weight of DM water;
• Comparative composition (C) comprises Comparative component (b2) which is Glyoxylic acid (40%) and component (c) which is H 3 P0 4 (85%) in DM water in a weight ratio of 14/0.43/85.57;
• Comparative component (b3) is citric acid (40%) in 14% by weight of DM water
• Comparative composition (D) comprises Comparative component (b3) which is Citric acid (40%) and component (c) which is H 3 P0 4 (85%) in DM water in a weight ratio of 14/0.43/85.57;
• Comparative component (b4) is maleic anhydride (40%) in 14% by weight of DM water;
• Comparative composition (E) comprises Comparative component (b4) which is maleic anhydride (40%) and component (c) which is H 3 P0 4 (85%) in DM water in a weight ratio of 14/0.43/85.57.
• the mixing time was 2 min and mixing temperature was 55 C
• the component (b) is 0.9 ppm of glyoxal (40%) in DM water
• the 0.9 ppm of component (c) comprises 0.87 ppm of glyoxal (40%) and 0.03 ppm of H 3 P0 4 (85%) in DM [i.e. 97% by weight of glyoxal (40%) and 3% by weight of H3P04 (85%) in DM]
• the component (a) is 50% active ethoxylated nonyl phenol cardanol formaldehyde resin, which is ethoxylated condensation product of 90% by weight of nonyl phenol and 10% by weight of cardanol.
• composition of the present invention demonstrates 90% efficiency as against 56% or 74% efficiency of the comparative compositions.
• the mixing time was again 2 min and mixing temperature was again 55°C
• the component (b) is 0.9 ppm of glyoxal (40%) in DM water
• the 0.9 ppm of component (c) comprises 0.846 ppm of glyoxal (40%) and 0.054 ppm of H 3 P0 4 (85%) in DM [i.e.
• component (a) is 50% active ethoxylated nonyl phenol para tertiary amyl phenol formaldehyde resin, which is ethoxylated condensation product of 50% by weight of nonyl phenol and 50% by weight of para tertiary amyl phenol.
• composition of the present invention demonstrates 84% efficiency as against 60% or 74% efficiency of the comparative compositions.
• the mixing time was again 2 min and mixing temperature was again 55°C
• the component (b) is 1.2 ppm of glyoxal (40%) in DM water
• the 1.2 ppm of component (c) comprises 1.164 ppm of glyoxal (40%) and 0.036 ppm of H 3 P0 4 (85%) in DM [i.e.
• component (a) is 50% active ethoxylated nonyl phenol para tertiary butyl phenol formaldehyde resin, which is ethoxylated condensation product of 90% by weight of nonyl phenol and 10% by weight of para tertiary butyl phenol.
• composition of the present invention demonstrates 84% efficiency as against 56% or 74% efficiency of the comparative compositions.
• the present additive composition and the prior art or comparative additive composition was added to the water-in-oil emulsion of water and crude oil formed after mixing of water and crude oil.

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• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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