Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
  • C10L1/2456—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds sulfur with oxygen and/or nitrogen in the ring, e.g. thiazoles

Definitions

• the present invention relates to the stabilization of gasoline for preventing gum formation, specifically it relates to gasolines obtained by steam cracking.
• the stabilizing composition according to the invention is also effective in the stabilization of gasolines outputted from thermal (e.g., Visbreaking, coking and the like) , or catalytic (e.g. Fluidized Catalytic Cracking) cracking plants .
• the stabilization according to the invention is obtained by use of a composition comprising phenothiazine (PNTZ) and tert.butyl catechol, unexpectedly providing, at certain use ratios, a synergistic stabilizing effect.
• PNTZ phenothiazine
• tert.butyl catechol tert.butyl catechol
• gasolines refers to the fuels for the normal internal combustion engines, made of blends of hydrocarbons that may widely differ one from the other according to the production process thereof.
• the stability problem is particularly critical for gasolines produced by a steam cracking process.
• the problem concerns any thermal (visbreaking, coking, thermal cracking), as well as catalytic (FCC, LC finer, Mild Hydrocracking, HDS) cracked gasoline.
• the stability is evaluated as resistance to degradation caused by oxygen contact.
• stabilizers added to the gasoline for enhancing the stability thereof were used.
• Effective stabilizers for gasolines of the prior art belong to the class of the aromatic amines.
• PDA paraphenylenediamines
• other materials like, e.g., the nitrdxides (US-A-5, 711, 767 ) or the hindered phenols (US- A-5,509, 944) .
• phenotiazine alone or in admixture with other materials, is known to stabilize monomers and as an antifouling agent in oil or petrochemical processes, and overall as a polymerization inhibitor of vinyl aromatic compounds (US-A-4 , 061, 545) .
• the TBC is used in many stabilizing- antifouling agent combinations when an inhibition of polymerization reactions is required, (US-A-3 553 990) , and as a retarding agent in the formation of coke and of fouling in petrochemical processes.
• the stabilizer of the present invention is a blend, comprising in a certain weight ratio:
• PNTZ substituted or unsubstituted phenothiazine
• Ri and R 2 represent H, an alkyl Ci - C 20 or a cycloalkyl C 5 - C 20 group and R 3 represents H, an alkyl Ci - C 2 o or cycloalkil C 5 - C 20 and phenyl group, said alkyl and cycloalkyl groups possibly also containing functional groups, or dimer phenothiazine; and
• esther or carboxylic acid groups and derivatives thereof of the type
• R 4 is H, OH, R 3 , -ORi, or -OR 3 ; alcohol or esther groups of the -0-R 3 type; amino groups of the type
• a novel solution to the problem of gasolines stabilization and prevention of gum formation is provided by the use of a composition of PNTZ and of TBC in a suitably balanced ratio therebetween, having low toxicity and high effectiveness, equal to or higher than that of the PDA, and void of carcinogenic hazards, in the stabilization of pyrolisis gasolines, particularly of catalytic cracking gasolines.
• the subject-matter of the present invention is a gasoline stabilizing composition for preventing the gum formation and the degradation thereof, characterized in that it comprises, as effective preventing components, substituted or unsubstituted phenothiazine (PNTZ) or dimer, and tert.butyl-catechol
• PNTZ substituted or unsubstituted phenothiazine
• dimer dimer
• the gasoline stabilization is carried out by adding to the gasoline 5 to 1000 ppm of a stabilizer, comprising as active stabilizing ingredients PNTZ and TBC in a weight ratio therebetween of 5:95 to 80:20, preferably of 27:75 to 40:60, even more preferably of 30:70 to 35:65, with an optimum value of about 33.3:66.6.
• a stabilizer comprising as active stabilizing ingredients PNTZ and TBC in a weight ratio therebetween of 5:95 to 80:20, preferably of 27:75 to 40:60, even more preferably of 30:70 to 35:65, with an optimum value of about 33.3:66.6.
• the dosage of the additive with respect to the gasoline, as well as the ratio of the two compounds, can vary with particular reference to the Bromine number and to the diene value.
• composition according to the invention may contain, besides the two above-mentioned components, PTNZ and TBC, other PTNZ- and TBC- compatible components and additive carriers commonly used in stabilizing compositions.
• Particularly suitable solvents are the aromatic solvents, like benzene, toluol and the like, as well as dimethyl-formamide and dimethyl-acetamide .
• the combined use of the compounds in the blend yields a synergistic effect that is particularly significant at the preferred weight ratio values of the compounds .
• Stability measurement tests use an assay for measuring the stability to degradation of the gasolines denominated Induction Period (Time?) Method ASTM D525. This method is deemed the most suitable for measuring the stability of the gasolines, by virtue of the predictive capacity thereof of the gum formation due to a gasoline polymerization in presence of oxygen.
• Such method provides the heating at 100°C (98°C- 102°C) of a 50 ml sample in a bomb, sealed and subjected to a 690 kPa (100 psi) air pressure.
• the test attains a break point, represented by the instant when, on the pressure gauging curve, first a pressure drop of at least 14 kPa (2 psi) over 15 minutes, and then, over the next 15 minutes, another drop of at least 14 kPa (2 psi) take place.
• the induction time is determined by the time elapsed from the test start (positioning of the bomb inside the heating bath) to the break point.
• the induction time is a direct expression of the gasoline liability to gum formation during storage. This evaluation parameter is highly significant for highly unstable gasolines, like the cracked ones.
• the table shows the predictable result that, when used individually, the best products are the PDA and the TBC, in accordance to long-time refinery practice.
• the blend TBC+PNTZ according to the invention emerges as a stabilizer having an effectiveness even greater than that of the PDA, therefore being capable of replacing the latter with improvement of performance, as well as toxicity elimination .
• EXAMPLE 2 A test series was carried out in order to assess the optimal ratio between the two components of the TBC+PNTZ blend, on the basis of the induction time method. The results are reported in the following Table 2.
• TBP tert .butyl-phenols
• test results reported in Table 5 should be compared to those of Table 4. They refer to tests carried out in order to simulate a wide range of cracked products, with gasoline characteristics, like, e.g. the Bromine number and the diene value, differing thereamong. This tests prove that the blend PNTZ/TBC of the present invention can replace, even with a higher effectiveness, the PDA+TBP blends, completely avoiding any toxicity hazard deriving from the use of the aromatic amines.
• the induction time test is applied also in the following examples 5-9, in which the effectiveness of the additive according to the invention (PNTZ-TBC in a 1:2 ratio) is compared to that of other stabilizers of the known art.
• the test is carried out on gasolines outputted by various industrial FCC (Fluid Catalytic Cracking) plants located in various European countries .
• FCC Fluid Catalytic Cracking
• the first gasoline sample is made of 26% C5 hydrocarbon cut, 60% light gasoline and 14% medium gasoline . Cut characteristics: Light gasoline Medium gasoline
• the second gasoline sample has the following characteristics . Cut characteristics: Density 0.678
• the fourth sample is a light gasoline having the following characteristics. Cut characteristics: Density 0.6638
• the fifth sample is a medium gasoline having the following characteristics. Cut characteristics:
• test battery was carried out using a different ASTM test method, always related to the gasoline stability, carried out on a gasoline sample additioned with 100 ppm stabilizer, stored at 40°C for 43 days in a blanketed flask.
• the so-called existent gums i.e. the quantity of polymers formed (in mg/100 ml gasoline) following a brisk evaporation of a gasoline quantity in a preheated air jet at 160-165 °C, are determined through the ASTM D381/94 method, entitled «Standard test method for existent gum in fuels by Jet Evaporation» .
• Carrying out the same method on specimens of the gasoline stored at 40°C, additioned and not, at T 0 and at day 8, 22, 29 and 43 an increasing trend of said quantity of formed polymers (gums) is observed, which evidently is inversely proportional to the stabilizing effectiveness of the added additive.
• the results in mg/100 ml of a cracked gasoline sample are the following:

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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Publications (3)

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• 1999
  • 1999-05-07 IT IT1999RM000286A patent/IT1306138B1/it active
• 2000
  • 2000-05-05 AU AU46110/00A patent/AU4611000A/en not_active Abandoned
  • 2000-05-05 ES ES00927725T patent/ES2231192T3/es not_active Expired - Lifetime
  • 2000-05-05 AT AT00927725T patent/ATE280211T1/de active
  • 2000-05-05 DK DK00927725T patent/DK1144553T3/da active
  • 2000-05-05 WO PCT/IT2000/000175 patent/WO2000068343A2/en active IP Right Grant
  • 2000-05-05 DE DE60015073T patent/DE60015073T2/de not_active Expired - Lifetime
  • 2000-05-05 PT PT00927725T patent/PT1144553E/pt unknown
  • 2000-05-05 EP EP00927725A patent/EP1144553B1/de not_active Expired - Lifetime
• 2001
  • 2001-01-04 NO NO20010051A patent/NO20010051L/no not_active Application Discontinuation

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