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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
  • C10G1/045—Separation of insoluble materials
• • 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
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/003—Solvent de-asphalting
• • 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

Definitions

• This invention is concerned generally with the removal of suspended solids from an oil. More particularly it relates to a process for producing a solids-reduced hydrocarbon oil in which suspended solids in the oil are agglomerated by adding to the oil a mixture of solids-agglomerating agents comprising a demulsifying agent and a polymer and thereafter separating the agglomerated solids from the oil.
• Patents 4,085,031; 4,253,937; 4,048,054 and 4,045,328 produces a solvent-coal slurry containing insoluble particles.
• Other liquids from coal are produced in its conversion processes by, for example, in its gasification, coke preparation and other processes involving the pyrolysis of coal.
• These liquid hydrocarbon streams contain insoluble particles which are desirably removed or reduced in level to allow for their use as a fuel oil or as a feedstock for producing other products.
• liquid hydrocarbon streams oftentimes are routed to a settling tank wherein the solid particles (catalyst fines, coke, inorganic matter, are allowed to gravity settle over an extended period of time whereby an upper layer of substantially particle-free liquid hydrocarbons can be decanted off for product use. Settling of the particles may also be provided for in intermediate or shipping tanks. Unfortunately gravity settling is too slow for the refinery, coal conversion and chemical processes now in use.
• Electrofiltration was handicapped by lack of a regenerable filter media which is stated to have been overcome by the use of hard, smooth spherical glass beads as taught in U.S. Patents 3,799,855 and 3,799,856. Unfortunately these techniques are further limited since the typical oil-suspendible solids have average diameters of size below about 100 microns (commonly described in the art as difficultly filterable 'solids) which size makes satisfactory separation by mechanical separation techniques, including filtration, centrifugation and settling difficult to impossible.
• Gravity settling can also be enhanced by the presence of a surface-active agent as taught in U.S. 2,952,620 wherein solid particles of a silica-alumina cracking catalyst suspended in a'heavy gas oil was separated from the oil by treating the suspension with an aqueous solution of a nonionic surface-active agent, e.g., a condensation product of diisobutyl phenol and 9-10 moles of-ethylene oxide.
• a nonionic surface-active agent e.g., a condensation product of diisobutyl phenol and 9-10 moles of-ethylene oxide.
• Gravity settling can be induced by use of a settling vessel in which the hydrocarbon oil containing the solids is subjected to a temperature gradient (see U.S. 4,048,063).
• Japanese Published Patent Application 53-34806 of 1978 regenerates used, iron-contaminated lubricating oil by the addition of water-soluble polymers as water-in-oil emulsions to coagulate the iron whereby it becomes suitable for mechanical removal.
• the residual hydrocarbon oils from petroleum and coal conversion processes can be readily reduced in solids, preferably inorganic solids, content to an oil having less than 500 weight parts per million (WPPM) of filterable solids when admixed with from 25 to 1000, preferably 50 to 250 ppm of a mixture of an ethoxylated-propoxylated C 4-C9 alkyl phenol formaldehyde resin glycol ester of 2,000 to 15,000 weight average of molecular weight (Mw) and a water-soluble polyelectrolyte of 1,000 to 25,000,000 M w at a temperature of from 35 to 210°C and allowed to gravity settle for from 0.3 to 10 days.
• WPPM weight parts per million
• the demulsifier agglomeration aid is preferably of the class of oxyalkylated phenol formaldehyde resin glycol esters of Rw ranging from 500 to 50,000, preferably 2,000 to 15,000, optimally 5,000 to 8,000.
• the optimal is the reaction product of a phenol formaldehyde resin and propylene oxide which product is then reacted with ethylene oxide and finally esterified as by reaction with maleic anhydride or succinic anhydride, which collectively is designated herein as a succinate.
• the water-soluble polyelectrolytes are macromolecular and generally of 1,000 to 25 million, preferably 10,000 to 15 million, in molecular weight and preferably of a combined water-polyelectrolyte aggregate size of 0.5 to 50 microns such as would be exhibited by water-in-oil emulsions of water-soluble vinyl addition polymers of Mw ranging from 10,000 to 25 million.
• These polyelectrolytes include the cationic, nonionic and anionic types.
• the liquid hydrocarbon feedstock is subjected to the processing conditions of elevated temperature and sometimes elevated pressure to accomplish the desired cracking.
• the resultant effluent of the reactor is then fractionated into the desired fractions of gases, light liquid hydrocarbons and heavy liquid hydrocarbons, with the heaviest and highest boiling fraction being the steam cracker tar or from a catalytic cracker which contain the insoluble particles.
• the coal liquefication process involves contacting particulate coal with a hydrogen (e.g., a hydrogen donor solvent) under liquefication conditions producing a hydrocarbon stream containing insoluble particles.
• the hydrocarbvon stream can be fractionated to produce gases, light liquid hydrocarbons and heavy liquid hydrocarbons with the heaviest fraction being the bottoms containing the particles.
• Other liquids from coal are produced by coal conversion process utilizing the pyrolysis of coal.
• this invention broadly treats any liquid hydrocarbon stream containing insoluble' solids or particles, particularly fine inorganic solids and liquid hydrocarbons to remove or substantially reduce the solids content of the hydrocarbon oil and is_ particularly applicable to oils containing finely divided suspended solids.
• Finely divided oil-suspended solids are effectively removed from the oil by the process of the invention.
• Those common properties which engender oil suspendability of these particles for example, particle size, density, charge and the like, are also believed to render them susceptible to effective agglomeration and removal by the present process.
• Representatie solids include mineral ash-forming impurities, coal coke, carbonaceous solids, catalyst and spent shale fines, natural and synthetic mineral oxides, organic and inorganic salts and mixtures thereof and the like in particulate form and for the unfilterable solids sized in the average diameter range below about 100 microns, especially below about 60 microns.
• Representative suspended-solids-containing oils suitable for use herein include shale oil, coal liquefaction oils as from extraction, hydrogenation, thermal treatment and combinations thereof, coal tars from coke manufacture, tar sand oils, petroleum refinery decant oils, oils from a fluid catalytic cracking process unit, resids, and like oils with all having less than about 10 weight percent of water.
• hydrocarbon oils are most effectively treated by the invention when the fraction treated boils in the range of 200°C to 550°C and has a total insoluble solids content greater than about 1,000 WPPM, e.g., from 1,000 to 50,000 WPPM more, normally an insoluble solids content in the range of 2,000 to 10,000 WPPM.
• a prime feature of the present process is the discovery of a unique solids-agglomerating agent which is enhanced in function in a hydrocarbon oil system by the presence of a water-soluble macromolecular polyelectrolyte.
• a solids-agglomerating additive to be useful and effective in this service, must promote essentially complete removal of solids from an oil and at the same time must leave the oil virtually intact.
• known solvents employed for recovering solids from an oil do not meet the latter requirement. The failure of these solvents is manifest in their inability to effectively solubilize both paraffinic-type hydrocarbons and asphaltene-type hydrocarbons.
• the most difficultly filterable solids are the inorganic particles for which the solvent approach is of no value.
• an appreciable portion of the oil is usually rejected (a loss to the process of desirable product precursors) in the form of tacky or flocculent solids.
• Preferred for use as a demulsifier agglomeration aid is an ethoxylated propoxylated C 4 -C 9 alkyl phenol formaldehyde resin ester of a C 4 -C 10 dicarboxylic acid anhydride, e.g., maleic or succinic anhydride, admixed with an equal weight amount of a Mannich amine polyelectrolyte such as a condensation product of polyacrylamide, formaldehyde and dimethylamine.
• a Mannich amine polyelectrolyte such as a condensation product of polyacrylamide, formaldehyde and dimethylamine.
• demulsifiers useful in the process of this invention include both water and_oil soluble products. They are well known in the art, and include, for example, oxyalkylated amines, alkylaryl sulfonic acid and salts thereof, oxyalkylated phenolic resins, polymeric amines, glycol resin esters, polyoxyalkylated glycol esters, fatty acid esters, oxyalkylated polyols, low molecular weight oxyalkylated resins, bisphenol glycol ethers and esters and polyoxyalkylene glycols. This enumeration is, of course, not exhaustive and other demulsifying agents or mixtures thereof will occur to one skilled in the art. Most demulsifiers which are commercially available' fall into chemical classifications such as those enumerated above in which the Mw generally ranges from 500 to 50,000.
• glycol resin esters are derived from alkyl phenol formaldehyde resins having molecular weights of 500 to 50,000 which are alkoxylated and thereafter esterified by reaction with an ethyleneically unsaturated dicarboxylic acid or anhydride such as maleic anhydride.
• Such glycol resin esters are typified by an oxyalkylated C 4- C 9 alkyl phenol formaldehyde glycol resin esters having a Mw within the range of 500 to 50,000, preferably 2,000 to 15,000.
• the bisphenol glycol ethers and esters are obtained by the alkoxylation of bisphenol A to molecular weights of from 3,000 to 5,000 and for the esters the ether products are esterified by feaction with organic acids such as adipic, acetic, oxalic, benzoic, and succinic including maleic anhydride.
• the salts of alkyl aryl sulfonic acids include those of ammonium, sodium, calcium, and lithium.
• the useful alkyl aryl sulfonic acids can be obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum by distillation and/or extraction or by the alkylation of aromatic hydrocarbons as, for example, those obtained by alkylating benzene; toluene, xylene, naphthalene, diphenyl and the halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
• the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to about 15, preferably 9-12, carbon atoms.
• Preferred sulfonic acids are those obtained by the sulfonation of hydrocarbons prepared by the alkylation of benzene or toluene.
• the alkaryl sulfonates contain from 7-21 carbon atoms, preferably from 15-18 carbon atoms per alkyl substituted aromatic moiety.
• Oxyalkylated amines are represented by the ethylene oxide, propylene oxide and mixtures of ethylene/butylene oxides derivatives of organic amines such as ethylene diamine, ethyl amine, propyl amine, aniline and alkylene polyamines.
• Polyelectrolytes as used herein refer to a polymer water-soluble or water-dispersible which contains polyions.
• the polyelectrolytes have molecular weights ranging from 1,000 to 25 million with those having (Mw)'s in excess of 0.5 million preferred.
• the polyelectrolyte may be either cationic or anionic and, in some instances, the ionic charges are sufficiently slight so that the polymers may be considered as nonionic.
• water-soluble polymers and copolymers of allyl, dially amines, 'or dimethylaminoethylmethacrylate are cationic.
• Polymers such as polyvinyl alcohol are .nonionic, and polymers such as polyacrylic acid or polystyrene sulfonates are anionic. All of these polymers are considered useful polyelectrolytes and may be used in the practice of the invention.
• the molecular weight of the polyelectrolytes described above may vary over a wide range, e.g., 1,000-25,000,000, although it is preferred to use nitrogen containing (such as acrylamide) polymers whose molecular weights are in excess of 1,000,000.
• nitrogen containing (such as acrylamide) polymers whose molecular weights are in excess of 1,000,000.
• These polyelectrolytes are well known and generally available as articles of commerce.
• those polyelectrolytes which have utility in combination with the water-soluble demulsifying agents such as the alkoxylated esters according to the process of this invention include:
• One class of preferred polyelectrolytes are the water-soluble vinyl addition polymers which are well known in the art, widely described in the literature, and generally commercially available as water-in-oil emulsions.
• the emulsion type polymers most commonly used in industrial applications are acrylamide polymers which include polyacrylamide and its water-soluble copolymeric derivatives such as, for instance, acrylamide-acrylic acid, and acrylamide-acrylic acid salt copolymers which contain from about 95-5% by weight of acrylamide.
• copolymers of acrylamide with other vinyl monomers such as maleic anhydride, acrylonitrile, styrene and the like.
• Other water-soluble vinyl polymers are described in detail in the following U.S.
• These polymers may be produced by any known method of conducting polymerization reactions. Thus, solution, suspension or emulsion polymerization techniques may be used.
• the emulsion polymerization generally produces polymers or gums having concentrations within the range of 0.1 to 20% by weight.
• the aqueous solutions of polymers have a solution concentration of 0.2-2.0% by weight.
• the water-in-oil emulsions generally contain oil to water weight range of 5:i to 1:10 with preferred emulsions being prepared in the ratio of 2:1 to 1:10.
• the aggregate polymer-water gel-like particle in the water-in-oil emulsion ranges from 0.5 to 50 microns in diameter.
• Particularly useful commercially available representatives of this class are partially quaternized amine polymers consisting of complex structures of 1°, 2° and 3° amines, and optionally epi- chloro-hydrin.
• Another class of particularly useful polyelectrolytes are the water-soluble Mannich amine polymers of the general formula of which a commercial representative is Jayfloc® 854 solid by Exxon Chemical Americas of Houston, Texas.
• the weight ratio of demulsifier to polyelectrolyte ranges from 0.5:99.5 to 99.5:0.5, preferably 1:4 to 4:1, optimally 1:2 to 2:1.
• the solids-containing hydrocarbon contains from 0.05 to 10 weight percent of water
• silicone defoamants may be also added as well as other nonionic and anionic surfactants. All Mw given herein are weight average molecular weights as determined by gel permeation chromatography or light scattering as appropriate.
• Agglomeration conditions for use in the process of the invention will vary depending upon such process factors as the type and solids content of the hydrocarbon oil, the size distribution of the solids and the properties of the oil being processed.
• the most satisfactory process temperature will range from 35°C to 250°C, preferably from 50°C to 225°C and optimally from 75°C to 210°C.
• the process residence time required to reach the desired ash level of less than 0.05 weight percent will range broadly from-0.3 to 10, more'usually 2 to 5, days.
• the agglomeration aid and, if desired, the supplemental additives such as a water deshedding aid are introduced into the hydrocarbon oil stream to be treated prior to or at the point at which said stream is introduced into the top of the settling _tank.
• the product of the process is withdrawn from a point intermediate (on the side) while the- solids settle by gravity to the bottom of the tank.
• the flow rates and unit sizings in the process system are adjusted to provide the desired residence time in the settling tank.
• the settled solids in the settling tank are withdrawn generally as a sludge for direct disposal or further_treatment to recover additional hydrocarbon oil.
• hydrocarbon oil bottom fractions obtained from four different refineries having suspended solids with the following general physical characteristics were used:
• the hydrocarbon oil bottom fraction obtained from the refinery was charged into a kilogram glass reactor which was electrically heated and equipped with a mechanical agitator.
• the 200 ml charge of oil was pretreated by heating to 80°C prior to admixture with a blend containing the indicated agglomeration aid at a blend treat rate of 500 ppm for the oils from Refineries Nos. 1-3 and at both 100 and 200 ppm for the oil from Refinery No. 4.
• the treated charge was allowed to agitate for 2 minutes and then settle for 72 hours while holding the temperature at 79°C, thereafter 50 ml was drawn off from the upper region of the reactor and subjected to filtration to determine the filterable solids in weight parts per million (WPPM) according to the following technique.
• WPPM weight parts per million
• the 50 ml sample is weighed as is the filter paper (0.8 microns pore size) used for the test.
• the sample is preheated to 70-80°C, then mixed with 150 to 200 ml of hot xylene (heated above 55°C) and the admixture poured into the vacuum filter.
• the container and filter paper are fully rinsed with hot xylene and thereafter with heptane.
• the now fully rinsed paper is dried at 82°C for 30 minutes and then placed in a desicator for 30 minutes.
• the weight of the solids found on the filter paper provides the means for measuring the weight parts per million (WPPM) of filterable solids of the original sample.
• WPPM weight parts per million

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Separation Of Suspended Particles By Flocculating Agents (AREA)

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Citations (4)

• 1986
  • 1986-03-26 EP EP86302284A patent/EP0197716A3/de not_active Withdrawn
  • 1986-03-26 AU AU55545/86A patent/AU5554586A/en not_active Abandoned

Patent Citations (4)

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