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
• • 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

Definitions

• the present invention relates to methods and compositions for separating emulsions of hydrocarbons and water, and more particularly relates, in one embodiment, to methods and compositions for transferring metal-containing components to an aqueous phase in an emulsion breaking process
• Desalting is the resolution of the natural emulsion of water which accompanies the crude oil by creating another emulsion in which about 5 percent relative wash water is dispersed into the oil using a mix valve.
• the emulsion mix is directed into a desalter vessel containing a parallel series of electrically charged plates. Under this arrangement, the oil and water emulsion is exposed to the applied electrical field. An induced dipole is formed on each water droplet within the emulsion which causes electrostatic attraction and coalescence of the water droplets into larger and larger droplets.
• the emulsion resolves into two separate phases — the oil phase (top layer) and the water phase (bottom layer).
• the streams of desalted crude oil and effluent water are separately discharged from the desalter.
• the entire desalting process is a continuous flow procedure as opposed to a batch process.
• chemical additives are injected before the mix valve to help resolve the oil/water emulsion in addition to the electrostatic coalescence. These additives effectively allow small water droplets to more easily coalesce by lowering the oil/water interfacial tension.
• Crude oil which contains a high percent of paniculate solids can complicate the desalting process.
• the particulate solids by nature, would prefer to transfer to the water phase.
• oil-wetted solids in high concentration in the crude may help form tight oil and water emulsions which are difficult to resolve.
• These tight emulsions are often referred to as "rag" and may exist as a layer between the separated oil and water phases.
• the rag layer inside the desalter vessel may grow to such an extent that some of it will be inadvertently discharged with the water phase. This is a problem for the waste water treatment plant since the rag layer still contains a high percentage of unresolved emulsified oil.
• iron As mentioned, much of the solids encountered during crude oil desalting consists of iron, most commonly as particulate iron such as iron oxide, iron sulfide, etc. Some of the metals, including iron, may be present in a soluble form. The metals may be present in inorganic or organic forms. In addition to complicating the desalter operation, iron and other metals are of particular concern to further downstream processing. This includes the coking operation since iron and other metals remaining in the processed hydrocarbon yields a lower grade of coke. Removing the metals from the crude oil early in the hydrocarbon processing stages is desired to eventually yield high quality coke as well as to limit corrosion and fouling processing problems.
• Yet another object of the invention is to provide a method and composition to transfer metal-containing components out of a hydrocarbon phase without the use of nonyl phenol resins.
• a method of transferring metal-containing components from a hydrocarbon phase to a water phase by adding to an emulsion of hydrocarbon and water an effective amount of a composition.
• the composition includes at least two of the following components: a diepoxide polymer; a polyol; and an acid selected from the group of sulfonic acids and carboxylic acids
• An aromatic solvent may also be present
• the blend includes high molecular weight polyglycol and polymerized polyols from diepoxide, additionally with the presence of a small amount of an aromatic sulfonic acid
• the blend contains at least two of these three components a diepoxide polymer, a polyol, and an acid
• the acid may be a sulfonic acid and/or a carboxylic acid
• composition and method of the invention will be valuable to produce high quality (i.e., high purity) coke from crude which may originally contain high concentrations of metals and solids, in particular, iron-based solids Further, the invention advances the technology by removing inorganic material, such as iron, from the crude oil without discharging any oil or emulsion to the waste treatment plant
• metal-containing component includes, but is not necessarily limited to, inorganic species, such as elemental metal, metal oxides, e.g. iron oxides, but also organic metal-containing species, such as iron porphyrin, naphthenate salts of iron, and any other metal- containing material, compound or chemical
• metal-containing components may be in particulate or solid form, or in solubilized form
• iron is often mentioned as the metal element removed by the compositions and methods of this invention, that the invention is not limited to iron removal, but is expected to be useful to remove other metals, such as nickel and vanadium, in a further non-limiting embodiment
• Nickel and vanadium are known poisons for catalysts used in fluid catalytic cracking units (FCCUs) downstream
• the composition of the invention is a blend of at least two of a diepoxide polymer, a polyol, and an acid
• the diepoxide polymer is one of the components
• the composition is a diepoxide polymer and a polyol, in the absence of a sulfonic acid and/or a carboxylic acid
• all three are employed
• the proportion of these three components may be diepoxide polymer in the range of from about 5 to about 99 8 wt %, a polyol in the range of from about 0 1 to about 75 wt %, and an aromatic sulfonic acid in the range of from about 0 1 to about 20 wt %
• the proportion of these three components may be diepoxide polymer in the range of from about 10 to about 85 wt %, a polyol in
• the composition has an absence of ammonium ion and/or an absence of an alkoxylated formaldehyde resin
• diepoxide polymer any diepoxide reaction product with a polyol It will be appreciated that the recitation of “a diepoxide polymer” includes the possibility of more than one diepoxide polymer
• the diepoxide polymer may have a molecular weight in the range from about 15,000 to about 30,000 It will be understood that all molecular weights expressed herein are number average molecular weights Preferably, the diepoxide polymer may have a molecular weight in the range from about 20,000 to about 25,000
• the diepoxide polymers are reaction products of polyols with glycidyl ethers from a compound containing at least one phenolic group
• suitable diepoxide polymer include, but are not necessarily limited to, reaction products of bisphenol-A diglycidyl ethers or copolymers of bisphenol-A and epichlorohydrin or Epon 828 with polyols, and the like
• the polyol include, but are not necessarily limited to, reaction products of bis
• the polyol may have a molecular weight in the range from about 10,000 to about 60,000 Preferably, the polyol may have a molecular weight in the range from about 11,000 to about 28,000 It will be appreciated that the recitation of "a polyol" includes the possibility of more than one polyol Specific, non-limiting examples of suitable polyols include, but are not necessarily limited to, those polyols discussed above with respect to the diepoxide polymers
• an acid includes the possibility of more than one sulfonic and/or carboxylic acid
• suitable diepoxide polymers include, but are not necessarily limited to, dodecyl benzene sulfonic acid (DDBSA), naphthalene sulfonic acid, dialkylbenzene sulfonic acid, isopropyl sulfonic acid (IPSA), alkylsulfonic acids such as decanesulfonic acid, carboxylic acids such as citric acid and erythorbic acid (rf-erythro-ascorbic acid, isoascorbic acid), and the like
• DBSA dodecyl benzene sulfonic acid
• IPSA isopropyl sulfonic acid
• alkylsulfonic acids such as decanesulfonic acid
• carboxylic acids such as citric acid and erythorbic acid (rf-erythro-ascorbic acid, isoascorbic acid)
• the additive blend of this invention is injected into the flowing crude oil before the mix valve in neat form or diluted in a suitable aromatic solvent at a rate to provide effective oil/water separation
• suitable aromatic solvents include, but are not necessarily limited to, heavy aromatic solvent, ethyl benzene, xylene, toluene, heavy aromatic naphthalene such as Panasol AN-3N, FAS 150, EXXON 150, and the like
• the amount of solvent used may range from about 10 to about 95 wt %, based on the total blend with the other three components, preferably from about 20 to about 10 wt %
• the concentration of the additive blend composition of this invention to be used in the crude oil to be effective is very difficult to predict in advance since it depends on multiple, interrelated factors including, but not limited to, the composition of the crude, the desalting conditions (temperature, pressure, etc ), the flow rate of the crude and its residence time in the desalter, among others Nevertheless, for the purposes of non-limiting illustration, the proportion of the active blend that may be used in the crude (not including any aromatic solvent) may range from 1 to 500 ppm- w A preferable concentration will range from 10 to 100 ppm-w
• metal-containing components transfer to the aqueous phase
• 25% or less metal-containing component is present in the hydrocarbon phase after desalting, preferably 20% or less metal- containing component remains, most preferably only 10% or less remains
• Electrostatic Desalting Dehydration Apparatus (EDDA) Test Method was employed to screen possible blend compositions
• the EDDA is a laboratory test device to simulate the desalting process
• EDDA Test Method Add 800, 600 or 400 ml of crude oil to be tested minus the percent of wash water (depending on the number of tubes the EDDA will hold) to a Waring blender Add the required percentage of wash water to the blender to bring the total volume up to 800, 600 or 400 ml Mix at 50% speed (on the Nariac) for 30 seconds The speed can be reduced if the DP on the mix valve is low Pour the mixture into the EDDA tubes to just below the 100 ml line Place the tubes in the EDDA heating block that is at the desired test temperature (99°C) Add the desired quantity of demulsifier, in ppm, to each tube With every test, a blank must be run for comparison purposes Place the screw top electrode in the tubes and allow the samples to heat for approximately 15 minutes Tighten the caps and shake each tube 100-200 times and place back in the heating block to reheat for five minutes Place the electrode cover over the tubes and lock into place Make sure that there is good contact between the cover and the electrode caps Set the time for five minutes and run at 1500-3
• N(aq) volume of acidic acid solution in iron Chemetrics test, in ml
• V(o ⁇ i) volume of oil ashed, in ml
• Examples 1 through 29 demonstrate the amount of iron left in the oil phase after the EDDA test using the indicated components
• 5% wash water was used, except for the Examples of Tables V and NIII, where 3% wash water was used
• the test temperature was 98°C (208°F)
• Ten ml aliquots were removed at each indicated time interval

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2000
  • 2000-03-03 EP EP00913766A patent/EP1165723A1/de not_active Withdrawn
  • 2000-03-03 WO PCT/US2000/005845 patent/WO2000052114A1/en active Search and Examination
  • 2000-03-03 AU AU35146/00A patent/AU3514600A/en not_active Abandoned

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