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
  • 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
  • C10G29/24—Aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/20—Use of additives, e.g. for stabilisation
• • 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
• • 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
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• • 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
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/302—Viscosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T137/00—Fluid handling
  • Y10T137/0318—Processes
  • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

• This invention relates to methods and compositions for reducing the viscosity of circulating media used in primary fractionators of ethylene plants.
• hot cracked gases from furnaces need to be cooled down (quenched) for further processing and fractionation.
• This cooling process takes place in the quench system, which in the case of liquid and mixed feed crackers, consists of a series of transfer line exchangers (TLX or TLE), primary fractionator or quench oil tower, quench oil loop, and auxiliary equipment (i.e. filters, optional fuel oil stripper, etc.).
• TLE transfer line exchangers
• primary fractionator or quench oil tower quench oil loop
• auxiliary equipment i.e. filters, optional fuel oil stripper, etc.
• cracked products are fed to the distillation tower (primary fractionator or quench oil tower), which separates light products to the top (pyrolysis gasoline) and heavier hydrocarbons to the bottoms.
• a portion of the bottom product is circulated via the quench oil loop back to the TLX as the quenching medium.
• the immense heat recovered through the quench oil system is used to produce dilution steam, which in turn is returned to the cracking furnaces aiding in overall heat recovery.
• High temperatures and long residence times in the circulation (quench oil) loop are conducive to the heavy molecules produced in the cracking furnaces to agglomerate into large polynuclear aromatic species, often referred to as tars.
• Tars increase the viscosity of the circulating media thus increasing the potential for fouling in the tower and in turn negatively affecting heat recovery and proper fractionation.
• the quenching material's viscosity increases, its heat transfer coefficient drops. Over time this can result in severely reduced heat recovery, less steam production in dilution steam systems, and significant costs of import steam required for cracking.
• the media becomes harder to pump, it works less effectively, or needs to be supplemented with imported flux oil. In some cases the quenching media becomes so ineffectual that at least some portions of the plants must be operated at temperatures beyond their design limitations. All this results in significant costs and problems with maintenance and product quality.
• Prior art methods of mitigating viscosity increases in quench media involve adding specially formulated antifoulants that prevent heavy tars from aggregating and depositing, thereby improving the tar's flow characteristics.
• US Patent 5,985,940 describes the use of phenol-formaldehyde resins to control viscosity in quenching media.
• the prior art methods lose effectiveness when significant amounts of residual reactive monomers are present in the effluent of the cracking process.
• Recent changes in industry practice involve using different feedstocks which result in large amounts of residual reactive monomers which impair the effectiveness of these antifoulants. This is causing unpredictable changes in the mechanisms and characteristics of the quenching media and is once again resulting in significant problems in cost, product quality and maintenance.
• At least one embodiment of the invention is directed to a method of reducing an increase in viscosity or maintaining viscosity and a drop in the heat transfer coefficient of quenching media which is repeatedly circulated through a hot circulation system.
• the method comprises the step of adding a preserving composition to the quenching media.
• the composition comprises: a) high temperature polymerization inhibitor, b) a tar dispersant, and c) a viscosity reducer.
• the composition may further comprise a high boiling point solvent.
• the high temperature polymerization inhibitor may be 1 naphthol, or hindered phenol, or a combination thereof.
• the tar dispersant may be alkyl substituted phenol formaldehyde resin.
• the viscosity reducer may be alpha olefin-alkyl maleate co-polymer.
• the composition may be added to the quenching media to result in an amount of 100- 10000 ppm.
• the quenching media may be quench oil.
• the hot circulation loop may be a primary fractionator quench oil loop in an ethylene plant.
• the hot circulation loop may be one selected from the list consisting of a primary fractionator in ethylene plant or an EDC/VCM application.
• the residence time of the quenching media in the reaction vessel may be highly variable.
• the temperature of the quenching media in the reaction vessel may be between 20 and 300° C.
• High Temperature Polymerization Inhibitor means a composition of matter that inhibits the formation of polymers from monomer units present in temperatures in excess of 150°C, which includes but is not limited to hindered phenols, 1-naphthol, aryl substituted aromatic diamines, alkyl substituted aromatic diamines, and combinations thereof.
• Tar Dispersant means a composition of matter comprising a molecule having a hydrocarbon group, a polar group (for example a nitrogen or oxygen functional group), and a connecting group connected to both the hydrocarbon group and the polar group, the composition capable of effectively inhibiting the agglomeration or breaking up agglomerates of tars in a liquid, and dispersing them throughout the liquid, which includes but is not limited to alkyl substituted phenol-formaldehyde resins, alkyl substituted phenol— polyethylene-polyamine— formaldehyde resins, polyacrylate copolymers, and combinations thereof.
• Viscosity Reducer means a composition of matter that reduces viscosity of hydrocarbon mixtures at elevated temperatures above 150°C which includes but is not limited to ⁇ —olefin maleic acid copolymers.
• the performance properties of a quenching medium which is repeatedly circulated into cracked material to cool the material is preserved by adding a novel composition of matter.
• the composition comprises a high temperature polymerization inhibitor, a tar dispersant, and a viscosity reducer.
• the composition further comprises a high boiling point solvent. This composition prevents tars from
• agglomerating inhibits polymerization of residual monomers from the cracking process (such as styrene, indene, monounsaturated hydrocarbons, polyunsaturated hydrocarbons, and any combination thereof) and prevents these materials from interacting, thus effectively reducing viscosity of the quenching material.
• the prevention persists even when the quenching media is re -circulated many times over a long period of time.
• the prevention resulting from the composition is an unexpected effect that results from a synergism caused by the combination of these three components. This causes the observed degree of prevention to exceed the sum of each of the individual prevention effects of each of the three components.
• the tar dispersant is one selected from the list consisting of alkyl substituted phenol formaldehyde resins, polyacrylate copolymer, alkyl substituted phenol polyethylene-polyamine formaldehyde resins, and any combination thereof.
• representative tar dispersants are those described in US Patent 5,985,940.
• the polymerization inhibitor is 1-naphthol or a hindered phenol.
• the polymerization inhibitor is an amine antioxidant. While a composition comprising an amine antioxidant and a phenol formaldehyde resin is described in Chinese Patent Application CN 101062880, it does not disclose adding a viscosity reducer. Moreover this reference makes no teaching or suggestion that the combination of the three would result in a preservation effect in excess of the sum of each of the individual prevention effects of each of the three components.
• the composition is effective for a cracked material in which reactive monomers exceeds 1% of the cracked material. In at least one embodiment the composition is effective for a cracked material in which reactive monomers are between 1- 10% of the cracked material.
• composition is effective because it allows the inhibition effect to be present throughout the entire system being quenched and not only in one portion of it.
• the physical properties of the inhibitors limit them to the top portion of a fractionator and therefore they do not function effectively in the bottoms of the
• composition of matter allows the inhibitor to mamfest at the bottoms as well and as a result causes a much greater preservative effect.
• the composition comprises 1-10% (preferably 5%) tar dispersant, 1-10% (preferably 5%) hindered phenol, 1-naphthol, or a combination of hindered phenol and 1-naphthol, 8-30% (preferably 20%) viscosity reducer, and 50- 90% (preferably 70%) of heavy aromatic naphtha.
• 1-10% preferably 5%
• hindered phenol 1, 10-%
• 1-naphthol 1, 2-naphthol
• a combination of hindered phenol and 1-naphthol 1, 6-butanediol
• 8-30% preferably 20%
• viscosity reducer 1, 5-fluoride
• 50- 90% preferably 70% of heavy aromatic naphtha.
• the composition comprises 1-10% (preferably 5%) tar dispersant, 1-10% (preferably 5%) hindered phenol, 1-naphthol, or a combination of hindered phenol and 1-naphthol, 8-30% (preferably
• naphtha functions as the solvent.
• the composition is added in a dosage of 100 to 10,000 ppb in the quenching medium.
• the ideal dosage of composition may vary based on the viscosity of the medium and more viscous media require greater dosages of composition.
• the composition is directly injected into the circulation loop.
• the residence time is 1 hour to 10 days (preferably 2-5 days).
• the composition prevents viscosity increases and heat transfer coefficient drops in quenching media in industrial facilities including but not limited to quench oil loops of primary fractionators in ethylene plants, EDC/VCM applications, and any combination thereof.
• a portion of quench oil from a circulation loop of primary fractionator in an ethylene plant was obtained. Laboratory analysis of the portion showed that it contained 1-2% reactive monomers.
• the portion was then divided into a number of samples to which various amounts of native pyrolysis gasoline was added to simulate conditions of the quench oil loop. This resulted in samples having as much as 1 - 10% reactive monomers.
• the samples then had various amounts of one, two, or all three components of the inventive composition added to them.
• Viscosity profiles were taken of the refluxed samples after specific periods of time (4 to 20 hours) and were measured over a range of temperatures 40-150°C using a Brookfield rheometer with Thermosel® attachment. The percent reductions in viscosity are reported on Tables 1 and 2 for the low and high endpoints of the measurements taken.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Analytical Chemistry (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• Water Supply & Treatment (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Lubricants (AREA)
• Polymerisation Methods In General (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
• Liquid Carbonaceous Fuels (AREA)

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• 2011
  • 2011-10-19 US US13/276,599 patent/US9505988B2/en active Active
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