WO2003072531A1 - Procede et appareil pour recuperer des particules magnetiques dans un reacteur a phase de suspension - Google Patents
Procede et appareil pour recuperer des particules magnetiques dans un reacteur a phase de suspension Download PDFInfo
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- WO2003072531A1 WO2003072531A1 PCT/US2003/002888 US0302888W WO03072531A1 WO 2003072531 A1 WO2003072531 A1 WO 2003072531A1 US 0302888 W US0302888 W US 0302888W WO 03072531 A1 WO03072531 A1 WO 03072531A1
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- WO
- WIPO (PCT)
- Prior art keywords
- magnetic
- slurry
- particles
- container
- separator
- Prior art date
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
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- 239000006148 magnetic separator Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 46
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- 229910017052 cobalt Inorganic materials 0.000 claims 4
- 239000010941 cobalt Substances 0.000 claims 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/28—Magnetic plugs and dipsticks
- B03C1/286—Magnetic plugs and dipsticks disposed at the inner circumference of a recipient, e.g. magnetic drain bolt
-
- 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
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/226—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement internally, i.e. the particles rotate within the vessel
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
-
- 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
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00292—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant solids
- B01J2208/003—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant solids involving reactant slurries
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- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00654—Controlling the process by measures relating to the particulate material
- B01J2208/00672—Particle size selection
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- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00761—Discharging
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- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00769—Details of feeding or discharging
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- 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
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
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- 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
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/085—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy creating magnetic fields
- B01J2219/0852—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy creating magnetic fields employing permanent magnets
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- 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
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/089—Liquid-solid
Definitions
- This invention relates to processes and apparatus for employing continuous magnetic separation to separate strongly magnetic solid catalyst particles from a reactor slurry in a slurry phase reactor particularly while carrying out Fischer-Tropsch reactions.
- Slurry phase reaction systems have become popular for carrying out chemical reactions, particularly exothermal gaseous or gas-liquid reactions involving a particulate catalyst.
- the advantages of this type of reactor include temperature control, because the liquid acts as a heat sink for the exothermal heat of reaction.
- Another advantage is ease of addition and withdrawal of catalyst, as compared to a fixed bed catalytic reactor.
- Still another advantage of slurry phase reaction systems is the ability to maintain a uniform temperature in the slurry bed, allowing greater selectivity.
- Slurry phase reaction systems are often advanced versions of processes which have previously been carried out in fixed bed catalytic reactors.
- the liquid phase of the slurry may comprise either an inert liquid, a reactant, or a reaction product.
- a particulate catalyst may be a tablet or pellet such as an extrudate, or a powder, or some combination of these.
- the catalyst may be of a size, shape and density intended to be retained in the reactor and separated in a separation zone from liquids and gases rising through a slurry bed in a reactor or may be entrained in the liquid and possibly recycled through a pump.
- slurry phase reaction systems include Fisher-Tropsch synthesis wherein a gas phase comprising carbon monoxide and hydrogen is fed into a slurry phase comprising wax products of the synthesis and catalyst wherein various hydrocarbon products are produced.
- Iron based catalysts are often used for Fischer-Tropsch synthesis reactions.
- Methanol can also be synthesized from carbon monoxide and hydrogen in a slurry phase as taught by Mednick in U.S. 4,639,470 generally using an inert liquid phase with a copper catalyst suspended therein.
- solids separation has often been performed outside the reactor in elaborate filtering or settling systems
- Other slurry reaction systems have used batch operated mechanical filtration elements within the slurry reactor to remove catalytic particles from the slurry.
- Another slurry reaction system disclosed in U.S. 5,844,006 utilizes filter elements which are within the slurry reactor to remove catalyst particles from the slurry phase of Fischer- Tropsch reactions, and periodic back flushing to remove the solids.
- HGMS High Gradient Magnetic Separation
- HGMS High Gradient Magnetic Separation
- a magnetized filter element containing a matrix such as steel wool based on high magnetic field gradients created by the magnetized matrix.
- HGMS High Gradient Magnetic Separation
- a variant on the Kolm HGMS is U.S. 3,902,994 to Marston, which discloses a plurality of matrix containing elements on a carousel, so that one or more elements can be cleaned while another is in service.
- the concentration of catalyst in the slurry (20 or 30 wt. per cent) is higher than desirable as a feed-stock for high gradient magnetic separation which is best used as a polishing separator with concentrations of the magnetic fraction of the feed in the 2% to 3% range.
- Conventional HGMS methods are restricted when the concentration of magnetics in the feed exceeds this range, because of excessive capture-matrix loading which leads to poor non-magnetics weight yields. This effect has been discussed in the following paper which is hereby inco ⁇ orated herein by reference: R.R.
- Another type of magnetic separator separates particles in a slurry from each other according to their susceptibility or charge as opposed from removing particles from the liquid in the slurry as in the HGMS separators.
- This type of separator is useful for selective separation of components of complex particle systems.
- Such devices are often in the form of an elongated housing with a slurry feed at the top and a number of outlet channels at the bottom for collection of slurries concentrated with solids of differing magnetic properties.
- One such device, disclosed by Kelland in U.S. 4,261,815 utilizes a plurality of ferromagnetic rods located within the housing and oriented along the axis of the housing.
- each rod Downstream of each rod are four channels for collection of slurries relatively concentrated in particles having different magnetic properties.
- Another variant by Kelland is 4,663,029 in which a single rod is located outside and adjacent to an elongated canister parallel to the axis of the canister.
- the canister has an inlet at the top and a plurality of outlet ports at the bottom for collection of particles according to their size and magnetic susceptibility.
- a somewhat related separator is disclosed by Stelzer in 5,169,006, wherein a magnetic separator comprises an elongated housing with flow inlet at one end and a number of channels at the other end, with a three dimensional array of rods within the housing which are pe ⁇ endicular to the direction of flow.
- the rods are comprised of alternating ferromagnetic and non-ferromagnetic sections.
- a plurality of ferromagnetic rods are disposed at an angle between parallel and pe ⁇ endicular with the rods terminating at opposite sides of the housing.
- a force gradient is created between adjacent rods by providing an external magnetic field with a field direction parallel to the direction of slurry flow.
- triangular cross section rods were employed. Particles are deflected into the different channels by the rods.
- U.S. 5,868,939 Oder disclosed a continuous magnetic separator for breaking emulsions of immiscible liquids by magnetostatic coalescence.
- One embodiment of that device comprises a vertical separator means having an inlet below a top and above a bottom, outlets at the top and bottom for separately withdrawing a continuous phase and a coalesced phase containing a magnetic additive and a magnetic field in a horizontal plane pe ⁇ endicular to the direction of flow.
- the above device may comprise vertical magnetic rods onto which the magnetically doped dispersed phase coalesces and flows to the bottom of the separator where there is an interface between the continuous phase and the coalesced magnetically doped dispersed phase.
- slurry phase reactions such as Fischer-Tropsch synthesis conducted using catalyst particles
- a particularly desirable form of separation would be a device which acts as both a continuous clarifier and thickening device wherein a slurry stream would be continuously separated into a substantially catalyst free liquid product and a concentrated catalyst slurry. The slurry would be recycled to the reactor to recover catalyst.
- continuous flow separations are greatly preferred to batch and semi-batch separations such as filtration.
- a still further need is for a truly continuous magnetic separation apparatus and method which could be inco ⁇ orated within a slurry reactor.
- This invention provides methods and apparatus for conducting a reaction in a reactor having a slurry zone where the slurry comprises a liquid phase and a solid phase, wherein the solid phase of the slurry comprises solid magnetic particles, preferably strongly magnetic particles such as those exhibiting forms of collective magnetism, for example, ferromagnetism, antiferromagnetism, or supe ⁇ aramagnetism, and preferably paramagnetic particles with field induced moments greater than or equal to 1 emu/gm in the magnetic field employed in the continuous separator.
- the particles may range in size from nominally a millimeter down to sub-microns. Most preferably they range in size from a few hundred microns down to one micron.
- the upper limit on the particle size is determined by requirements for a stable flowable suspension. At this time, the lower limit on particle size is not known. Their concentration in the slurry fed to the separator should be low enough for the slurry to flow, most preferably lower than 50 Wt.% of the slurry.
- the liquid may be a reaction product or an inert carrier. Often one or more gaseous components are added to the reactor and react with each other in the slurry phase or with the liquid or solid phase.
- the solid particles are often catalyst particles. It is generally desired to remove the solid particles from the liquid phase, in order to recover the particles, upgrade the liquid, and/or recover the liquid.
- a preferred system for practice of the invention is the so-called slurry phase Fischer- Tropsch process in which synthesis gas comprising carbon monoxide and hydrogen is added to a slurry phase in a reactor which is at appropriate elevated temperature and pressure.
- the slurry phase is made of a liquid phase comprising hydrocarbons produced from the synthesis gas, including waxes.
- the solid phase comprises catalyst particles.
- a common catalyst family for Fischer-Tropsch synthesis comprise iron as a major component and are strongly magnetic.
- the liquid phase is a portion of the hydrocarbon product which is formed by the catalytic reaction of carbon monoxide and hydrogen.
- the liquid contains waxes that will generally be upgraded by refining processes. It is necessary to remove the catalyst particles from the liquid in order to facilitate further refining of the liquid as well as to recover the valuable catalyst for recycle.
- the invention employs methods and apparatus for using continuous magnetic separation to separate solid strongly magnetic particles from a reaction slurry in a slurry phase reactor.
- a continuous magnetic separator is an apparatus comprising a container having a slurry inlet, an overflow outlet, and an underflow outlet.
- the overflow outlet is disposed at approximately the top of separator
- the underflow outlet is disposed at approximately the bottom of the separator
- the slurry inlet is disposed to deliver slurry feed between the overflow and the underflow.
- the apparatus comprises at least one magnetic rod disposed approximately vertically within the container. Preferably, there is more than one magnetic rod.
- At least one rod may be made of a permanent magnet material or may be of a magnetically soft material such as carbon steel or ferritic stainless steel which is magnetized by an extemal magnetic field produced by an electromagnet, a superconducting magnet, or a permanent magnet, the field being substantially transverse to the substantially vertical orientation of the rods.
- the container should be made from a nonmagnetic material such as the austenitic stainless steels.
- a magnetic concentrate which is a concentrated slurry of magnetic particles, which flows out through the underflow outlet, while a clarified stream produced by removal of magnetic particles from the slurry flows out through the overflow outlet.
- It is preferable to control the performance of the separator by controlling the feed rate to the separator and varying the ratio of the magnetic concentrate withdrawal rate to the clarified stream withdrawal rate, the magnetic concentrate withdrawal rate being enough to force particles down the rods and out of the underflow outlet.
- a preferred embodiment of the continuous magnetic separator further comprises flow control means for controlling this ratio.
- flow control means examples include valves and flow restrictions that may be located in series with the overflow outlet and/or underflow outlet.
- the preferred embodiment still further comprises means for controlling the slurry feed rate to the separator.
- the preferred means for controlling feed rate includes valves, flow restrictions and pumps in series with the inlet.
- the preferred means of controlling the feed rate and ratio of underflow rate to overflow rate depends on the environment in which the continuous magnetic separator is used.
- the continuous magnetic separator is located within the reactor slurry zone so that the clarified liquid is removed from the slurry zone through an outlet from the reactor and the magnetic concentrate slurry is returned to the reactor slurry zone, preferably at a position near the bottom of the slurry zone.
- the slurry is preferably continuously pumped into the slurry inlet by a pump that draws slurry from the reactor slurry zone.
- the pump may be of the type that is internal to the reactor, such as a canned pump, or may be outside of the reactor drawing slurry through a nozzle extending through the reactor wall.
- the split between overflow and underflow is preferably controlled by control valves or flow restrictors on either the overflow outlet, the underflow outlet or both.
- the continuous magnetic separator is located outside of the slurry reactor.
- the slurry is made to continuously flow into the separator, the clarified liquid is taken as a product or for further processing and the magnetic concentrate is returned to the reactor slurry zone, preferably by pumping. It is often desirable to use more than one continuous separator in series, sending the clarified liquid to the inlet of a second separator.
- a secondary separation unit In either embodiment it may be desired to further remove additional magnetic particles from the clarified liquid in a secondary separation unit.
- a secondary separation unit is high gradient magnetic separation (HGMS) because HGMS is suitable for clarifying low concentration slurries and very fine particles.
- HGMS high gradient magnetic separation
- Alternative secondary separations such as mechanical filtration, preferably cross flow filtration are also acceptable.
- the solids recovered from the secondary separation unit may be recycled to the slurry zone of the reactor, however a valuable feature of the invention is that it is possible to recycle most of the magnetic particles which are removed in the continuous magnetic separator without recycling the smallest particles which are removed in the secondary separation unit. Removal of very fine particles is often important to prevent the build up of fines in the slurry reactor. In slurry reactions, it is usually observed that the particles undergo size reduction in the reactor, and fines thereby produced will accumulate if they are not selectively removed.
- Processing a simulated Fischer-Tropsch reactor slurry containing about 20% (wt.) of magnetic catalyst with a continuous magnetic separator according to this invention produced a clarified liquid of 0.2% (wt.) solids and a further clarified product produced by HGMS having less than 500 ppm of particles.
- the magnetic concentrate produced in the continuous magnetic separator was sufficiently concentrated to maintain an approximately constant concentration of catalyst in the slurry reactor.
- the magnetic separator is capable of treating very small particles.
- 78%> of the particles fed to the separator were smaller than 10 microns.
- Figure IA is a schematic front view of a continuous magnetic separator.
- Figure IB is a schematic top view of a continuous magnetic separator.
- Figure 2 is a schematic front view of a continuous magnetic separator showing the rods and magnetic particles during operation.
- Figure 3 shows a rod of the continuous magnetic separator during operation.
- Figure 4 is a flow diagram showing a continuously operating magnetic separator externally coupled with a slurry reactor.
- Figure 5 is a flow diagram showing a continuously operating magnetic separator internal to a slurry reactor.
- Figure 6A, 6B and 6C are an end view, a front view of a vertical section through the center, and a top view of a continuous magnetic separator housed within a horizontal solenoidal magnet with transverse access at the top and bottom of the separator midway along its length.
- the instant invention provides improved apparatus and methods for carrying out a slurry phase reaction, such as a Fischer-Tropsch reactor, where the slurry comprises a liquid and solid magnetic particles suspended therein.
- a slurry phase reaction such as a Fischer-Tropsch reactor
- the invention will be used in a gas- liquid-solid reaction system, where the slurry is kept agitated by the gas flow through the reactor.
- the solid phase of the slurry should comprise solid magnetic particles which preferably comprise strongly magnetic particles, most preferably those exhibiting forms of collective magnetism such as ferromagnetism, antiferromagnetism, or supe ⁇ aramagnetism and preferably paramagnetic particles with field induced magnetic moments greater than or equal to 1 emu/gm in the magnetic field employed in the continuous separator.
- the liquid may be a reaction product or an inert carrier. Often one or more gaseous components are added to the reactor and react with each other in the slurry phase or with the liquid or solid phase.
- the solid particles are often catalyst particles. It is generally desired to remove the solid particles from the liquid phase, in order to recover the particles, upgrade the liquid, and/or recover the liquid.
- a preferred system for practice of the invention is the so-called slurry phase Fischer- Tropsch process in which synthesis gas comprising carbon monoxide and hydrogen is added to a slurry phase in a reactor which is at appropriate elevated temperature and pressure.
- the slurry phase is made of a liquid phase comprising hydrocarbons produced from the synthesis gas, including waxes.
- the solid phase comprises catalyst particles.
- a common catalyst family for Fischer-Tropsch synthesis comprises iron as a major component and is strongly magnetic.
- the liquid phase is a hydrocarbon portion of the product which is synthesized from the catalytic reaction of carbon monoxide and hydrogen.
- the hydrocarbon liquid includes waxes which will generally be upgraded by refining processes.
- a continuous magnetic separator is a separator which achieves a steady state where it receives a continuous flow of slurry feed and continuously separates it into a clarified liquid overflow and an underflow magnetic concentrate of the strongly magnetic particles.
- Continuous is used in the ordinary chemical engineering sense which refers to the fact that in normal operation the separator achieves a steady state flow condition where the sum of the overflow and underflow rates equals the inlet flow rate.
- a continuous magnetic separator is specifically distinguished from batch separator where one component, generally the magnetic solid is retained in the separator and periodically removed.
- the continuous separator is also distinguished from a sequence or carrousel of batch reactors that are sequenced to simulate steady flow. In the context of this invention, continuous does not imply that a separator operate without occasional shutdowns or changes in operation.
- the continuous magnetic separator of this invention is also specifically distinguished from other so-called continuous magnetic separators that separate the magnetic solids from each other based on the magnetic properties of the solids.
- the continuous magnetic separator of this invention refers to a device that continuously separates a suspension into a clarified liquid stream and a concentrated slurry of the magnetic solids.
- a continuous magnetic separator is an apparatus comprising a container 10 having a slurry inlet 16, an overflow outlet 18, and an underflow outlet 14.
- the overflow outlet 18 is disposed at approximately the top of separator
- the underflow outlet 14 is disposed at approximately the bottom of the separator
- the slurry inlet 16 is disposed to deliver slurry feed between the overflow outlet and the underflow outlet.
- the apparatus contains at least one magnetic rod 12 disposed approximately vertically within the container. Preferably, there will be.more than one magnetic rod.
- the rods may be made of a permanent magnet material or may be a magnetically soft material such as carbon steel or the 400 series ferritic stainless steels which is magnetized by an extemal magnetic field produced by an electromagnet 28, a superconducting magnet, or a permanent magnet with the field substantially transverse to the vertical orientation of the rods.
- preferred materials to use for separating iron based Fischer-Tropsch catalyst are alnico, ceramic ferrites, samarium cobalt, and neodymium-iron boron permanent magnets as described in "Permanent Magnet Materials and Their Application” by Peter Campbell, Cambridge University Press, 1994.
- the container is made from a non-magnetic material such as 316 stainless steel.
- a slurry of magnetic particles is fed into the slurry inlet the magnetic particles are attracted to the magnetic rods and are made to slide down the magnetic rods by gravity and flow forces to form a magnetic concentrate, which is a concentrated slurry of magnetic particles, which flows out through the underflow outlet, while a clarified stream produced by removal of magnetic particles into the magnetic concentrate, exits through the overflow outlet.
- a preferred embodiment of the continuous magnetic separator further comprises flow control means for controlling the ratio of the rate of withdrawal of magnetic concentrate to the rate of withdrawal of the clarified stream.
- flow control means include valves 20, 22, and 24 or other flow restrictions such as orifices, flow restrictors and pumps whose use is well known to those skilled in the art, which may be located in series with the overflow outlet and/or underflow outlet.
- the preferred control means will depend on the particular embodiment of the invention, so that controls will not necessarily be needed for each line in each embodiment.
- Figure 2 shows a magnetic separator between the poles of an electromagnet during operation
- Figure 3 shows a single magnet rod of a magnetic separator.
- Rods 12 may be permanent magnets or may be a magnetically soft material such as carbon steel or the 400 series ferritic stainless steels, which is magnetized by an external magnetic field produced by an electromagnet 28 or a superconducting magnet or a permanent magnet with the field substantially transverse to the vertical orientation of the rods, and have a fringing field 36.
- the slurry flow is visualized as splitting into two flows filling the space around the rods. One, 31a, flows upward, the other, 31b, flows downward.
- Magnetic catalyst particles 38 are attracted to the rods 12 where they build a layer of particles 34 until sliding friction originating from the magnetic compressive force can no longer support their weight. The particles slide down the rods and form a magnetic concentrate 35 at the bottom of the rods. Once this weight is too great to be supported magnetically, a high concentration catalyst/wax slurry will flow continuously from the bottom of the separator (underflow outlet). A clarified slurry with a low concentration of magnetic particles flows from the overflow outlet 18.
- FIG. 6A, 6B, and 6C A somewhat different embodiment of a magnetic separator, of the type where the rods are magnetized by an external field, is shown in Figures 6A, 6B, and 6C.
- the previously described embodiments of continuous magnetic separators were illustrated with a container which has the general shape of a vertical cylinder with vertical rods disposed within the container which are generally parallel to the axis of the cylinder. Flow into the vertical cylinder could be axially, up or down, radially, or tangentially.
- FIGS 6A, 6B, and 6C An alternative embodiment is shown in Figures 6A, 6B, and 6C.
- Figures 6A and 6C are end and top views respectively and 6B is a view from the side of a vertical section through a magnetic separator contained within a solenoid magnet.
- a magnetic separator comprising a container 150 having two slurry inlets 154, an overflow outlet 151, and an underflow outlet 152.
- the container 150 has the general shape of a horizontal cylindrical with rods 156 hanging inside the container 150 in a generally vertical position which is pe ⁇ endicular to the axis of the cylinder.
- the container is surrounded by a solenoid magnet which generates a magnetic field transverse to the hanging rods.
- the solenoid magnet is shown comprising an iron frame 164 and pole pieces 160 and 162 surrounding the solenoid 158.
- the operation of the novel separator is governed by magnetic and flow forces under the influence of flow restrictors which force the majority of the flow out the underflow exit.
- the separator is designed to produce an overflow in which the concentration of magnetic particles is greatly diminished and an underflow carrying the greatest portion of the particles in a substantial portion of the incoming fluid.
- Flow restrictors are employed to force the greatest flow through the underflow exit.
- the flow moves in and around the rods more or less transverse to their lengths.
- the capture radius Whenever the magnetic particles in this flow come within a certain distance from the surfaces of the rods, called the capture radius, they will be attracted toward the rods thus separating the particles from the fluid which brought them near the rods. Some particles will collide with the rods and will stick to their surface, depending upon flow conditions around the rods. Others will be entrained in the flow moving to the underflow exit.
- the fluid from which the particles has been separated is lighter than the slurry and will rise in the separator and exit at the overflow outlet.
- the concentrated slurry is forced to flow out of the separator at the bottom.
- the ratio of the overflow rate and the underflow rates is adjusted by flow restrictors on the overflow and the underflow. This arrangement drags the majority of the particles out the underflow.
- the probability of capture on the magnetic rod in the continuous magnetic separator is related to the ratio of the time for the particle to migrate to the capture surface to the residence time in the separator. This is governed by the magnetic force on the particle, by the viscous drag on the particle, and by the time required by the liquid wax to move through the capture cell.
- V m is the velocity of particles directed toward the capture surface when the magnetic force and the viscous drag are equal.
- a dimensionless parameter can be defined which helps to identify the important physical parameters controlling the separation. It is given by
- C is the drag coefficient for motion of particles relative to the fluid, a flowing suspension of magnetic particles in a liquid
- A is the particle cross-sectional area transverse to the flow
- p f is the density of the fluid
- v the fluid underflow velocity relative to the particle
- m the particle mass
- dB/dx is the gradient of the magnetic field at the surface of the rod
- g is the acceleration due to gravity
- ⁇ is the coefficient of friction.
- the surface field strength is 850 gauss and the field gradient is 2700 gauss 2 /cm.
- the separator itself has an internal impedance to flow which changes with time until steady state flow conditions are developed.
- the slurry entering through inlet port 16 immediately encounters the magnetized rods. Magnetic particles flowing within a capture radius of the rods surface will migrate to the rod and stick to its surface, separating them from flow. As inlet slurry flow continues, more particles are captured and a layer of particles accumulates on the surfaces of the rods. Once the layer becomes sufficiently thick, the magnetic compressive force is unable to support its weight. Downward flow in the separator will, then, drag particles off of the rods. This is the balance expressed by the above inequality.
- the operation of the continuous magnetic separator is certainly more complex than the inequality expressed above and the inequality is not intended to be limiting on the method and bounds of the invention. That is, meeting the criteria does not guarantee acceptable operation and failure to meet the criterion does not guarantee failure.
- experimental testing is customarily employed to guide the design and operation of equipment such as is used in this invention. An example of the type of testing used is illustrated in Example 1, below. The theory expressed will be useful for minimizing the amount of testing that will be required.
- One preferred arrangement is to have a first separator with large diameter rods to produce an intermediate quality of clarified liquid followed by a second separator using the clarified liquid product from the first unit as its feed.
- the second separator preferably has more rods than the first unit and the rods preferably have a smaller diameter.
- R recycle ratio
- R recycle ratio
- the overflow rate is 98 cm 3 /sec when the underflow rate is 980 cm 3 /sec and the feed rate is 1078 cm3/sec.
- Figure 4 is a flow diagram of one preferred embodiment of the invention.
- Synthesis gas comprising hydrogen and carbon monoxide is added at the bottom of the reactor at line 51.
- Vapors are removed from the reactor through line 54.
- Slurry is drawn from the slurry zone 52 through line 60 into vapor liquid separator 58.
- Vapors are returned through line 56.
- the slurry flows through line 62 and then through valve 64 into the slurry inlet 66 of continuous magnetic separator 68.
- the slurry proceeds around the magnetic rods 70 such that the magnetic particles are attracted to the rods and then are caused to move down the surfaces of the rods by gravity and flow forces.
- the particles separated from the slurry form a magnetic concentrate 73 at the bottom of the continuous separator.
- the magnetic concentrate exits through line 71 to the inlet of pump 65 from where it is pumped back into the reactor to recycle the catalyst particles.
- the exit stream 71 is shown passing through a demagnetizing coil 77 which is energized through a power supply 78.
- the coil and supply are of the type supplied by R. B. Annis Co., Inc., Indianapolis, IN, and can be purchased from McMaster Carr Supply Company of Cleveland, Ohio.
- the demagnetization operation is optional. It can be employed to break up magnetic agglomerates for catalyst particles which exhibit hysteresis with a large remnant magnetization. Otherwise it is unnecessary.
- a clarified liquid 75 forms from the slurry with the magnetic particles removed at the top of the continuous magnetic separator.
- the clarified liquid exits through line 69 and then through valve 67 to a secondary separator 72 wherefrom a further clarified liquid is withdrawn through line 76 and additional magnetic particles are withdrawn through 74.
- the exit stream 74 from separator 72 passes through optional demagnetization coil 79 which is energized by power supply 80.
- a preferred secondary separator is a high gradient magnetic separator, though other filters may be used as well. Note that the secondary separator 72 is shown as a conceptual block and the feed and product arrows are not indicative that the process conducted therein is a continuous process. It is not as important that this process step be continuous since it is not integrated into the synthesis process.
- Operation of the separator 68 shown in Figure 4 is redundant.
- operation of the separator 68 is controlled by inlet valve 64, overflow valve 67, and slurry pump 65.
- Flow restrictors, such as valves or pipe orifices, and pumps are an integral part of this invention and are required for control of its operation. However, in most cases control devices are not necessary on all three connections to the separator, feed, overflow, and underflow.
- the valve 64 is primarily used to keep a constant slurry level in the reactor 52. Any two controls can be used and in the special case where flow from the column reactor is reasonably steady and sufficient to force flow through the separator, and the weight of the column of underflow is sufficient to cause it to flow back into the column reactor, 50, only one control valve is required.
- the clarified liquid produced by the continuous magnetic separator should preferably contain less than 1.5% catalyst particles, more preferably less than 0.8 % catalyst particles, and still more preferably less than 0.25%. About 0.25% corresponds approximately with the fresh catalyst addition rate required to maintain constant catalyst activity in the Fischer-Tropsch reactor, so it is particularly desirable to operate at about this product clarity.
- the required performance of the secondary separator will depend on the requirements of the downstream processing planned for the waxy product.
- a level in the range of from about 5 ppm to about 500 ppm will be desirable.
- the catalyst which remains in the clarified liquid is selectively enriched in fines. It will therefore be desirable in some applications to include part or all of the catalyst recovered in the secondary separator to be among the catalyst that is withdrawn from service and not returned to the reactor.
- the continuous magnetic separator is shown in Figure 4 without an external magnet, though it could just as well be of the type shown in Figure 1 with an extemal magnet, such as an electromagnet or a superconducting magnet or permanent magnets. Also, while the reactor and reaction system have been described in terms a Fischer-Tropsch reactor, the invention could just as well be another reaction carried out in a slurry comprising a liquid and a strongly magnetic solid slurried therein.
- the need for a secondary separator depends solely on the way that the waxy liquid will be used. In some case, the product made from the continuous magnetic separator may not need to be processed through a secondary separator.
- Figure 5 shows a second preferred embodiment of the invention, characterized by a continuous magnetic separator 102 mounted within a Fischer-Tropsch reactor 100, preferably within the slurry zone 104.
- Synthesis gas 118 is pumped into the reactor 100 and reacts with strongly magnetic catalyst particles present in the slurry zone to form hydrocarbon liquids including waxes which is the liquid component of the slurry.
- Slurry is pumped into the slurry inlet 112 of the continuous magnetic separator 102 from the discharge of pump 120 which draws its inlet from the slurry zone 104.
- the pump 120 is shown exterior to the reactor, though it can also be a pump, such as a canned pump, which is submerged within the reactor, preferably within the slurry zone.
- Strongly magnetic particles of iron based Fischer-Tropsch catalyst are drawn to magnetic rods 103 and are made to slide down the rods by gravity and flow forces to form a magnetic concentrate 105 at the bottom of the continuous magnetic separator which flows through the underflow outlet 114 through demagnetizing coal 81 and valve 116 into the slurry zone 104 of the reactor.
- the exit stream 114 is shown passing through a demagnetizing coil 81 which is energized through a power supply 82.
- the coil and supply are of the type described above.
- the demagnetization operation is optional. It can be employed to break up magnetic agglomerates for catalyst particles which exhibit hysteresis with a large remnant magnetization. Otherwise it is unnecessary.
- Valve 116 could be replaced by a flow restrictor such as a pipe of fixed inside diameter.
- Clarified liquid 107 is formed from the slurry and flows through the top of the continuous magnetic separator to the overflow outlet 110 and then through valve 108.
- the clarified liquid flows into separator 122.
- the gaseous product is returned to the top of the reactor through 121 where it joins the other gaseous product and exits through line 106.
- the preferred method of controlling the ratio of clarified liquid to magnetic concentrate is manipulation of valve 108 and pump 120.
- Valve 116 is not used. If the separator 102 operates at the same pressure as the reactor 100, the flow through the separator is controlled by manipulation of valves 108 and 116.
- the clarified liquid flow into a secondary separator 126, wherefrom a further clarified liquid 130 is withdrawn and the magnetic solids 128 are withdrawn through demagnetizing coal 83.
- the exit stream 128 from separator 126 passes through demagnetization coil 83 which is energized by power supply 84.
- the demagnetizing coil 83 is optional. If the catalysts 128 exhibit hysteresis with a large value of remnant magnetism and are to be returned to the reactor, then demagnetizing coil 83 can be used to break up magnetic agglomerates if desired. Otherwise, the coil would not be used.
- the rods be permanent magnets rather than being magnetized by an external magnet. It is certainly possible, however to use an external superconducting magnet, though the cost would probably be higher because of the large size of the magnets placed outside the Fischer-Tropsch reactor. It is certainly possible that large-scale high temperature superconductors would substantially reduce the cost of this option.
- Example 1 Testing of a continuous magnetic separator - Room Temperature Tests on a Continuous Magnetic Separator using an external electromagnet.
- a continuous magnetic separator was tested in the laboratory at conditions chosen to simulate a Fischer-Tropsch reaction slurry. The tests were run with an iron-based catalyst that is a precipitated iron catalyst with a atomic ratio of 100 Fe: 4.4 Si. The catalyst was supplied in the unactivated form. Hexadecane was chosen to be used as an analog liquid for room temperature experiments. The analog was chosen to have a room temperature density and viscosity similar to the F-T waxes at process temperatures.
- Hexadecane has a density of 0J733 g/ml, and a viscosity of 3.3 cP, which are very close to the densities (0.625-0.9317 g/ml) and viscosities (2.4-11.9 cP) for F-T waxes reported in the literature (see, Zhou, P. Z., "Status Review of Fischer-Tropsch Slurry Reactor Catalyst/Wax Separation Techniques," Prepared by Bums and Roe Services Co ⁇ oration for the U.S. DOE Pittsburgh Energy Technology Center under Contract No. DE-AC22-89PC88400, Subtask 43.02, February 1991; and Marano, J.J. and Holder, G.D.
- the catalyst was activated in Durasyn® 164 Polyalphaolefin (BP Amoco Chemicals Company, Naperville, IL) at a concentration of 50 Wt.% solids.
- the activated catalyst slurry was diluted with hexadecane to a concentration of 20 Wt.% solids. Hexadecane and Durasyn were therefore in a ratio of 3:1, which had a density of OJ85 g/ml and a viscosity of 6.5 cP.
- the continuous magnetic separator container was a 23 cm long brass vessel with a 1.8 cm x 3.5 cm internal cross section and contained carbon steel rods which were nine inches long and 0.063 inches in diameter. Either 2 or 4 rods were used.
- the tests were conducted in a continuous loop circuit, where slurry was circulated out of a reservoir, pumped to the inlet of a continuous magnetic separator, separated into a clarified liquid overflow and a magnetic concentrate underflow, recombined and returned to the reservoir.
- the overflow and underflow were periodically sampled and analyzed.
- Teflon tubing was used to return the clarified liquid and underflow streams to the beaker reservoir. Every 30 minutes samples of the product and underflow streams were withdrawn for analysis. After analysis was completed (approximately 5-10 minutes), the samples were returned to the feed container. The recycle ratio was adjusted by means of pinch clamps on the tubing for the overflow and underflow streams. An exact recycle ratio could not be chosen precisely because only coarse adjustments were possible with the pinch clamps.
- Catalyst concentrations as low as 0.1 % were obtained. No separation was noted without - an applied magnetic field. The tests processed up to 650 cell exchanges showing no accumulation of catalyst build up.
- Example 3 Separation with Permanent Magnets.
- Treating the clarified liquid with high gradient magnetic separation (HGMS) to further reduce catalyst concentration has shown that the concentration can be reduced at least as low as 500 ppm.
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Abstract
Priority Applications (1)
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AU2003214956A AU2003214956A1 (en) | 2002-02-01 | 2003-01-31 | Process and apparatus for recovery of magnetic particles in a slurry phase reactor |
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US35332402P | 2002-02-01 | 2002-02-01 | |
US60/353,324 | 2002-02-01 |
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PCT/US2003/002888 WO2003072531A1 (fr) | 2002-02-01 | 2003-01-31 | Procede et appareil pour recuperer des particules magnetiques dans un reacteur a phase de suspension |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110039952A1 (en) * | 2008-03-14 | 2011-02-17 | Kazuhiko Tasaka | METHOD OF REMOVING MAGNETIC PARTICLE FROM FISCHER-TROPSCH SYNTHETIC CRUDE OIL AND METHOD OF PRODUCING FISCHER-SYNTHETIC CRUDE OIL (As Amended) |
CN102146296A (zh) * | 2011-01-30 | 2011-08-10 | 山东大学 | 一种基于可磁分离负载型磷钨酸铯盐催化剂的氧化脱硫方法 |
CN106622039A (zh) * | 2016-12-12 | 2017-05-10 | 中北大学 | 合成聚α‑烯烃(PAO)的反应分离一体化工艺及装置 |
EP2192987B1 (fr) * | 2007-09-21 | 2020-04-22 | Qiagen GmbH | Dispositif et procédé de traitement de liquides avec des particules magnétiques |
CN112246193A (zh) * | 2020-11-11 | 2021-01-22 | 北京大学 | 非均相反应中磁性颗粒循环反应并连续分离的设备及方法 |
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US5827903A (en) * | 1996-01-31 | 1998-10-27 | The United States Of America As Represented By The Department Of Energy | Separation of catalyst from Fischer-Tropsch slurry |
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2003
- 2003-01-31 WO PCT/US2003/002888 patent/WO2003072531A1/fr not_active Application Discontinuation
- 2003-01-31 AU AU2003214956A patent/AU2003214956A1/en not_active Abandoned
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US4085037A (en) * | 1975-12-29 | 1978-04-18 | Union Carbide Corporation | Process for separation of non-magnetic particles with ferromagnetic media |
US4605678A (en) * | 1984-03-12 | 1986-08-12 | Mobil Oil Corporation | Separation of catalyst from slurry bubble column wax and catalyst recycle |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2192987B1 (fr) * | 2007-09-21 | 2020-04-22 | Qiagen GmbH | Dispositif et procédé de traitement de liquides avec des particules magnétiques |
US20110039952A1 (en) * | 2008-03-14 | 2011-02-17 | Kazuhiko Tasaka | METHOD OF REMOVING MAGNETIC PARTICLE FROM FISCHER-TROPSCH SYNTHETIC CRUDE OIL AND METHOD OF PRODUCING FISCHER-SYNTHETIC CRUDE OIL (As Amended) |
CN102146296A (zh) * | 2011-01-30 | 2011-08-10 | 山东大学 | 一种基于可磁分离负载型磷钨酸铯盐催化剂的氧化脱硫方法 |
CN102146296B (zh) * | 2011-01-30 | 2013-07-31 | 山东大学 | 一种基于可磁分离负载型磷钨酸铯盐催化剂的氧化脱硫方法 |
CN106622039A (zh) * | 2016-12-12 | 2017-05-10 | 中北大学 | 合成聚α‑烯烃(PAO)的反应分离一体化工艺及装置 |
CN112246193A (zh) * | 2020-11-11 | 2021-01-22 | 北京大学 | 非均相反应中磁性颗粒循环反应并连续分离的设备及方法 |
CN112246193B (zh) * | 2020-11-11 | 2024-05-17 | 北京大学 | 非均相反应中磁性颗粒循环反应并连续分离的设备及方法 |
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