WO2014177924A1 - Additif pour le traitement d'hydrocarbures de poids moléculaire élevé et son procédé d'obtention - Google Patents

Additif pour le traitement d'hydrocarbures de poids moléculaire élevé et son procédé d'obtention Download PDF

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Publication number
WO2014177924A1
WO2014177924A1 PCT/IB2014/000635 IB2014000635W WO2014177924A1 WO 2014177924 A1 WO2014177924 A1 WO 2014177924A1 IB 2014000635 W IB2014000635 W IB 2014000635W WO 2014177924 A1 WO2014177924 A1 WO 2014177924A1
Authority
WO
WIPO (PCT)
Prior art keywords
additive
condensed
additive according
rpm
sulfuric acid
Prior art date
Application number
PCT/IB2014/000635
Other languages
English (en)
Spanish (es)
Inventor
Carlos Alberto Pareja Uribe
Edgar Francisco Pantoja Agredo
Héctor Julio PICON HERNÁNDEZ
Jesús Alberto CASTRO GUALDRON
Judith Rocio SANTA JAIMES
Original Assignee
Ecopetrol S.A.
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 Ecopetrol S.A. filed Critical Ecopetrol S.A.
Priority to MX2015010762A priority Critical patent/MX2015010762A/es
Publication of WO2014177924A1 publication Critical patent/WO2014177924A1/fr

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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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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

Definitions

  • the present invention relates to an additive for dispersing high molecular weight hydrocarbons, which comprises the synthesis of condensed alkylphenolsulfonic acids and aminoalkylphenols, together with a hydrogen donor compound of high thermal stability, as well as the process of obtaining said additive .
  • This additive is characterized by being a stable, neutral pH mixture and having a synergistic effect on the stability of asphaltenes, which improves the thermal conversion processes of hydrocarbon streams with high molecular weight.
  • the present invention relates to an additive for dispersing high molecular weight hydrocarbons, used to mitigate and inhibit fouling by asphalt precipitation and subsequent coke formation, during thermal conversion processes of hydrocarbon streams with high molecular weight.
  • the additive of the present invention is used to:
  • the additive substantially reduces the problems of obstruction caused by the formation of coke in the equipment involved in the operation such as ovens, plates of the fractional towers and transfer lines, allowing the unit to operate more reliably with its respective increase in the factor of service.
  • Coke is an insulating material and its deposition in the tubes significantly increases the resistance to heat transfer from the wall outside of the tubes towards the material that circulates inside. By decreasing the thickness of the coke layer inside the furnace tubes, the operating temperatures decrease, which implies a lower gas consumption.
  • the additive improves and maintains the stability of processed hydrocarbons, allowing it to operate at higher severities to obtain higher yields on valuable products.
  • the additive is a dispersing agent of high molecular weight hydrocarbons, particularly asphalts, which allows to process loads with greater fouling power, without significantly reducing yields
  • Coke deposits formed during the application of the additive are of porous and fragile consistency, making their removal easier and increasing the life of the furnace tubes and towers of the towers. Additionally, solvent consumption decreases, since the additive decreases the viscosity of the breasts produced in the thermal conversion processes.
  • Asphalt agglomerates are promoters of coke formation, and generate obstructions in the furnace tubes, in the plates, beds of the fractional towers and in the transfer lines, of the thermal conversion units. Additionally, asphaltene agglomerates are responsible for the increase in the viscosity of products of interest such as breas. These inconveniences require reducing the severity of operation of the units and subjecting them to periodic cleaning, resulting in low yields of valuable products and high maintenance costs.
  • additives generally consist of one or several peptizing agents, thermo-cracking initiators, deactivators, hydrogen donors or polymerization blockers, all mixed with surfactants and dissolved in a vehicle, in order to maintain the homogeneity and stability of the additive.
  • additives marketed as asphaltene dispersants are usually classified according to the surfactant they contain, in anionic, non-ionic and polymeric.
  • the additive of the present invention aims to at least partially overcome the four limitations indicated above, as presented in the detailed description of the invention.
  • the present patent application represents an advance in relation to previously filed patent applications WO2008068624, WO2008068628, since the present invention relates a synergistic composition of alkylated aromatics that mitigate and inhibit fouling during thermal conversion processes for hydrocarbon streams of high molecular weight Its active components are linked directly to the reaction system, blocking the condensation of free radicals, and thus preventing the formation of deposits of asphaltic material, which are the promoters of coke. Likewise, it acts as a stabilizing agent in hydrocarbon streams rich in asphaltenes. The main differences are:
  • the additive is of high thermal stability and neutral pH.
  • the additive has high storage stability.
  • the high molecular weight hydrocarbon dispersant additive of the present invention uses phenolic extracts, naphtha, sulfuric acid, mono or diethanolamine, formaldehyde and a hydrogen donor compound, preferably naphthenic based, as raw materials. All these compounds are obtained from refinery streams without prior treatment, or separation and concentration stages, reducing the production costs of the additive.
  • the additive consists of three active substances: 1. Condensed alkylphenylsulfonic acids
  • the aliphenylsulfonic acids used as active substance in the additive of the present invention are compounds of formula type (I):
  • R- ⁇ is a C 15 to C 8 alkyl radical inherent in the molecule
  • R 2 is a C 10 to C 14 alkyl radical, preferably a C 12 alkyl.
  • the aliphenolsulfonic acids are synthesized from phenolic extracts obtained from the phenol plants, with naphtha from the oligomerization of butane and propane, in a reaction catalyzed by sulfuric acid, followed by a condensation with 37% formaldehyde by weight.
  • aminoalkylphenols used as the second active substance in the additive of the present invention are compounds of formula type (II):
  • R 3 is a C15 to C 18 alkyl radical inherent in the molecule
  • R 4 is a C10 to C 14 alkyl radical, preferably a C-
  • the aminoalkylphenols are synthesized from phenolic extracts obtained from the phenol plants, with naphtha from the oligomerization of butane and propane, in a reaction catalyzed by sulfuric acid, and subsequently amined with mono or diethanolamine.
  • the hydrogen donor compound used as the third active substance in the additive of the present invention is selected from the group comprising tetralins, anthracene derivatives and naphthenic bases.
  • a naphthenic base is selected.
  • the additive of the present invention obtains from the synergistic mixture between 5 to 20% condensed alkylphenolsulfonic acids, 5 to 20% of the aminoalkylphenols and between 60 and 90% of the naphthenic base.
  • the mixture obtained between 10 to 12% condensed alkylphenolsulfonic acids, 10 to 12% aminoalkylphenols and 76 to 80% of the naphthenic base is preferred.
  • the additive of the present invention does not need neutralization steps as it has a neutral pH, usually in the range of 6.5-7.5.
  • the additive is of a stable, homogeneous nature, and does not exhibit decomposition even under operating temperatures above 480 ° C.
  • the production methodology is divided into two phases
  • the decantation of the aqueous phase is preferably carried out at a temperature between 22-30 ° C, by controlled cooling.
  • monoethanolamine is dosed between 12 to 13.5% m, keeping the temperature variable controlled between 65-78 ° C and ensuring mixing between 300-500 rpm.
  • the dosage of monoethanolamine is finished, the dosage of formaldehyde at 37% m is started between 12 to 14.5% m, maintaining the same initial conditions for decantation.
  • the decantation of the aqueous phase is preferably carried out at a temperature between 22-30 ° C, by controlled cooling.
  • concentrated sulfuric acid (98% m) is measured between 6.5 to 8.5% m keeping the temperature variable controlled between 67-79 ° C and ensuring mixing between 300-500 rpm.
  • the decantation process of the aqueous phase is started preferably at a temperature between 22-30 ° C, by controlled cooling.
  • formaldehyde is dosed at 37% m between 12 to 15.5% m, keeping the temperature variable controlled between 65-78 ° C and ensuring mixing between 300-500 rpm.
  • the naphthenic base is mixed between 60 and 90% m maintaining the variable temperature and speed of the impeller between 27-38 ° C and 600-750 rpm and add between 5 and 20% m of the condensed alkylphenolsulfonic acids. Maintaining the same mixing conditions, the aminoalkylphenol is added between 5 and 20% m.
  • the additive substantially reduces the problems of obstruction or fouling caused by the formation of coke in the equipment involved in the operation such as ovens, plates of the fractional towers and transfer lines, allowing the unit to operate more reliably with its respective increase in The service factor. • Fuel gas savings
  • the coke formed from the agglomeration of asphaltenes and its deposition in the tubes significantly increases the resistance to heat transfer from the outer wall of the tubes to the material that circulates inside, because it is an insulating material.
  • the operating temperatures decrease, which implies a lower consumption of combustible gas.
  • the additive is characterized by a neutral pH (6.5-7.5)
  • the present additive for handling neutral pH guarantees the integrity and reliability of the process system because it does not require special metallurgy for its application. Likewise, the storage system does not require special treatment and metallurgy.
  • This additive is characterized by presenting corrosion values on the copper foil of the order of 1.A.
  • the additive improves and maintains the stability of processed hydrocarbons, allowing it to operate at higher severities to obtain higher yields on valuable products.
  • the additive is a heavy hydrocarbon dispersing agent, especially asphalt, which allows to process loads with greater fouling power without significantly reducing yields.
  • Coke deposits formed during the application of the additive are of porous and fragile consistency, making their removal easier and increasing the life of the furnace tubes and towers of the towers. Additionally, solvent consumption decreases, since the additive decreases the viscosity of the breasts produced in the thermal conversion processes.
  • Example 2 Between 13 and 14% m of 37% formaldehyde was mixed with the organic phase extracted in Example 2. The mixture was brought to a temperature between 70 and 80 ° C for two (2) hours.
  • the additive of the present invention was tested in a viscoreductive unit of a refinery.
  • the injection was made in the furnace loading line, and only a storage tank for the additive, a metering pump and a pipe connecting the storage tank with the injection point were required.
  • the additive was stored during the injection time at atmospheric pressure and temperature, without altering its homogeneity, stability, pH or dispersing effect.
  • EXAMPLE 7 Effect of the additive on operating temperatures and pressure drop.
  • the additive allowed the viscoreductive industrial unit to operate at greater severities, producing an increase in the yields of valuable products. Additionally, when the injection of the additive was completely suspended, it was confirmed that the additive has a residual effect, see Figure 4.
  • the additive of the present invention decreases the viscosity in visco-reduced bottoms, increasing the ⁇ / ⁇ (Determination of Mix Number) of the obtained breasts, which in turn implies a significant decrease in solvent consumption in the preparation of breas with lower viscosity see Figure 5.
  • the additive of this application is a synergistic compound of alkylated aromatics that mitigate and inhibit fouling during thermal conversion processes for high molecular weight hydrocarbon streams.

Landscapes

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

Abstract

La présente invention concerne un additif destiné à être utilisé dans des flux d'hydrocarbures lourds. Sa composition repose sur deux composés actifs principaux constitués par des acides alkylphénolsulfoniques condensés et des aminoalkylphénols respectivement, et en outre sur un troisième composé qui est une base naphténique et qui agit comme un composé donneur d'hydrogènes. Ces trois composés ensemble forment une substance synergique à grande homogénéité, à stabilité élevée à des pH neutres et parviennent principalement à disperser les molécules d'asphaltène, empêchant la formation d'agglomérats. Ledit effet implique d'autres avantages, comme la diminution des temps de fonctionnement des unités de conversion thermique, une économie d'énergie, une diminution des coûts d'entretien et de fonctionnement, entre autres.
PCT/IB2014/000635 2013-04-30 2014-04-29 Additif pour le traitement d'hydrocarbures de poids moléculaire élevé et son procédé d'obtention WO2014177924A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
MX2015010762A MX2015010762A (es) 2013-04-30 2014-04-29 Aditivo para el procesamiento de hidrocarburos de alto peso molecular y su proceso de obtencion.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CO13109529A CO7100263A1 (es) 2013-04-30 2013-04-30 Aditivo para el procesamiento de hidrocarburos de alto peso molecular y su proceso de obtención
CO13109529 2013-04-30

Publications (1)

Publication Number Publication Date
WO2014177924A1 true WO2014177924A1 (fr) 2014-11-06

Family

ID=51843225

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2014/000635 WO2014177924A1 (fr) 2013-04-30 2014-04-29 Additif pour le traitement d'hydrocarbures de poids moléculaire élevé et son procédé d'obtention

Country Status (3)

Country Link
CO (1) CO7100263A1 (fr)
MX (1) MX2015010762A (fr)
WO (1) WO2014177924A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100082A (en) * 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
EP0824142A2 (fr) * 1996-08-12 1998-02-18 Nalco/Exxon Energy Chemicals, L.P. Prévention de dépÔts d'encrassement dans les laveurs caustiques
WO2002072737A2 (fr) * 2001-03-09 2002-09-19 Exxonmobil Research And Engineering Company Desemulsifiant de petroles bruts, a base d'acide sulfonique aromatique
WO2008068628A2 (fr) * 2006-12-06 2008-06-12 Ecopetrol S.A. Additif anticokéfiant stabilisant d'asphaltène et procédé d'obtention de celui-ci
WO2008068624A2 (fr) * 2006-12-06 2008-06-12 Ecopetrol S.A. Additifs antigommes, antisalissures et dispersants d'asphalte et procédé d'obtention de ceux-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100082A (en) * 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
EP0824142A2 (fr) * 1996-08-12 1998-02-18 Nalco/Exxon Energy Chemicals, L.P. Prévention de dépÔts d'encrassement dans les laveurs caustiques
WO2002072737A2 (fr) * 2001-03-09 2002-09-19 Exxonmobil Research And Engineering Company Desemulsifiant de petroles bruts, a base d'acide sulfonique aromatique
WO2008068628A2 (fr) * 2006-12-06 2008-06-12 Ecopetrol S.A. Additif anticokéfiant stabilisant d'asphaltène et procédé d'obtention de celui-ci
WO2008068624A2 (fr) * 2006-12-06 2008-06-12 Ecopetrol S.A. Additifs antigommes, antisalissures et dispersants d'asphalte et procédé d'obtention de ceux-ci

Also Published As

Publication number Publication date
CO7100263A1 (es) 2014-10-31
MX2015010762A (es) 2016-05-09

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