US3437583A - Anti-foulant agents for petroleum hydrocarbons - Google Patents

Anti-foulant agents for petroleum hydrocarbons Download PDF

Info

Publication number
US3437583A
US3437583A US645590A US3437583DA US3437583A US 3437583 A US3437583 A US 3437583A US 645590 A US645590 A US 645590A US 3437583D A US3437583D A US 3437583DA US 3437583 A US3437583 A US 3437583A
Authority
US
United States
Prior art keywords
inclusive
value
employed
alkyl
phenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US645590A
Inventor
Gerardo A Gonzalez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suez WTS USA Inc
Original Assignee
Betz Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Betz Laboratories Inc filed Critical Betz Laboratories Inc
Application granted granted Critical
Publication of US3437583A publication Critical patent/US3437583A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/143Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1835Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/198Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981Condensation polymers of aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/228Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the hydrocarbons are commonly heated to temperatures in excess of 250 F.
  • such petroleum compounds are frequently subjected to heat exchange during processing and are often used as the heating medium on the hot side of heating and heat exchange systems.
  • the petroleum hydrocarbons experience elevated temperatures which produce a separate phase commonly referred to as fouling deposits, within the petroleum compound.
  • fouling deposits are highly undesirable in that they reduce the bore or capacity of conduits and vessels to impede process throughput, impair thermal transfer, and clog filter screens, valves and traps.
  • the deposits form an insulating layer upon the heat exchange surface to impair heat transfer and necessitate frequent shutdowns for cleaning, extended processing cycles, and increased coolant flow.
  • phenolic compounds utilized in the practice of the invention are monoand dialkyl substituted phenols, and the condensates of such phenols, including nitrogen containing phenolic condensates. These phenolic compounds and condensates may be represented by the formula:
  • Ri R 38/111 (1 in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15, m and c are integers having a value of between zero to one, b is an integer having a value of between zero to 4, and the sum total of a and d is no more than 25. It should be noted that when an excess of phenol is employed in the preparation of these condensates, Y will be the alkyl phenol which is employed in the condensation reaction. In other cases, methylol termination will be experienced and Y will be OH.
  • alkyl substituents R and R are probably the primary factor contributing to the hydrocarbon solubility or dispersibility of these phenolic compounds and condensates. This solubility, when enhanced by the synergistic activity which is realized when the phenolic compounds are combined with the metal deactivator, yields the highly improved results which are realized with the invention.
  • nitrogen substituted alkyl phenol condensates are preferred ingredients of the inventive composition, highly satisfactory, and synergistically enhanced compositions have also been prepared from both the noncondensed alkyl phenols, and alkyl phenolic condensates which do not contain a nitrogen substituent.
  • Suitable alkyl phenols include butyl, octyl, nonyl, dioctyl and dinonyl phenol, although octyl phenol is a preferred material in respect to either the condensed or noncondensed compositions.
  • branched alkyl substituents e.g. t-octyl, t-butyl, etc., enhance the hydrocarbon solubility or dispersibility of the inventive compounds and are preferred on that basis.
  • the suitable alkyl phenol condensates include both unsubstituted and nitrogen substituted condensates.
  • the unsubstituted condensates are prepared by conventional means, employing either acidic or basic catalysts, to yield reaction products of the following type:
  • the nitrogen substituted reaction products may be prepared by condensing the alkyl or dialkyl phenol with either an ammonium compound, e.g., ammonium hydroxide, or an amine, e.g. ethylene diamine, propylene diamine, 1,3 diamino propane, etc.
  • an ammonium compound e.g., ammonium hydroxide
  • an amine e.g. ethylene diamine, propylene diamine, 1,3 diamino propane, etc.
  • the reaction conditions which are employed may determine whether the ammonium compound constitutes a nitrogen substituent to the resulting condensate, or merely catalyzes a reaction yielding a condensate such as that shown by Formula I above.
  • high reaction temperatures e.g.
  • a nitrogen determination e.g. Kjeldahl, will permit the adjustment of the reaction conditions to yield the desired condensate, i.e. substituted or unsubstituted by nitrogen.
  • formaldehyde is employed as the co reactant with the alkyl phenol regardless of whether a nitrogen donating third reactant, i.e. amine or ammonium compound, is utilized.
  • a phenol:formaldehydezammonium hydroxide molar ratio of 1.5:l:2 is preferred.
  • the excess ammonium compensates for losses due to violatility which may be further reduced through the use of a closed reaction system, whereas the excess of unreacted phenol serves as a satisfactory diluent, and as previously noted, even the uncondensed alkyl phenol is capable of contributing to the synergistic effect of the invention. While an excess of formaldehyde does not yield a beneficial effect, it does not appreciably impair the efficacy of the invention.
  • the ammonium compound is employed to merely catalyze, and not enter into the reaction, e.g. in a high temperature reaction, a substantial excess or this compound may be employed.
  • a phenol:formaldehydezamine molar ratio of 4:4:1 is preferred. Such as a ratio yields a desirable frequency of the nitrogen substituents, while an amine deficiency yields results similar to those obtained with the previously discussed condensates Formula I which are devoid of a nitrogen substituent. Similarly, a higher amine content, either as an unreacted excess, or as a more frequently occurring substituent, does not impair the efficacy of the invention.
  • EXAlNIPtLE 1 Octyl phenol, formaldehyde and ammonium hydroxide were employed in a 1.5:l:2 ratio. The octyl phenol and ammonium hydroxide were admixed, and an aqueous solution of formaldehyde (37% by weight of formaldehyde) was added thereto and further admixed. This reaction admixture was maintained at 170 F. for a period of 4 hours and then gradually elevated to a tem perature of 360 F. during an additional 3 hour period. The reactants were maintained at 360 F. for an additional 20 minute period, during which time water was removed by distillation.
  • reaction product was then cooled to room temperature and admixed with an equal quantity of xylene.
  • a Kjeldahl determination indicated that less than 1% nitrogen was present in the reaction product, and the molecular weight (A.H.T. Molecular Weight Apparatus determination) indicated a condensate of the following average structure:
  • Example 2 The reaction of Example 1 was repeated with a 0.6:1:0.8 ratio of octyl phenolzformaldehydezammonium hydroxide, with the reaction temperature reduced to 280 F. A Kjeldahl determination of the resulting condensate revealed 3.6% nitrogen which would indicate the presence of an ammonium molecule for each 1.7 mols of octyl phenol and 1.7 mols of formaldehyde.
  • Examples 1 and 2 have been employed to demonstrate that ammonium hydroxide may serve merely as a condensation catalyst, or may directly participate in the reaction to become a constituent of the reaction product.
  • the substituted succinic compounds may be prepared by merely reacting maleic anhydride and a polyolefin or (
  • EXAMPLE 4 halogenated polyolefin at temperatures in the range of An admixture of 4 parts by weight of octyl phenol and 1 part of formaldehyde were reacted in the presence of 0.2% by weight of 90% formic acid.
  • the present invention employs the combination of a metal deactivator and a phenolic compound.
  • the inventive combination of ingredients provides a synergistic effect in that the cooperative action of the two ingredients is such that the total effect of the combination is greater than the sum of the effects of the two ingredients taken separately.
  • the total quantity of anti-foulant employed may be reduced with appreciable reductions in the cost of the treatment, and less possibility of the formation of ancillary deposits from the anti-foulant. This reduction in the quantity of anti-foulant required, represents a substantial improvement over the anti-foulant agents of the prior art.
  • the metal deactivator employed in the practice of the present invention is N,N'-disalicylidene-1,2-propanediamine, havving the formula:
  • succinic derivatives employed in the practice of the invention are reaction products of polyamines and substit'uted succinic acids or substituted succinic anhydrides.
  • R is an alkyl or alkenyl radical having from 30 to 200 carbon atoms in the carbon chain and w is an integer having a value of between 1 to 5 inclusive.
  • Suitable polyolefinic reactants include polyethylene, polypropylene, polybutene, polyisobutylene, polyamylene, polyisoamylene, polyisohexylene, etc. Syntheses of this type are disclosed by US. 3,271,295, British Patent 922,831 and U.S. 3,240,575, and a preferred preparation is described by Example 5, below.
  • EXAMPLE 5 One hundred and eighty parts by weight of a polyisobutylene polymer (95%, balance isoparaflins) having an average molecular weight of 890 was pre-heated to F. and placed in a reactor with 43 parts by weight of maleic anhydride. The admixture was vigorously agitated until visibly homogeneous and elevated to a temperature of 560 F. over a period of 7 hours. The resultant reaction product was predominantly the substituted succinic anhydride. Approximately one-half of the reaction product was admixed with water and heated to 200 F. for a period of 4 hours to convert the anhydride to substituted succinic acid. The water was then removed by means of azeotropic distillation.
  • x is an integer having a value of between 1 to 10 inclusive
  • y is an integer having a value of zero or 1
  • z is an integer having a value of between 1 to 10 inclusive.
  • EXAMPLE 6 The substituted succinic anhydride of Example 5 (180 parts by weight) was admixed with diethylene triamine (12 parts by weight) and xylene (85 parts by weight), heated to 180 F. and maintained at that temperature for 30 minutes under reflux, and then elevated to 280 F. in order to strip off the Xylene.
  • Example 6 was repeated with the substitution of 17 parts by weight of propylene diamine for the diethylene triamine, and the substitution of an equal quantity of the substituted succinic acid of Example 5 for the substi tuted succinic anhydride which was employed in Example 6.
  • the metal deactivator, phenolic compound and succinic derivative are employed in a weight ratio of 1:1.5 :5.
  • the metal deactivator is the most costly ingredient at the present time and the limitation of quantity of this material which is employed yields a desirable cost:anti-fouling performance ratio.
  • effective performance is realized when the inventive combination of ingredients is employed at a level of between 0.5 to 10,000 parts by weight of the inventive anti-foulant for each one million parts by weight of the material, e.g. petroleum hydrocarbon, which is treated.
  • the anti-foulant Preferably to 100 parts per million of the anti-foulant are employed although much larger quantities may be tolerated if an increased treatment cost and/ or decreased costzanti-fouling performance ratio may be tolerated. It is also preferable to employ the inventive combination of ingredients in a weight ratio in which none of the three ingredients, e.g. metal deactivator, phenolic compound or succinic derivative, is present as a quantity of less than by weight of the totalantifoulant exclusive of detergents, solvent or carriers. In the latter regard, it should be noted that the inventivve antifoulants may be employed while dispersed in a suitable carrier. While many carriers are suitable, petroleum hydrocarbon derivatives such as kerosene or a naphtha solvent are preferred as the result of their compatibility and miscibility with the materials to be treated.
  • inventive anti-foulants may be readily added to the material to be treated by mere addition with moderate agitation.
  • their addition to a process stream at a point characterized by some flow or turbulence will facilitate their dispersion.
  • the combined ingredients yield a total elimination of fouling deposits
  • the individual ingredients permit the formation of appreciable quantities of fouling deposits, despite the fact that they are employed in quantities ranging between 2 to 4 times the quantities employed in the inventive combinaiton.
  • Tests 7 and 8 have been included in Table 1 for the purpose of demonstrating that other ratios of the ingredients of the inventive compositions are also suitable and highly efiicient.
  • the inventive products also yield a substantial heat transfer improvement.
  • the U value average final heat transfer coefficient in B.t.u./F-ft. hr.
  • the inventive composition employed in Test 6 of Table 1 yielded a heat transfer value which represented a 71% improvement of the control (devoid of anti-foulant) with which it was contrasted.
  • compositions and methods for the treatment of liquid petroleum hydrocarbons have been provided, that such methods and compositions provide eifective control over the formation of fouling deposits as well as losses in heat transfer, that such control represents a substantial improvement over the prior art and a synergistic improvement over the results obtainable with the individual ingredients of the inventive compositions, and particularly over the results obtainable at temperatures in excess of 500 F., and that low cost, elfective methods and materials are therefore provided.
  • a method for controlling the formation of fouling deposits in petroleum hydrocarbon during processing at elevated temperatures comprising dispersing within said hydrocarbon an anti-foulant comprising the combination of (I) a phenolic compound having the formula R Rn in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, n is an integer having a value of between zero to 1 inclusive, and X is a substituent selected from the group consisting of hydrogen and a phenolic group having the formula in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms inclusive, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15 inclusive, m and c are integers having a value of between zero to 1 inclusive, 1) is an integer having a value of between zero to 4
  • a method as claimed by claim 1 in which between 10 0.5 to 10,000 parts by weight of said anti-foulant are dispersed in each one million parts by weight of said petroleum hydrocarbon.
  • said phenolic compound is the condensate of formaldehyde, a nitrogen containing compound and an alkyl phenol having the formula R Rn in which R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive, and n is an integer having a .value of between zero to 1 inclusive.
  • a method as claimed by claim 4 in which said nitro: gen containing compound is selected from the group consisting of ammonium hydroxide, ethylene diamine, propylene diamine and 1,3 diamino propane.
  • An anti-foulant composition consisting essentiallyof (I) a phenolic compound having the formula in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, 11 is an integer having a value of between zero to 1 inclusive, and X is a substituent selected from the group consisting of hydrogen and a phenolic group having the formula in which R is an alkyl groupv attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atombs, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms inclusive, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15 inclusive, m and c are integers having a value of between zero to 1 inclusive, b is an integer having a value of between zero to 4 inclusive, and the sum totalof a and d is no more than 25, (II) the reaction product of a polyamine having
  • composition as claimed by claim 6 in which said phenolic compound is present in a quantity of between 0.5 to 3 parts by weight for each part by weight of said N,N'-disalicylidene-1,2-propane.
  • composition as claimed by claim 6 in which said phenolic compound is the condensate of formaldehyde, a nitrogen containing compound and an alkyl phenol having the formula R Rn R Rn
  • R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive
  • n is an integer having a value of between zero to 1 inclusive.
  • composition as claimed by claim 6 in which said phenolic compound is the condensate of formaldehyde and alkyl phenol having the formula ll.
  • R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive
  • n is an integer having a value of between zero and 1 inclusive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

Unite States Patent Ser. No. 645,590
Int. Cl. C231? 11/00; C09k 3/00; 'C10g 9/16 15 Claims U.S. Cl. 208-48 ABSTRACT OF THE DISCLOSURE Anti-foulants for petroleum hydrocarbon streams and feedstocks which employ the combination of a metal deactivator, a phenolic compound and substituted succinic acids or anhydrides.
The present invention is a continuation-in-part of copending US. application Ser. No. 595,045 which was filed on Nov. 17, 1966.
In the processing of petroleum hydrocarbons and feedstocks such as petroleum process intermediates, petrochemicals and petrochemical intermediates, e.g., gas oils and reformer stocks, the hydrocarbons are commonly heated to temperatures in excess of 250 F. Similarly, such petroleum compounds are frequently subjected to heat exchange during processing and are often used as the heating medium on the hot side of heating and heat exchange systems. During such processing the petroleum hydrocarbons experience elevated temperatures which produce a separate phase commonly referred to as fouling deposits, within the petroleum compound. Such deposits are highly undesirable in that they reduce the bore or capacity of conduits and vessels to impede process throughput, impair thermal transfer, and clog filter screens, valves and traps. In the case of heat exchange systems, the deposits form an insulating layer upon the heat exchange surface to impair heat transfer and necessitate frequent shutdowns for cleaning, extended processing cycles, and increased coolant flow.
While the nature of such fouling deposits defies precise analysis, they appear to contain both carbonaceous phases of a coke-like nature, and polymers or condensates formed from the petroleum compound or impurities entrained therein. These condensates appear to interadhere the carbonaceous phase and to facilitate its adhesion to available surfaces. The catalysis of the formation of these polymers or condensates has been attributed to metal compounds such as copper or iron which are present in the petroleum compounds as impurities, or derived from the metallic receptacles in which the petroleum compounds are processed. For example, such metals may accelerate the hydrocarbon oxidation rate by promoting degenerative chain branching, while the resultant free radicals initiate oxidation and polymerization reactions which form gums and sediments.
In previous attempts to combat the formation of fouling deposits, it has been found that improvements may be realized by preventing the actual formation of these deposits, or preventing the adhesion of the deposits to available surfaces when formed. In addition, when heat transfer is the primary consideration in respect to such deposits, it has been found that desirable effects may be realized by influencing the density, and consequently the thermal insulating effect, of any deposits which may form and adhere to the heat transfer surfaces.
Previous attempts to control fouling deposits have employed phenolic compounds, e.g., U.S. 3,132,085 to Summers. Succinic derivatives have also been employed for this purpose, e.g., U.S. 3,271,295 and U.S. 3,271,296.
In the inventors co-pending application Ser. No. 595,045, which was filed on Nov. 17, 1966, it was found that the combination of certain disclosed phenolic compounds and metal deactivators yield synergistic results as anti-fouling agents in petroleum compounds which are subjected to high temperatures. The present invention is based upon the discovery that a further synergistic improvement is realized when certain succinic derivatives are employed with the phenolic-metal deactivator compound.
The ingredients of the anti-fouling agents of the present invention may be characterized as follows:
PHENOLIC COMPOUNDS The phenolic compounds utilized in the practice of the invention are monoand dialkyl substituted phenols, and the condensates of such phenols, including nitrogen containing phenolic condensates. These phenolic compounds and condensates may be represented by the formula:
R Rn
Ri R 38/111 (1 in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15, m and c are integers having a value of between zero to one, b is an integer having a value of between zero to 4, and the sum total of a and d is no more than 25. It should be noted that when an excess of phenol is employed in the preparation of these condensates, Y will be the alkyl phenol which is employed in the condensation reaction. In other cases, methylol termination will be experienced and Y will be OH.
It should be noted that the alkyl substituents R and R are probably the primary factor contributing to the hydrocarbon solubility or dispersibility of these phenolic compounds and condensates. This solubility, when enhanced by the synergistic activity which is realized when the phenolic compounds are combined with the metal deactivator, yields the highly improved results which are realized with the invention.
While the nitrogen substituted alkyl phenol condensates are preferred ingredients of the inventive composition, highly satisfactory, and synergistically enhanced compositions have also been prepared from both the noncondensed alkyl phenols, and alkyl phenolic condensates which do not contain a nitrogen substituent.
Suitable alkyl phenols include butyl, octyl, nonyl, dioctyl and dinonyl phenol, although octyl phenol is a preferred material in respect to either the condensed or noncondensed compositions. In addition it appears that branched alkyl substituents, e.g. t-octyl, t-butyl, etc., enhance the hydrocarbon solubility or dispersibility of the inventive compounds and are preferred on that basis.
The suitable alkyl phenol condensates include both unsubstituted and nitrogen substituted condensates. The unsubstituted condensates are prepared by conventional means, employing either acidic or basic catalysts, to yield reaction products of the following type:
R Rn x in which x is an integer having a value of between 1 to 25. While a 1:1 molar ratio of alkyl phenokformaldehyde is preferred, a quantity of either reactant in excess of theret ical is acceptable. It should also be noted that when an excess of the alkyl phenol is employed, the uncondensed excess serves not only as a highly satisfactory diluent, but also contributes to the desired anti-fouling effect, since the prescribed alkyl phenols function as hydrocarbon dispersible anti-foulants in an uncondensed form and are synergized in the presence of the metal deactivatOI'.
The nitrogen substituted reaction products may be prepared by condensing the alkyl or dialkyl phenol with either an ammonium compound, e.g., ammonium hydroxide, or an amine, e.g. ethylene diamine, propylene diamine, 1,3 diamino propane, etc. However, it should be noted that when the alkyl phenol is condensed with an ammonium compound such as ammonium hydroxide, the reaction conditions which are employed may determine whether the ammonium compound constitutes a nitrogen substituent to the resulting condensate, or merely catalyzes a reaction yielding a condensate such as that shown by Formula I above. Specifically, it has been found that high reaction temperatures, e.g. in excess of 150 C., may result in the temporary introduction of nitrogen within the condensate structure, but that the heat will eventually evolve the nitrogen to yield an unsubstituted condensate. However, a nitrogen determination, e.g. Kjeldahl, will permit the adjustment of the reaction conditions to yield the desired condensate, i.e. substituted or unsubstituted by nitrogen.
In the formation of all of the phenolic condensates of the invention, formaldehyde is employed as the co reactant with the alkyl phenol regardless of whether a nitrogen donating third reactant, i.e. amine or ammonium compound, is utilized.
In the condensation reactions employing ammonium hydroxide for the preparation of nitrogen substituted condensates, a phenol:formaldehydezammonium hydroxide molar ratio of 1.5:l:2 is preferred. The excess ammonium compensates for losses due to violatility which may be further reduced through the use of a closed reaction system, whereas the excess of unreacted phenol serves as a satisfactory diluent, and as previously noted, even the uncondensed alkyl phenol is capable of contributing to the synergistic effect of the invention. While an excess of formaldehyde does not yield a beneficial effect, it does not appreciably impair the efficacy of the invention. When the ammonium compound is employed to merely catalyze, and not enter into the reaction, e.g. in a high temperature reaction, a substantial excess or this compound may be employed.
In the preparation of nitrogen substituted condensates from amines, a phenol:formaldehydezamine molar ratio of 4:4:1 is preferred. Such as a ratio yields a desirable frequency of the nitrogen substituents, while an amine deficiency yields results similar to those obtained with the previously discussed condensates Formula I which are devoid of a nitrogen substituent. Similarly, a higher amine content, either as an unreacted excess, or as a more frequently occurring substituent, does not impair the efficacy of the invention.
Descriptions of the preparation of several phenolic compounds which have proved suitable for the practice of the invention, are provided by the following examples:
EXAlNIPtLE 1 Octyl phenol, formaldehyde and ammonium hydroxide were employed in a 1.5:l:2 ratio. The octyl phenol and ammonium hydroxide were admixed, and an aqueous solution of formaldehyde (37% by weight of formaldehyde) was added thereto and further admixed. This reaction admixture was maintained at 170 F. for a period of 4 hours and then gradually elevated to a tem perature of 360 F. during an additional 3 hour period. The reactants were maintained at 360 F. for an additional 20 minute period, during which time water was removed by distillation. The reaction product was then cooled to room temperature and admixed with an equal quantity of xylene. A Kjeldahl determination indicated that less than 1% nitrogen was present in the reaction product, and the molecular weight (A.H.T. Molecular Weight Apparatus determination) indicated a condensate of the following average structure:
OH I (6H CH2 -CH2OH CsHn CsHir The existence of this structure was further supported by infra-red and ultra-violet analyses, and solubility and fusability tests. The reaction product was also found to contain 12% by weight of unreacted octyl phenol.
EXAMPLE 2 The reaction of Example 1 was repeated with a 0.6:1:0.8 ratio of octyl phenolzformaldehydezammonium hydroxide, with the reaction temperature reduced to 280 F. A Kjeldahl determination of the resulting condensate revealed 3.6% nitrogen which would indicate the presence of an ammonium molecule for each 1.7 mols of octyl phenol and 1.7 mols of formaldehyde.
Examples 1 and 2 have been employed to demonstrate that ammonium hydroxide may serve merely as a condensation catalyst, or may directly participate in the reaction to become a constituent of the reaction product.
EXAMPLE 3 Octyl phenol, formaldehyde and ethylene diamine were reacted in a 4:4:1 ratio by the method of Example 1. The formaldehyde employed was a solution of paraformaldehyde. The reaction product was admixed with 60% by weight of a kerosenezxylene blend (1:3). Anal ysis revealed the presence of 2% of unreacted phenol The substituted succinic compounds may be prepared by merely reacting maleic anhydride and a polyolefin or (|)H I- (|)H I- OH (|)H CH CH2 'NHCH2CH2NH CH2 CI-Iz CH2OH 5H" Cs i1 3 Cs n 2 C 3H1 8 EXAMPLE 4 halogenated polyolefin at temperatures in the range of An admixture of 4 parts by weight of octyl phenol and 1 part of formaldehyde were reacted in the presence of 0.2% by weight of 90% formic acid.
METAL DEACTIVATOR More precisely, the present invention employs the combination of a metal deactivator and a phenolic compound. The inventive combination of ingredients provides a synergistic effect in that the cooperative action of the two ingredients is such that the total effect of the combination is greater than the sum of the effects of the two ingredients taken separately. As a consequence of the described synergism, the total quantity of anti-foulant employed may be reduced with appreciable reductions in the cost of the treatment, and less possibility of the formation of ancillary deposits from the anti-foulant. This reduction in the quantity of anti-foulant required, represents a substantial improvement over the anti-foulant agents of the prior art.
The metal deactivator employed in the practice of the present invention is N,N'-disalicylidene-1,2-propanediamine, havving the formula:
\ metal ion SUCCINIC DERIVATIVES The succinic derivatives employed in the practice of the invention are reaction products of polyamines and substit'uted succinic acids or substituted succinic anhydrides.
The substituted succinic acids and anhydrides utilized are represented by the formulae:
in which R is an alkyl or alkenyl radical having from 30 to 200 carbon atoms in the carbon chain and w is an integer having a value of between 1 to 5 inclusive.
to 300 C. Suitable polyolefinic reactants include polyethylene, polypropylene, polybutene, polyisobutylene, polyamylene, polyisoamylene, polyisohexylene, etc. Syntheses of this type are disclosed by US. 3,271,295, British Patent 922,831 and U.S. 3,240,575, and a preferred preparation is described by Example 5, below.
EXAMPLE 5 One hundred and eighty parts by weight of a polyisobutylene polymer (95%, balance isoparaflins) having an average molecular weight of 890 was pre-heated to F. and placed in a reactor with 43 parts by weight of maleic anhydride. The admixture was vigorously agitated until visibly homogeneous and elevated to a temperature of 560 F. over a period of 7 hours. The resultant reaction product was predominantly the substituted succinic anhydride. Approximately one-half of the reaction product was admixed with water and heated to 200 F. for a period of 4 hours to convert the anhydride to substituted succinic acid. The water was then removed by means of azeotropic distillation.
As previously noted, the foregoing substituted succinic acids and anhydrides are intermediates in relation to the practice of the invention and are further reacted with polyamines prior to their use in the invention. Such reaction is disclosed by U.S 3,271,295 and 3,271,296. Polyamines suitable as reactants include diethylene triamine, pentaethylene hexamine, 1,3-diamino propane, 1,6-diamino hexane, triethylene tetramine, ethylene diamine, propylene diamine, etc., which are represented by the formula:
HzN L oxHzfloHfl Nfljl in which x is an integer having a value of between 1 to 10 inclusive, y is an integer having a value of zero or 1 and z is an integer having a value of between 1 to 10 inclusive.
Preparations of the final succinic derivative, i.e. reaction product of the substituted succinic acid or anhydride and the amine, are illustrated by Examples 6 and 7 below.
EXAMPLE 6 The substituted succinic anhydride of Example 5 (180 parts by weight) was admixed with diethylene triamine (12 parts by weight) and xylene (85 parts by weight), heated to 180 F. and maintained at that temperature for 30 minutes under reflux, and then elevated to 280 F. in order to strip off the Xylene.
EXAMPLE 7 Example 6 was repeated with the substitution of 17 parts by weight of propylene diamine for the diethylene triamine, and the substitution of an equal quantity of the substituted succinic acid of Example 5 for the substi tuted succinic anhydride which was employed in Example 6.
In the preferred practice of the invention, the metal deactivator, phenolic compound and succinic derivative are employed in a weight ratio of 1:1.5 :5. However, only economic considerations influence the use of much greater ranges of each ingredient. For example, the metal deactivator is the most costly ingredient at the present time and the limitation of quantity of this material which is employed yields a desirable cost:anti-fouling performance ratio. In addition, effective performance is realized when the inventive combination of ingredients is employed at a level of between 0.5 to 10,000 parts by weight of the inventive anti-foulant for each one million parts by weight of the material, e.g. petroleum hydrocarbon, which is treated. Preferably to 100 parts per million of the anti-foulant are employed although much larger quantities may be tolerated if an increased treatment cost and/ or decreased costzanti-fouling performance ratio may be tolerated. It is also preferable to employ the inventive combination of ingredients in a weight ratio in which none of the three ingredients, e.g. metal deactivator, phenolic compound or succinic derivative, is present as a quantity of less than by weight of the totalantifoulant exclusive of detergents, solvent or carriers. In the latter regard, it should be noted that the inventivve antifoulants may be employed while dispersed in a suitable carrier. While many carriers are suitable, petroleum hydrocarbon derivatives such as kerosene or a naphtha solvent are preferred as the result of their compatibility and miscibility with the materials to be treated.
Similarly, the inventive anti-foulants may be readily added to the material to be treated by mere addition with moderate agitation. For example, their addition to a process stream at a point characterized by some flow or turbulence will facilitate their dispersion.
In regard to the efficacy of the inventive compounds as anti-foulants, studies yielding the data set forth in Table l were conducted. In these studies, a #2 raw fuel oil (undesulfurized light virgin furnace oil) was admixed with the specified quantities of anti-foulant agent and recycled through heated tubes having an outer diameter of inch at the rate of 0.6 gallon per hour for a period of hours. During the study, the oil exiting from the tubes was maintained at a temperature of between 530- 570 F. Upon the completion of each list, the tubes, which had been weighed prior to the test, were drained, oven-dried and weighed to yield the weight of fouling deposits which had accumulated during the test.
The synergistic effect yielded by the invention, i.e., the cooperative action of the discrete ingredients yield a total eifect which is greater than the sum of the eifects of the ingredients, is clearly demonstrated by the foregoing data.
In the first instance, the combined ingredients (Test 6) yield a total elimination of fouling deposits, while the individual ingredients (Tests 2, 3 and 4) permit the formation of appreciable quantities of fouling deposits, despite the fact that they are employed in quantities ranging between 2 to 4 times the quantities employed in the inventive combinaiton.
Secondly, an improvement over the results (Test 5) realized by the inventors co-pending invention (Ser. No. 595,045) is demonstrated by a comparison of the results obtained with Test 6 with the results of Test 5. Similarly, a synergistic improvement over the results realized with the copending invention is demonstrated by a comparison of the results of Test 6 with the results of Tests 4 and 5. In the first instance, the reduced fouling which is experienced with the combination of the metal deactivator and phenolic compound is completely eliminated when the same quantity of the foregoing ingredients is combined with the succinic derivative. In the second case, one-half of the quantity of the succinic derivative, and the same quantities of metal deactivator and phenolic compound (Test 6) yield the complete elimination of fouling, whereas the ingredients employed separately (Tests 4 and 5), and with much greater quantity of the succinic derivative (Test 4) yield appreciable fouling.
Tests 7 and 8 have been included in Table 1 for the purpose of demonstrating that other ratios of the ingredients of the inventive compositions are also suitable and highly efiicient.
TAB LE 1 Quantity Total Weight of Test Anti-foulants employed of each quantity fouling No. (p.p.m.) antiof antideposits ioulant ioulant (milli- (p.p.m.) (p.p.m.) grams) 1 (con- 0 0 0 566 trol Metal deactivator 5 5 328 Phenolic compound 15 15 435 Succinic derivative 25 25 55 Metal deactivator 2. 5 6. 25 103 Phenolic compound 3. 75 Metal deactivator 2. 5 Phenolic compound 3. 75 18.75 0 Succlnic derivative 12. 5
7 Metal deactivator 1 3. 3
Phenolic compound 5. 0 l6. 3 15 Succinic derivative 8. O
8 Metal dcactivator 1 4 Phenolic compound 6 15 6 Succinic derivative 5 1 N,N-disalicylidenel,Z-propanedlamine. 2 Phenolic condensate of Example 3. 1 Reaction product of Example 6.
TABLE 2 Quantity 01 Quantity of Anti-Ioulant anti-loulant fouling de- (p.p.m.) posits (mgs.)
Commercial antlioulant No. 1... 318 B Commercial antifoulant No. 2... 100 159 Composition of Test No. 6 on Table 1 18. 75 0 In relation to Table 2, it should be noted that the inventive composition completely eliminated fouling deposits while the standard commercial anti-foulants, even though employed in quantities 5 times as great, permitted the formation of substantial fouling deposits.
Finally, the inventive products also yield a substantial heat transfer improvement. Specifically, the U value (average final heat transfer coefficient in B.t.u./F-ft. hr.) demonstrated a substantial improvement in the tests previously discussed. For example, the inventive composition employed in Test 6 of Table 1 yielded a heat transfer value which represented a 71% improvement of the control (devoid of anti-foulant) with which it was contrasted.
It is apparent that various compositions and methods for the treatment of liquid petroleum hydrocarbons have been provided, that such methods and compositions provide eifective control over the formation of fouling deposits as well as losses in heat transfer, that such control represents a substantial improvement over the prior art and a synergistic improvement over the results obtainable with the individual ingredients of the inventive compositions, and particularly over the results obtainable at temperatures in excess of 500 F., and that low cost, elfective methods and materials are therefore provided.
It is also obvious that various alterations, substitutions and modifications of the methods and compositions of the present invention may be adopted without departing from the spirit of the invention as defined by the following claims.
I claim:
1. A method for controlling the formation of fouling deposits in petroleum hydrocarbon during processing at elevated temperatures, comprising dispersing within said hydrocarbon an anti-foulant comprising the combination of (I) a phenolic compound having the formula R Rn in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, n is an integer having a value of between zero to 1 inclusive, and X is a substituent selected from the group consisting of hydrogen and a phenolic group having the formula in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms inclusive, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15 inclusive, m and c are integers having a value of between zero to 1 inclusive, 1) is an integer having a value of between zero to 4 inclusive, and the sum total of a and d is no mode than 25, (II) the reaction product of a polyamine having the formula in which x is an integer having a value of between 1 to inclusive, y is an integer having a value of between zero to '1 inclusive, and z is an integer having a value of between 1 to 10 inclusive, and a succinic compound selected from the group consisting of substituted succinic anhydrides having the formula H R -H (EH-o0 o CHrCO w and substituted succinic acids having the formula of said anti-foulant.
3. A method as claimed by claim 1 in which between 10 0.5 to 10,000 parts by weight of said anti-foulant are dispersed in each one million parts by weight of said petroleum hydrocarbon.
4. A method as claimed by claim 1 in which said phenolic compound is the condensate of formaldehyde, a nitrogen containing compound and an alkyl phenol having the formula R Rn in which R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive, and n is an integer having a .value of between zero to 1 inclusive.
5. A method as claimed by claim 4 in which said nitro: gen containing compound is selected from the group consisting of ammonium hydroxide, ethylene diamine, propylene diamine and 1,3 diamino propane.
6. An anti-foulant composition consisting essentiallyof (I) a phenolic compound having the formula in which R is an alkyl group attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atoms, 11 is an integer having a value of between zero to 1 inclusive, and X is a substituent selected from the group consisting of hydrogen and a phenolic group having the formula in which R is an alkyl groupv attached to a carbon atom of the aromatic ring and contains between 4 to 12 carbon atombs, R" is a divalent hydrocarbon radical containing between 1 to 4 carbon atoms inclusive, Y is selected from the group consisting of hydroxyl and alkyl phenol, a and d are integers having a value of between zero to 15 inclusive, m and c are integers having a value of between zero to 1 inclusive, b is an integer having a value of between zero to 4 inclusive, and the sum totalof a and d is no more than 25, (II) the reaction product of a polyamine having the formula in which x is an integer having a value of between 1 to 10 inclusive, y is an integer having a value of between zero to 1 inclusive, and z is an integer having a value of between 1 to 10 inclusive, and a succinic compound selected from the group consisting of substituted succinic anhydrides having the formula and substituted succinic acids having the formula in which R' is selected from the group consisting of alkyl and alkenyl radicals having between 30 to 200 carbon atoms inclusive in the carbon chain and w is an integer having a value of between 1 to inclusive, and (III) N,N'- disalicylidene-1,2-propane diamine in which said phenolic compound, said reaction product and said N,N-disalicylidene-1,2-propane-diamine are each present in a quantity which is at least equal to of the total weight of said anti-foulant.
7. A composition as claimed by claim 6 in which said phenolic compound is present in a quantity of between 0.5 to 3 parts by weight for each part by weight of said N,N'-disalicylidene-1,2-propane.
8. A composition as claimed by claim 6 in which said phenolic compound is the condensate of formaldehyde, a nitrogen containing compound and an alkyl phenol having the formula R Rn R Rn
in which R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive, and n is an integer having a value of between zero to 1 inclusive.
11. A composition as claimed by claim 6 in which said alkyl phenol is t-octyl phenol.
12. A composition as claimed by claim 6 in which said phenolic compound is the condensate of formaldehyde and alkyl phenol having the formula ll. Rn
in which R is an alkyl group attached to a carbon atom of the aromatic ring of said phenol and contains between 4 to 12 carbon atoms inclusive, and n is an integer having a value of between zero and 1 inclusive.
13. A composition as claimed by claim 6 in which said reaction product has the formula in which R is selected from the group consisting of alkyl and alkenyl radicals having between 30 to 200 carbon atoms inclusive in the carbon chain, w is an integer having a value of between 1 to 5 inclusive, x and z are integers having a value of between 1 to 10 inclusive, and y is an integer having a value of between zero to 1 inclusive.
14. A composition as claimed by claim 6 in which said reactant product has the formula n-n n Um-ooo-BJ euro o 0-3 w in which R' is selected from the group consisting of alkyl and alkenyl radicals having between 30 to 200 carbon atoms inclusive, w is an integer having a value of between 1 to 5 inclusive, B is selected from the group consisting of hydrogen and in which x and z are integers having a value of between 1 to 10 inclusive, and y is an integer having a value of between zero to 1 inclusive.
15. A composition as claimed by claim 6 in which said polyamine is selected from the group consisting of diethylene triamine, pentaethylene hexamine, 1,3-diamino propane, 1,6-diamino hexane, triethylene tetramine, ethylene diamine, and propylene diamine.
References Cited UNITED STATES PATENTS Re. 26,330 1/ 1968 Colfer 208-48 2,962,442 11/1960 Andress 252-515 3,034,876 5/1962 Gee et al 44-70 3,068,083 12/ 1962 Gee et al. 44-62 3,132,085 5/1964 Summers 208-48 3,271,296 7/ 1966 Gonzalez 208-48 DELBERT E. GANTZ, Primary Examiner. G. E. SCHMITKONS, Assistant Examiner.
US645590A 1967-06-13 1967-06-13 Anti-foulant agents for petroleum hydrocarbons Expired - Lifetime US3437583A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US64559067A 1967-06-13 1967-06-13

Publications (1)

Publication Number Publication Date
US3437583A true US3437583A (en) 1969-04-08

Family

ID=24589633

Family Applications (1)

Application Number Title Priority Date Filing Date
US645590A Expired - Lifetime US3437583A (en) 1967-06-13 1967-06-13 Anti-foulant agents for petroleum hydrocarbons

Country Status (1)

Country Link
US (1) US3437583A (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492219A (en) * 1967-07-17 1970-01-27 Nalco Chemical Co Reducing fouling in refining of petroleum products by salicylidene additive
US3526673A (en) * 1968-05-13 1970-09-01 Pennwalt Corp Inhibiting popcorn polymer formation with tertiary amino dialkyl phenol compound
US3546097A (en) * 1968-12-27 1970-12-08 Texaco Inc Fouling inhibitors and processes for using them
FR2354380A1 (en) * 1976-06-07 1978-01-06 Chevron Res BASIC COMPOSITION OF MANNICH AND LUBRICATING OIL CONTAINING THIS ADDITIVE
US4456526A (en) * 1982-09-24 1984-06-26 Atlantic Richfield Company Method for minimizing fouling of heat exchangers
US4511453A (en) * 1984-03-21 1985-04-16 International Coal Refining Company Corrosion inhibition when distilling coal liquids by adding cresols or phenols
US4578178A (en) * 1983-10-19 1986-03-25 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a petroleum hydrocarbon or petrochemical
EP0203692A1 (en) * 1985-04-26 1986-12-03 Exxon Chemical Patents Inc. Fuel oil compositions
EP0261795A1 (en) * 1986-09-05 1988-03-30 Betz Europe, Inc. Methods for deactivating metallic species in hydrocarbon fluids
EP0267715A1 (en) * 1986-10-31 1988-05-18 Betz Europe, Inc. Compositions comprising alkoxylated mannich products and their use
US4775458A (en) * 1986-12-18 1988-10-04 Betz Laboratories, Inc. Multifunctional antifoulant compositions and methods of use thereof
US4775459A (en) * 1986-11-14 1988-10-04 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US4804456A (en) * 1986-12-18 1989-02-14 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US4847415A (en) * 1988-06-01 1989-07-11 Betz Laboratories, Inc. Methods and composition for deactivating iron in hydrocarbon fluids
US4883580A (en) * 1988-06-01 1989-11-28 Betz Laboratories, Inc. Methods for deactivating iron in hydrocarbon fluids
US4927519A (en) * 1988-04-04 1990-05-22 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium using multifunctional antifoulant compositions
US4927561A (en) * 1986-12-18 1990-05-22 Betz Laboratories, Inc. Multifunctional antifoulant compositions
US5139643A (en) * 1991-03-13 1992-08-18 Betz Laboratories, Inc. Phosphorus derivatives of polyalkenylsuccinimides and methods of use thereof
US5171421A (en) * 1991-09-09 1992-12-15 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5171420A (en) * 1991-09-09 1992-12-15 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5183554A (en) * 1991-09-09 1993-02-02 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5194620A (en) * 1991-03-13 1993-03-16 Betz Laboratories, Inc. Compositions of phosphorus derivatives of polyalkenylsuccinimides
US5194142A (en) * 1991-08-26 1993-03-16 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5641394A (en) * 1995-04-06 1997-06-24 Nalco/Exxon Energy Chemicals, L.P. Stabilization of hydrocarbon fluids using metal deactivators
EP0839782A1 (en) * 1996-10-30 1998-05-06 Nalco/Exxon Energy Chemicals, L.P. Process for the inhibition of coke formation in pyrolysis furnaces
US5783109A (en) * 1994-04-29 1998-07-21 Nalco/Exxon Energy Chemicals, L.P. Dispersion of gums and iron sulfide in hydrocarbon streams with alkyl phenol-polyethylenepolyamine formaldehyde resins
FR2839315A1 (en) * 2002-05-03 2003-11-07 Totalfinaelf France ADDITIVE FOR IMPROVING THERMAL STABILITY OF HYDROCARBON COMPOSITIONS
ES2245872A1 (en) * 2004-03-22 2006-01-16 Repsol Ypf, S.A. Composition of gas oil or fuel disposal stabilized means. (Machine-translation by Google Translate, not legally binding)
US20080241095A1 (en) * 2007-03-26 2008-10-02 Syrinek Allen R Antifoulant for hydrocarbon processing equipment
WO2009040584A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040585A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040582A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009074606A1 (en) * 2007-12-11 2009-06-18 Basf Se Hydrocarbylphenols as intake valve clean-up boosters

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962442A (en) * 1957-01-03 1960-11-29 Socony Mobil Oil Co Inc Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same
US3034876A (en) * 1959-09-22 1962-05-15 Socony Mobil Oil Co Inc Stabilized jet combustion fuels
US3068083A (en) * 1959-07-31 1962-12-11 Socony Mobil Oil Co Thermally-stable jet combustion fuels
US3132085A (en) * 1960-09-22 1964-05-05 Gulf Research Development Co Process for reducing formation of carbonaceous deposits on heat transfer surfaces
US3271296A (en) * 1965-03-01 1966-09-06 Betz Laboratories Process of heat transfer
USRE26330E (en) * 1968-01-02 Method for inhibiting deposit for- mation in hydrocarbon feed stocks

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE26330E (en) * 1968-01-02 Method for inhibiting deposit for- mation in hydrocarbon feed stocks
US2962442A (en) * 1957-01-03 1960-11-29 Socony Mobil Oil Co Inc Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same
US3068083A (en) * 1959-07-31 1962-12-11 Socony Mobil Oil Co Thermally-stable jet combustion fuels
US3034876A (en) * 1959-09-22 1962-05-15 Socony Mobil Oil Co Inc Stabilized jet combustion fuels
US3132085A (en) * 1960-09-22 1964-05-05 Gulf Research Development Co Process for reducing formation of carbonaceous deposits on heat transfer surfaces
US3271296A (en) * 1965-03-01 1966-09-06 Betz Laboratories Process of heat transfer

Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492219A (en) * 1967-07-17 1970-01-27 Nalco Chemical Co Reducing fouling in refining of petroleum products by salicylidene additive
US3526673A (en) * 1968-05-13 1970-09-01 Pennwalt Corp Inhibiting popcorn polymer formation with tertiary amino dialkyl phenol compound
US3546097A (en) * 1968-12-27 1970-12-08 Texaco Inc Fouling inhibitors and processes for using them
FR2354380A1 (en) * 1976-06-07 1978-01-06 Chevron Res BASIC COMPOSITION OF MANNICH AND LUBRICATING OIL CONTAINING THIS ADDITIVE
US4456526A (en) * 1982-09-24 1984-06-26 Atlantic Richfield Company Method for minimizing fouling of heat exchangers
US4578178A (en) * 1983-10-19 1986-03-25 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a petroleum hydrocarbon or petrochemical
US4511453A (en) * 1984-03-21 1985-04-16 International Coal Refining Company Corrosion inhibition when distilling coal liquids by adding cresols or phenols
EP0203692A1 (en) * 1985-04-26 1986-12-03 Exxon Chemical Patents Inc. Fuel oil compositions
EP0261795A1 (en) * 1986-09-05 1988-03-30 Betz Europe, Inc. Methods for deactivating metallic species in hydrocarbon fluids
US4749468A (en) * 1986-09-05 1988-06-07 Betz Laboratories, Inc. Methods for deactivating copper in hydrocarbon fluids
US4894139A (en) * 1986-09-05 1990-01-16 Betz Laboratories, Inc. Methods for deactivating copper in hydrocarbon fluids
US4810354A (en) * 1986-10-31 1989-03-07 Betz Laboratories, Inc. Bifunctional antifoulant compositions and methods
EP0267715A1 (en) * 1986-10-31 1988-05-18 Betz Europe, Inc. Compositions comprising alkoxylated mannich products and their use
US4775459A (en) * 1986-11-14 1988-10-04 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US4804456A (en) * 1986-12-18 1989-02-14 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US4775458A (en) * 1986-12-18 1988-10-04 Betz Laboratories, Inc. Multifunctional antifoulant compositions and methods of use thereof
US4927561A (en) * 1986-12-18 1990-05-22 Betz Laboratories, Inc. Multifunctional antifoulant compositions
US4927519A (en) * 1988-04-04 1990-05-22 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium using multifunctional antifoulant compositions
US4847415A (en) * 1988-06-01 1989-07-11 Betz Laboratories, Inc. Methods and composition for deactivating iron in hydrocarbon fluids
US4883580A (en) * 1988-06-01 1989-11-28 Betz Laboratories, Inc. Methods for deactivating iron in hydrocarbon fluids
US5139643A (en) * 1991-03-13 1992-08-18 Betz Laboratories, Inc. Phosphorus derivatives of polyalkenylsuccinimides and methods of use thereof
US5194620A (en) * 1991-03-13 1993-03-16 Betz Laboratories, Inc. Compositions of phosphorus derivatives of polyalkenylsuccinimides
US5194142A (en) * 1991-08-26 1993-03-16 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5183554A (en) * 1991-09-09 1993-02-02 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5171420A (en) * 1991-09-09 1992-12-15 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5171421A (en) * 1991-09-09 1992-12-15 Betz Laboratories, Inc. Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5783109A (en) * 1994-04-29 1998-07-21 Nalco/Exxon Energy Chemicals, L.P. Dispersion of gums and iron sulfide in hydrocarbon streams with alkyl phenol-polyethylenepolyamine formaldehyde resins
US5641394A (en) * 1995-04-06 1997-06-24 Nalco/Exxon Energy Chemicals, L.P. Stabilization of hydrocarbon fluids using metal deactivators
EP0839782A1 (en) * 1996-10-30 1998-05-06 Nalco/Exxon Energy Chemicals, L.P. Process for the inhibition of coke formation in pyrolysis furnaces
FR2839315A1 (en) * 2002-05-03 2003-11-07 Totalfinaelf France ADDITIVE FOR IMPROVING THERMAL STABILITY OF HYDROCARBON COMPOSITIONS
WO2003095593A1 (en) * 2002-05-03 2003-11-20 Total France Additive for improving the thermal stability of hydrocarbon compositions
US20050223627A1 (en) * 2002-05-03 2005-10-13 Frank Eydoux Additive for improving the thermal stability of hydrocarbon compositions
ES2245872A1 (en) * 2004-03-22 2006-01-16 Repsol Ypf, S.A. Composition of gas oil or fuel disposal stabilized means. (Machine-translation by Google Translate, not legally binding)
US7682491B2 (en) 2007-03-26 2010-03-23 Nalco Company Antifoulant for hydrocarbon processing equipment
US20080241095A1 (en) * 2007-03-26 2008-10-02 Syrinek Allen R Antifoulant for hydrocarbon processing equipment
CN101874101A (en) * 2007-09-27 2010-10-27 因诺斯佩克有限公司 Fuel compositions
JP2010540710A (en) * 2007-09-27 2010-12-24 インノスペック リミテッド Fuel composition
EP3492562A1 (en) * 2007-09-27 2019-06-05 Innospec Limited Fuel compositions
WO2009040585A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
US20100263261A1 (en) * 2007-09-27 2010-10-21 Jacqueline Reid Fuel compositions
WO2009040584A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
US20100281760A1 (en) * 2007-09-27 2010-11-11 Innospec Limited Fuel Compositions
US20100299992A1 (en) * 2007-09-27 2010-12-02 Jacqueline Reid Fuel compositions
JP2010540712A (en) * 2007-09-27 2010-12-24 インノスペック リミテッド Fuel composition
WO2009040582A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
JP2010540713A (en) * 2007-09-27 2010-12-24 インノスペック リミテッド Fuel composition
GB2453248B (en) * 2007-09-27 2011-11-23 Innospec Ltd Fuel compositions
AU2008303343B2 (en) * 2007-09-27 2013-04-04 Innospec Limited Fuel compositions
US8715375B2 (en) 2007-09-27 2014-05-06 Innospec Limited Fuel compositions
US9157041B2 (en) 2007-09-27 2015-10-13 Innospec Limited Fuel compositions
US9243199B2 (en) 2007-09-27 2016-01-26 Innospec Limited Fuel compositions
US9315752B2 (en) 2007-09-27 2016-04-19 Innospec Limited Fuel compositions
WO2009074606A1 (en) * 2007-12-11 2009-06-18 Basf Se Hydrocarbylphenols as intake valve clean-up boosters

Similar Documents

Publication Publication Date Title
US3437583A (en) Anti-foulant agents for petroleum hydrocarbons
US3442791A (en) Anti-foulant agents for petroleum hydrocarbons
US4578178A (en) Method for controlling fouling deposit formation in a petroleum hydrocarbon or petrochemical
CA1338461C (en) Multifunctional antifoulant compositions and methods of use thereof
US4749468A (en) Methods for deactivating copper in hydrocarbon fluids
US4927561A (en) Multifunctional antifoulant compositions
US3224957A (en) Process of reducing deposition of deposits on heat exchange surfaces in petroleum refinery operations
US3095286A (en) Stabilized distillate fuel oil
US3497334A (en) Liquid hydrocarbon combustion fuels
JPH02292392A (en) Intermediate fraction fuel having improved stability
US4828674A (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5110997A (en) Process for preventing fouling in the production of ethylene dichloride
US4810354A (en) Bifunctional antifoulant compositions and methods
US4569750A (en) Method for inhibiting deposit formation in structures confining hydrocarbon fluids
US5342505A (en) Use of polyalkenyl succinimides-glycidol reaction products as antifoulants in hydrocarbon process media
US4804456A (en) Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
US5139643A (en) Phosphorus derivatives of polyalkenylsuccinimides and methods of use thereof
US4663018A (en) Method for coke retardant during hydrocarbon processing
US3585123A (en) Acylated hydrocarbon succinates and uses thereof
US5194142A (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
CA2017187A1 (en) Antifoulant compositions and methods
US4487981A (en) Inhibiting polymerization of vinyl aromatic monomers
CA2067853A1 (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
US5292425A (en) Use of the reaction products of polyalkenylsuccinimides, triazoles, and aldehydes as anti foulants in hydrocarbon process media
US5783109A (en) Dispersion of gums and iron sulfide in hydrocarbon streams with alkyl phenol-polyethylenepolyamine formaldehyde resins