WO2017129655A1 - Système d'exploitation du bitume et procédé associé - Google Patents

Système d'exploitation du bitume et procédé associé Download PDF

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Publication number
WO2017129655A1
WO2017129655A1 PCT/EP2017/051607 EP2017051607W WO2017129655A1 WO 2017129655 A1 WO2017129655 A1 WO 2017129655A1 EP 2017051607 W EP2017051607 W EP 2017051607W WO 2017129655 A1 WO2017129655 A1 WO 2017129655A1
Authority
WO
WIPO (PCT)
Prior art keywords
bitumen
conduit
gases
ashes
solid
Prior art date
Application number
PCT/EP2017/051607
Other languages
English (en)
Inventor
Giacomo Fernando Rispoli
Original Assignee
Eni Spa
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 Eni Spa filed Critical Eni Spa
Publication of WO2017129655A1 publication Critical patent/WO2017129655A1/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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/017—Combinations of electrostatic separation with other processes, not otherwise provided for
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/70—Incinerating particular products or waste
    • F23G2900/7013—Incinerating oil shales
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44—Details; Accessories
    • F23G5/46—Recuperation of heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/05—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste oils
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/20—Sulfur; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/60—Heavy metals; Compounds thereof

Definitions

  • the present invention relates to a system for the exploitation of bitumen and the related process.
  • the present invention relates to a system for the exploitation of the bitumens produced in the hydroconversion processes of heavy hydrocarbon residues, preferably in the Eni Slurry Technology (EST) processes owned by Eni.
  • EST Eni Slurry Technology
  • the present invention may be applied in the sector of refining heavy crude oils or other hydrocarbon sources, whose heavier processing residues or bitumens have a high metal content. Said metals are already contained in the crude oils fed to the refining system and/or in the heavy hydrocarbon residues fed to the hydroconversion plants; or they are the metals contained in the hydroconversion catalysts; finally they may be the result of undesired corrosion phenomena within the refining and/or hydroconversion processes.
  • the present invention may be applied in plants that could gain an advantage from the recovery of said metals and/or from the combustion of bitumen for producing high pressure steam.
  • heavy crude oils, bitumens or residues mean crude oils or derivatives (semi-processed products) in whose composition the hydrocarbon content having a boiling point greater than or equal to 500°C is predominant.
  • Products that have a high content of metals deriving from the refining of heavy crude oils are usually used as fuel either in refining plants or in other heavy industries, for example cement works.
  • Solutions used for the transformation of bitumens from hydroconversion plants are usually gasification plants, in which such bitumens are diluted in the charge to the gasifier in very low percentages (maximum between 5% and 10%), and whose main aim is not the recovery of the metals.
  • bitumens Another way of transforming bitumens is to exploit them as combustible material for producing heat in the form of steam by feeding them to a boiler.
  • Boilers allow the whole production of bitumen to be treated as it is, produced in
  • hydroconversion plants and in particular produced by EST. Furthermore, through the use of such boilers it is possible to totally recover the metals, such as molybdenum or other metals, in the form of oxides, reducing the variable costs of the plant, thanks to the reuse of molybdenum in the preparation of the precursor of the hydroconversion catalyst, preferably EST, starting from the ashes themselves. Furthermore, through combustion of the bitumen it is possible to exploit the enthalpy contribution by producing high pressure steam which can partially replace the hot-oil system used in hydroconversion processes, such as EST processes.
  • a further object of the present invention is that of the total recovery of the metals contained in the ashes deriving from the combustion of the bitumen produced in a hydroconversion process for the purpose of reusing the metals in the reformulation of the catalyst or in the economic exploitation of the same ashes in a metal recovery unit.
  • the subject matter of the present invention comprises a system for the exploitation of a bitumen produced in a hydroconversion process of heavy hydrocarbon residues, preferably in an Eni Slurry Technology (EST) hydroconversion process, said system comprising:
  • one or more boilers for burning the bitumen in which at least one pre-heater is located said boilers having a feed conduit for the bitumen, an air feed conduit, an output conduit of the combustion gases and a discharge conduit of the ashes and solid residues; said pre-heater having a water feed conduit and a steam outlet conduit;
  • one or more denitrification units for the abatement of the nitrogen oxides (DeNOx) and carbon monoxide, each connected in series to each boiler through the outlet conduit of the combustion gases; said denitrification unit having an outlet conduit of the denitrified gases and a conduit for the discharge of ashes and solid residues; one or more electrostatic precipitators (ESPs) for the reduction of the solid particulate from the denitrified gases, each connected in series to each DeNOx unit through the outlet conduit of the denitrified gases; said precipitator having an outlet conduit of the treated gases and a discharge conduit of the ashes and solid residues;
  • ESPs electrostatic precipitators
  • FGD flue gas desulphurization
  • further subject matter of the present invention comprises a process for the exploitation of a bitumen produced in a hydroconversion process of heavy hydrocarbon residues, preferably in an Eni Slurry Technology (EST) hydroconversion process, said process comprising:
  • AP high pressure steam
  • the system and the process described and claimed allow the in situ disposal of the bitumen produced in a hydroconversion process, with particular application to the EST process, fully exploiting its enthalpy contribution.
  • the ashes and solid residue recovered from the electrofilters which contain metals such as Mo, Ni and V and a percentage of coke, may be recovered in a metal reclaimer and the molybdenum can be completed reused in the hydroconversion plant.
  • the high pressure steam thus produced would partially substitute the hot oil system saving on other fixed and variable costs of the hydroconversion processes.
  • the overall heat recovery system of the hydroconversion processes would also be further optimized with this layout. In the layout of hydroconversion processes, and in particular of EST processes, there are some equipments that operate at high temperature, like for example the Hot High
  • the process and system described and claimed allow generating high-pressure steam (40 bar at temperatures higher than 400°C), by means of the heat of combustion that is obtainable by the claimed and described treatment of bitumen, and said high-pressure steam can substitute the diathermic oil used in the pipelines.
  • the diathermic oil In a hydroconversion process, preferably EST process, the diathermic oil must reach and keep the operative temperatures, preferably up to a maximum of 400°C due to stability constraints, and to this aim it is necessary to use a dedicated oven, a system of vessels and pumps in a closed circuit.
  • the condensations at high pressure derived from the pipelines of the hydroconversion process can be recirculated to the system according to the present invention for the subsequent regeneration of the High-Pressure Steam, with a consequent reduction of the use of boiler feed water and simultaneously limiting the generation of further effluents to be treated.
  • Figure 1 shows a simplified, preferred, diagram of the invention, wherein the bitumen produced in an EST process (A, 1 ) is fed to a combustion system (B) which includes the handling, storage and recovery of the solids contained in the bitumen.
  • Figure 2 shows a preferred embodiment, developed in more detail, of the system described and claimed.
  • the system comprises one or more boilers (E) for burning the bitumen.
  • Said boilers have a bitumen feed conduit (1 ), an air feed conduit (6), a combustion gas outlet conduit (12) and a discharge conduit of the ashes and solid residues (15).
  • Said pre-heaters (not shown in Figure 2) have a water feed conduit (Boiler Feed Water BFW, 10) and a high pressure steam outlet conduit (3).
  • the bitumen is fed to the boiler in a temperature range comprised between 170°C and 270 °C, preferably comprised between 190°C and 240°C.
  • the bitumen is possibly preheated both in the starting step in an external pre-heater (C) fed with a clean dedicated fuel, and under normal operating conditions of the unit.
  • the preheating temperatures vary from 170°C to 270°C, preferably from 190°C to 240°C.
  • the combustion takes place in the boiler using air as the comburent substance, which may possibly be preheated both in the starting step in an external pre-heater (D) fed with a dedicated clean fuel, and under normal operating conditions of the unit.
  • the boiler which operates at atmospheric pressure, the hot fumes generated during combustion transfer heat to the boiler feed water (BFW, 10) for generating steam.
  • the boiler generates steam at a suitable pressure for the heat level established by the temperature of the combustion unit.
  • the pressure of the steam produced is typically high pressure, 30- 40 kg/cm 2 g. It is also possible to generate superheated steam.
  • the air is preferably preheated before being fed to the boilers with part of the heat generated by the combustion itself.
  • the bitumen is preferably preheated before being fed to the boilers.
  • the bitumen enters the boiler and through burning generates the necessary heat for generating the high pressure steam and preheating the air.
  • the discharge gases generated in the starting pre-heaters are combined with the first discharge gas for subsequent treatment.
  • the combustion gas leaving the boilers and cooled is fed to one or more denitrification units, each connected in series to each boiler, for the abatement of the nitrogen oxides (DeNOx, F) and carbon monoxide.
  • the denitrification unit has an outlet conduit for the denitrified gases (13) and a discharge conduit for the ashes and solid residues (16).
  • the denitrified gas is then directly fed to one or more electrostatic precipitators (ESPs) (G) for the reduction of the solid particulate from the denitrified gases, each connected in series to each DeNOx unit through the outlet conduit of the denitrified gases.
  • the precipitator (G) has an outlet conduit for the treated gases (14) and a discharge conduit for the ashes and solid residues (16).
  • the treated gas is then directly sent to one or more flue gas desulfurization (FGD) units (H) for the reduction of sulfur dioxide.
  • FGD flue gas desulfurization
  • Each FGD unit is connected in series to each ESP unit through the treated gas outlet conduit.
  • the FGD unit has an outlet conduit for the desulfurized gases (2), which are clean gases, and a discharge conduit for the ashes and solid residues (17).
  • the DeNOx, ESP and FGD units have the object of producing a gas with a content of sulfurized and nitrified products and particulate below the maximum concentrations permitted by law for gaseous emissions into the atmosphere.
  • the metals contained in the ashes and solid residues produced with the system and process described and claimed are in the form of oxides.
  • Said oxides deriving from the combustion of bitumen may be recovered with different methods known in the state of the art, preferably such as recovery through acid attack, leaching, extraction with solvents and treatments with peroxides. Once recovered, they are used in the preparation of the precursor for the catalyst of hydroconversion processes, preferably EST.
  • bitumen to be exploited with the present invention is generated from the fraction of reagents not converted in the slurry phase.
  • the inert contents in bitumen comprise metals, such as molybdenum, nickel and vanadium that are to be recovered with the ashes and solid residues generated in combustion with the system described and claimed herein, for producing high pressure steam.
  • the present invention further relates to a process for the exploitation of a bitumen produced in a hydroconversion process of heavy hydrocarbon residues, preferably in an Eni Slurry Technology (EST) hydroconversion process.
  • EST Eni Slurry Technology
  • the bitumen is burned with air and the heat developed is exploited for generating high pressure steam (AP steam).
  • AP steam high pressure steam
  • the combustion generates a combustion gas, ashes and a solid residue.
  • Said combustion gas is directly subjected to a treatment for reducing the nitrogen oxides and carbon monoxide, generating a denitrified gas, ashes and a second solid residue.
  • said denitrified gas is subjected directly to a treatment for reducing the solid particulate, generating a treated gas and a third solid residue.
  • the bitumen (1 ) is fed to a pre-heater (C) using a clean fuel (5) and producing heat which heats the bitumen, and a secondary discharge gas (7).
  • the comburent air (6) is likewise preheated in the pre-heater (D) also in this case burning a clean starting fuel (5) and generating a secondary discharge gas (8).
  • the preheated air and bitumen are then fed to the boilers (E).
  • the secondary gases (7, 8) can possibly be added to the first discharge gas (12) and are then subsequently treated, together, in the subsequent DeNOx, ESP and FGD units.
  • Said process is preferably performed with the system for exploiting a bitumen described and claimed herein.
  • the burner of the boiler at the temperature of 200°C and 2 barg.
  • about 120 MW of thermal power is generated, which is transferred into the boiler to the BTW producing superheated steam at 40 barg.
  • the metals are recovered in the form of oxides with the ashes.
  • the waste combustion gases are treated and sent into the atmosphere with concentrations of pollutants within legal limits.

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

Abstract

La présente invention concerne un système d'exploitation du bitume produit lors d'un un processus d'hydroconversion de résidus d'hydrocarbures lourds, qui comprend une ou plusieurs chaudières pour brûler le bitume ; une ou plusieurs unités de dénitrification pour la réduction des oxydes d'azote (DeNOx) et du monoxyde de carbone ; un ou plusieurs précipitateurs électrostatiques (ESP) pour réduire les particules solides présentes dans les gaz dénitrifiés ; une ou plusieurs unités de désulfuration de gaz de combustion (FGD) pour réduire le dioxyde de soufre ; une ou plusieurs unités pour récupérer les métaux contenus dans les résidus solides et les cendres.
PCT/EP2017/051607 2016-01-27 2017-01-26 Système d'exploitation du bitume et procédé associé WO2017129655A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITUB2016A000372A ITUB20160372A1 (it) 2016-01-27 2016-01-27 Sistema di valorizzazione dei bitumi e relativo procedimento
IT102016000008040 2016-01-27

Publications (1)

Publication Number Publication Date
WO2017129655A1 true WO2017129655A1 (fr) 2017-08-03

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IT (1) ITUB20160372A1 (fr)
WO (1) WO2017129655A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5277795A (en) * 1989-06-13 1994-01-11 Thornhill Denis H Process and apparatus for recovering heavy metal from carbonaceous material
US5525317A (en) * 1994-11-04 1996-06-11 The Babcock & Wilcox Company Ammonia reagent application for NOX SOX and particulate emission control
WO2003068368A1 (fr) * 2002-02-15 2003-08-21 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Systeme de combustion generateur de vapeur et methode de reduction des emissions par enrichissement en oxygene
US20130075303A1 (en) * 2010-04-13 2013-03-28 IFP Energies Nouvelles Process for hydroconversion of petroleum feedstocks via a slurry technology allowing the recovery of metals from the catalyst and from the feedstock using a coking step

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5277795A (en) * 1989-06-13 1994-01-11 Thornhill Denis H Process and apparatus for recovering heavy metal from carbonaceous material
US5525317A (en) * 1994-11-04 1996-06-11 The Babcock & Wilcox Company Ammonia reagent application for NOX SOX and particulate emission control
WO2003068368A1 (fr) * 2002-02-15 2003-08-21 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Systeme de combustion generateur de vapeur et methode de reduction des emissions par enrichissement en oxygene
US20130075303A1 (en) * 2010-04-13 2013-03-28 IFP Energies Nouvelles Process for hydroconversion of petroleum feedstocks via a slurry technology allowing the recovery of metals from the catalyst and from the feedstock using a coking step

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Publication number Publication date
ITUB20160372A1 (it) 2017-07-27

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