US20200399545A1 - Method and device for treatment of liquid hydrocarbons - Google Patents

Method and device for treatment of liquid hydrocarbons Download PDF

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Publication number
US20200399545A1
US20200399545A1 US16/977,024 US201816977024A US2020399545A1 US 20200399545 A1 US20200399545 A1 US 20200399545A1 US 201816977024 A US201816977024 A US 201816977024A US 2020399545 A1 US2020399545 A1 US 2020399545A1
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United States
Prior art keywords
pressure
vessel
pump
sodium
liquid
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.)
Abandoned
Application number
US16/977,024
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English (en)
Inventor
Thomas Andreas Guenther
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ECOFUEL TECHNOLOGIES Ltd
Original Assignee
Gusher Management SL
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Filing date
Publication date
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Assigned to GUSHER MANAGEMENT S.L. reassignment GUSHER MANAGEMENT S.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GUENTHER, Thomas Andreas
Publication of US20200399545A1 publication Critical patent/US20200399545A1/en
Assigned to ECOFUEL TECHNOLOGIES LTD reassignment ECOFUEL TECHNOLOGIES LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GUSHER MANAGEMENT S.L.
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/271—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
    • B01F27/2711—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator provided with intermeshing elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/811—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles in two or more consecutive, i.e. successive, mixing receptacles or being consecutively arranged
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • 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
    • C10G29/04—Metals, or metals deposited on a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects

Definitions

  • the invention relates to a method and a device for treatment of liquid hydrocarbons including purification and desulfurization of liquid hydrocarbons using metallic sodium.
  • HDS Hydrogen-Desulfurization-Processes
  • HDS processes are based on addition of hydrogen, use of Ni—Mo or Co—Mo catalysts and are carried out in high-pressure reactors.
  • sulphur compounds are integrated in hydrocarbon chains in very different structures (e.g. Mercaptans, Sulfides, Thiophenes, Alkylated Thiopenes, Thiphenols, Benzothiopenes, Dibenzothiopenes, etc.) resulting in, that some sulphur components are quite easy and others are very difficult to remove.
  • SDD plants In comparison to HDS plants, size or throughput capacity of SDD plants can be adapted to the volume requirements of smaller fuel production plants, which makes economically feasible on site cleaning and desulphurisation of products possible even for small decentralized located fuel production plants.
  • the SDD-Process like it was first published in 1952, envisages removing sulphur from fuel products, reducing unpleasant odors and improving storage stability by using sodium dispersion.
  • the SDD-Process removes only a portion (predominantly mercaptans and sulfides) of the different sulphur components present in fuels.
  • sodium particles are subject to an agglomerating effect, from which, referred to exploitability, even significantly greater disadvantages arise than from the demixing effect.
  • the agglomeration effect quickly destroys part of the ultra fine comminution in the dispersion.
  • the smallest particles are particularly affected by the agglomeration effect.
  • the degree of effectiveness and exploitability of the sodium content for the treatment process is particularly determined by the amount of the finest particles.
  • the agglomeration effect starts immediately when finishing the dispersion preparation process and also concerns finest particles that have not settled but are in the flow of liquid.
  • the effective and exploitable reaction surface can already be reduced by 10-20% after a very short time.
  • Method and device disclosed herein has been developed with the aim of providing a plant technology for a sodium treatment process which optimizes exploitation of sodium input and seeks to be economically operated in industrial dimensions.
  • the device is composed of a vessel, having attached a pressurizable pump- and dispersing circuit comprising of a pumping unit and a dispersing unit and a flow pipe and a throttle valve.
  • liquid hydrocarbons can circulate constantly through the pressurizable pump- and dispersing circuit at adjustable temperatures, adjustable pressure rates and adjustable residence time, which has shown unexpected effects in addition to the expectable effects like process simplification and energy savings.
  • the highest amount of finest sodium particles are provided not only in the moment of input of the sodium dispersion into the device, but are constantly produced and kept on best during entire treatment time.
  • reaction products formed during the treatment process in which highly reactive ultra fine sodium particles may be locked in, will repeatedly torn open.
  • Sodium can be introduced via pressure lock sluice directly into the device.
  • Sodium may be introduced into the device in solid form or in molten form.
  • the liquid sodium metal is dispersed directly in the stream of the hydrocarbons to be treated.
  • ultra fine dispersed sodium particles for optimized exploitation conditions of sodium are formed and provided throughout the whole treatment time.
  • Highest reactivity surface of the sodium is not only available in the beginning, it is kept up throughout the whole treatment time.
  • the device disclosed in this application is based on the use of the SDD method, which is the state of the art since many years, but provides a plant technology showing significantly increased economic efficiency, significantly shorter treatment times, and new additional fields of application.
  • this device is simply scalable and therewith can provide a basis for use of the SDD-Process method in industrial dimensions.
  • FIG. 1 is a side schematic view illustrating an example of a possible embodiment of the device with individual pumping and dispersing units wherein the presentation of heaters or heat insulation is omitted.
  • FIG. 2 is a side schematic view illustrating an example of a possible embodiment of the device with a combined pumping and dispersing unit wherein the presentation of heaters or heat insulation is omitted.
  • FIG. 3 is a side view schematic view illustrating an example of a possible embodiment of a combined pumping- and dispersing unit comprising of one pumping impeller and two rotor-stator-disperger modules mounted in line on the same shaft in the same casing.
  • FIG. 1 there is shown a device for sodium treatment of liquid hydrocarbons for the purpose of purification, desulfurization and reducing of aromatic compounds.
  • Liquid hydrocarbons which should be anhydrous and preferably purified from coarse impurities and non-molecularly bound impurities, have to be introduced through entry 1 ) in liquid state into the vessel 4 ).
  • the liquids should be heated in the vessel 4 ) to the desired treatment temperature before the sodium input.
  • sodium can be introduced through input sluice 2 ) into the vessel 4 ).
  • fluid temperatures above 280° C. should prevail before entering the sodium through input sluice 2 ) into the vessel 4 ).
  • the hot fluid in the device then continuously flows from the lower part of the vessel 4 ) through pumping unit 7 ) through dispersing unit 8 ) through flow pipe 10 ) and through throttle valve 5 ), and is subjected to strong mechanical forces, high shear and adjustable pressure before returning at entry point 12 ) into vessel 4 ).
  • the minimal, stoichiometric sodium amount required in ppm is equivalent to 1.5 times the ppm of the sulphur contained in the hydrocarbon liquid, but also depends on the treatment objective and possible other ingredients that could react with sodium.
  • Sodium may be introduced into the device in solid or liquid state via the sodium input sluice 2 ), located at the upper part of the vessel 4 ).
  • the entered sodium immediately participates in the circulation through the pump- and dispersing circuit 7 ) 8 ) 10 ) 5 ) 12 ) and is kept from this moment, together with the oil to be treated, continuously in circulation and dispersing state throughout the entire treatment time.
  • vessel 4 If oils in the range of middle distillate, boiling on from 160° C., are treated, vessel 4 ) has only to be kept under pressure of 4-6 bar, what is usually enough to maintain the oils in liquid state at treatment temperature, at 280° C.
  • the pressure created by pumping unit 7 ) can be kept or can be adjusted to a desired value, until fluids return to the vessel 4 ).
  • the necessary treatment time of liquid hydrocarbons in the device can amount, from the moment of sodium input, between 2 and 120 minutes, but using optimal sodium amounts and optimal pressure adjustments a treatment time between 5 and 20 minutes is sufficient.
  • the oil and reaction products can leave the device through outlet 6 ), located at the lower part of the vessel 4 ), or through outlet 9 ), located after dispersing unit 8 ) in the pump- and dispersion circuit.
  • the liquids can be decompressed through valve 6 ) or valve 9 ) into a settling tank, into a centrifuge, or preferably into a distillation device, whereby heat previously supplied to the treatment process, can also be used for the distillation.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US16/977,024 2018-03-05 2018-05-30 Method and device for treatment of liquid hydrocarbons Abandoned US20200399545A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AU2018201581A AU2018201581B2 (en) 2018-03-05 2018-03-05 Method and Device for Treatment of of Liquid Hydrocarbons
AU2018201581 2018-03-05
PCT/EP2018/064235 WO2019170263A1 (fr) 2018-03-05 2018-05-30 Procédé et dispositif pour le traitement d'hydrocarbures liquides

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/064235 A-371-Of-International WO2019170263A1 (fr) 2018-03-05 2018-05-30 Procédé et dispositif pour le traitement d'hydrocarbures liquides

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/450,972 Division US12043805B2 (en) 2018-03-05 2023-08-16 Method and device for treatment of liquid hydrocarbons

Publications (1)

Publication Number Publication Date
US20200399545A1 true US20200399545A1 (en) 2020-12-24

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Family Applications (4)

Application Number Title Priority Date Filing Date
US16/977,024 Abandoned US20200399545A1 (en) 2018-03-05 2018-05-30 Method and device for treatment of liquid hydrocarbons
US18/450,972 Active US12043805B2 (en) 2018-03-05 2023-08-16 Method and device for treatment of liquid hydrocarbons
US18/749,322 Active US12281264B2 (en) 2018-03-05 2024-06-20 Method and device for treatment of liquid hydrocarbons
US19/096,377 Active US12540283B2 (en) 2018-03-05 2025-03-31 Method and device for treatment of liquid hydrocarbons

Family Applications After (3)

Application Number Title Priority Date Filing Date
US18/450,972 Active US12043805B2 (en) 2018-03-05 2023-08-16 Method and device for treatment of liquid hydrocarbons
US18/749,322 Active US12281264B2 (en) 2018-03-05 2024-06-20 Method and device for treatment of liquid hydrocarbons
US19/096,377 Active US12540283B2 (en) 2018-03-05 2025-03-31 Method and device for treatment of liquid hydrocarbons

Country Status (6)

Country Link
US (4) US20200399545A1 (fr)
EP (2) EP4495210A3 (fr)
AU (2) AU2018201581B2 (fr)
CA (1) CA3093178A1 (fr)
ES (1) ES3013907T3 (fr)
WO (1) WO2019170263A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018201581B2 (en) * 2018-03-05 2024-12-12 Ecofuel Technologies Ltd Method and Device for Treatment of of Liquid Hydrocarbons
CN112098261B (zh) * 2020-08-03 2022-03-11 中国原子能科学研究院 一种用于高温高压下液体金属钠蒸发的装置及操作方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130251613A1 (en) * 2012-03-21 2013-09-26 H R D Corporation Apparatus, system, and method for converting a first substance into a second substance

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA774540A (en) * 1967-12-26 National Distillers And Chemical Corporation Continuous process for sodium dispersions
GB759283A (en) 1952-12-24 1956-10-17 British Petroleum Co Improvements relating to the refining of petroleum hydrocarbons
US3166492A (en) 1960-12-13 1965-01-19 Degussa Desulfurization of hydrocarbons
CH595432A5 (en) * 1974-09-13 1978-02-15 Frank Barry Haskett Removal of sulphur cpds. from oil fractions
AU2018201581B2 (en) * 2018-03-05 2024-12-12 Ecofuel Technologies Ltd Method and Device for Treatment of of Liquid Hydrocarbons

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130251613A1 (en) * 2012-03-21 2013-09-26 H R D Corporation Apparatus, system, and method for converting a first substance into a second substance

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Publication number Publication date
US20250230367A1 (en) 2025-07-17
AU2025201757A1 (en) 2025-04-03
AU2018201581B2 (en) 2024-12-12
EP4495210A3 (fr) 2025-04-09
WO2019170263A1 (fr) 2019-09-12
US12043805B2 (en) 2024-07-23
EP3762474B8 (fr) 2025-02-19
US12281264B2 (en) 2025-04-22
EP4495210A2 (fr) 2025-01-22
US20240417630A1 (en) 2024-12-19
AU2018201581A1 (en) 2019-09-19
CA3093178A1 (fr) 2019-09-12
US20230392081A1 (en) 2023-12-07
EP3762474A1 (fr) 2021-01-13
US12540283B2 (en) 2026-02-03
EP3762474B1 (fr) 2024-12-25
EP3762474C0 (fr) 2024-12-25
ES3013907T3 (en) 2025-04-15

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