CN110180471A - A kind of paste state bed reactor and reaction system for F- T synthesis - Google Patents
A kind of paste state bed reactor and reaction system for F- T synthesis Download PDFInfo
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- CN110180471A CN110180471A CN201910456696.1A CN201910456696A CN110180471A CN 110180471 A CN110180471 A CN 110180471A CN 201910456696 A CN201910456696 A CN 201910456696A CN 110180471 A CN110180471 A CN 110180471A
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 110
- 239000007788 liquid Substances 0.000 claims description 52
- 238000011010 flushing procedure Methods 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 36
- 238000010992 reflux Methods 0.000 claims description 35
- 239000007921 spray Substances 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- 230000008676 import Effects 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 11
- 230000000712 assembly Effects 0.000 claims description 9
- 238000000429 assembly Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007600 charging Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 38
- 230000000694 effects Effects 0.000 description 10
- 238000013461 design Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000002826 coolant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008258 liquid foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique
Abstract
The present invention relates to a kind of paste state bed reactors and reaction system for F- T synthesis, reactor includes reactor body, the gas distributor of reactor body bottom is set, several groups heat-transfering device in reactor body and downspout matched with heat-transfering device are set, liquid-solid separation device is equipped between two groups of heat-transfering devices, the gas-solid washing separation device of reactor head is set, and reaction system includes reactor and matched filtering-rinsing module and wash.Compared with prior art, the present invention can effectively increase target product yield with commercial scale Fischer-Tropsch synthetic, reduce catalyst attrition and its separating difficulty with product.
Description
Technical field
The present invention relates to Fischer-Tropsch synthesis devices, more particularly, to a kind of paste state bed reactor for F- T synthesis and instead
Answer system.
Background technique
F- T synthesis (Fischer-Tropsch Synthesis, abbreviation FTS) be it is a kind of using group VIII metal (such as iron,
Cobalt) synthesis gas (carbon monoxide and hydrogen) converts fischer-tropsch product by catalyst (mainly hydro carbons further includes hydroxy-aldehydic acid ketone etc.)
Catalysis reaction.Fischer-Tropsch synthesis device is the key equipment of fischer-tropsch synthesis process, mainly there is fixed bed and slurry bed system two at present
Kind form.For traditional fixed bed reactors although simple process, temperature control is difficult, and catalyst easily ties carbon, operating cost compared with
It is high.Paste state bed reactor not only overcomes drawbacks described above, but also the mixing of its gas-liquid-solid three-phase is abundant, and mass-and heat-transfer effect is excellent
It is different, obtain extensive attention and application.
The industrial application of Fischer-Tropsch paste state bed reactor has quite long history, early in nineteen fifty-three Germany Rheinpreussen
Equal companies have built up First demonstration plant semi-industrial, but since international energy demand at that time changes from coal to petroleum, the dress
It sets and does not continue industrial amplification.South Africa Sasol company is on the basis of using for reference German paste state bed reactor the 1980s
The exploitation of syrup state bed Fischer Tropsch reactor is started, nineteen ninety builds up the pilot-plant of 75 barrels/day in Sasolburg, builds within 1996
At 5 meters of diameter, the industrial reactor of 2500 barrels/day, become first industrialized public affairs of realization paste state bed reactor in the world
Department.In addition, the U.S. Exoon, Rentech, Syntroleum have carried out the research and development of syrup state bed Fischer Tropsch reactor.
Fischer-Tropsch paste state bed reactor and the core of corollary system exploitation are to provide good reaction environment and effective product-
Catalyst separation method, background of related are as follows:
1. gas distributor: R.Schafer waits (Bubble size distributions in a bubble
column reactor under industrial conditions.Experimental Thermal and Fluid
Science, 2002,26:595-604) discovery gas distributor form is tested to slurry bed system especially penetration height gas below
Bubble distribution has significant effect, and good gas distributed effect is important to preventing reaction zone bottom overtemperature and distributor blocking from having
Meaning.Patent CN1283349C discloses a kind of paste state bed reactor using nozzle and quadratic distribution plate, and jet expansion has one
A spherical device for preventing slurries from flowing backwards, to solve the problems, such as that distributor blocking and gas are unevenly distributed.Its main problem is
Structure of distributor is complex not convenient for safeguarding, and the blocking of nozzle easily occurs in system shutdown.
2. false bottom: patent CN1233454C discloses a kind of false bottom design with tedge, the vacation bottom and gas distributor
Distance it is smaller, catalyst is not easy to deposit in reactor bottom, hot-spot problem caused by avoiding therefore.Its main problem
It is the mechanical strength that false bottom aperture will affect false bottom.
3. heat-transfering device: Marretto and Krishna (Design and optimization of a multi-stage
bubble column slurry reactor for Fischer-Tropsch.Catalysis Today,2001,66:241-
248) a kind of pipe heat exchanger for Fischer-Tropsch paste state bed reactor is proposed, by the pumping chamber Liang Ge and the casing being connected thereto
Tube bank composition, boiler feedwater are flowed downward by cannula center, are returned up from the annulus of periphery.Patent CN100522335C
A kind of cooling tube apparatus for Fischer-Tropsch synthesis device is disclosed, the cooler is by multiple groups tube bundle assembly and the collection being attached thereto
General pipeline composition, every group of tube bundle assembly are made of 4 or 6 casings and the pumping chamber Liang Ge being attached thereto, which can simplify cold
But the disassembly of pipe with reinstall.For above-mentioned cooler due to its design feature, heat exchanger tube layout density in the reactor is lower,
In the case where catalyst concn is higher or contingency condition, its exchange capability of heat is relatively limited.
4. downspout.Patent US6201031 discloses a kind of paste state bed reactor with downspout, proposes downspout
The calculation method of working principle and its slurries conveying capacity.Commercial test results disclosed in patent US5382748 show downspout
Effect is significantly improved to the axial concentration distribution of catalyst and Temperature Distribution.However above-mentioned patent does not refer to downspout
Key issues of size, arrangement, design principle.
5. liquid-solid separation device and filtration and washing component.Patent CN1233453C discloses a kind of for paste state bed reactor
Automatic fitration/flusher of solid-liquor separation passes through the program-controlled valve execution cycle being mounted on general pipeline using tubular structure
Filtering/flushing of property.
6. gas-solid washing separation device and wash.Patent US6265452 discloses a kind of in reactor head setting
Multilayer tower tray, top imports the scheme of returned cold condensate washing gas product, to reduce the catalyst content in gas.The design
The tower tray that scheme uses is similar to rectifying column tower tray, easily by catalyst blockage, and then influences washing effect and equipment safety.
It is known in the art, Fischer-Tropsch reaction is very sensitive to temperature and gas-liquid-solid three phase flow mixing, and product-catalyst
Separating difficulty it is larger.The design and product separation scheme that optimize reactor can effectively improve the effect of Fischer-Tropsch paste state bed reactor
Energy and stability.The generally existing reactor inner transmission matter heat-transfer effect of the prior art is not good enough, and product-catalyst separation method is multiple
The problems such as miscellaneous.
Chinese patent CN1233451C discloses a kind of gas-liquid-solid three-phase slurry bed system industrial reactor that can be operated continuously,
The reactor includes the inlet gas distributed elements for the progress even gas distribution being made of inlet gas distributor pipe, one or more layers is right
Bed carries out the heat exchanger tube component for heating/cooling down, one or more layers liquid-solid separator component that can be cleaned automatically, removes liquid foam
With the outlet dedusting demister component of solid entrainment.But decompression tube is not configured in the patent, therefore it is dead not can avoid bed bottom
The generation in area and hot spot.
Summary of the invention
It is closed it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is suitable for Fischer-Tropsch
At the paste state bed reactor and reaction system of technology, to continuous production Fischer-Tropsch synthetic.Fischer-tropsch product refers to hydro carbons (carbon number model
It is even higher to enclose 1~70) and oxygen-bearing organic matter (hydroxy-aldehydic acid ketone), the Fischer-Tropsch wax of liquid is divided into according to the phase under operating condition
With gaseous hydrocarbon products.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of paste state bed reactor for F- T synthesis, including
Reactor body,
The gas distributor of reactor body bottom is set,
Several groups heat-transfering device in reactor body and downspout matched with the heat-transfering device, two groups of shiftings are set
Liquid-solid separation device is equipped between thermal,
The gas-solid washing separation device of reactor head is set.
Unstripped gas is passed through in reactor and mixes with the Fischer-Tropsch wax and catalyst for being seated in inside reactor, and wherein unstripped gas refers to
The synthesis gas (carbon monoxide and hydrogen) or synthesis gas of gas unit (such as coal gas, natural gas shift) production processed and other works
The gaseous mixture of skill gas (fixed gas in such as gas products).Under the conditions of certain temperature and pressure, carbon monoxide and hydrogen exist
Catalyst surface is converted into fischer-tropsch product and releases amount of heat.Specifically, fischer-tropsch synthetic catalyst be iron, cobalt and other
One or more of mixing of group VIII metal catalyst, average particle size are 40~150 μm.Operating pressure be 1.0~
5.0MPaG, operation temperature are 200~300 DEG C, and superficial gas velocity is 0.2~0.5m/s.
The reactor body is vertical pressure vessel, and the diameter of reactor synthesizes throughput and superficial gas velocity according to import
Design, generally 0.5~15m；Reactor tangent line height includes structure in reaction zone height and gas-solid washing separation device, false bottom etc.
The size and mounting height of part, generally 30~60m.
False bottom is equipped between the bottom bulkhead and the gas distributor of the connection of reactor body bottom, which is circle
Partition constitutes the area Jia Di being isolated with reaction zone with bottom bulkhead, balance pipe is arranged between the area Jia Di and reactor outlet.Partition
Radian should be as small as possible, and play the role of optimizing the distribution of reaction zone bottom gas.The air scour that false bottom is sprayed by gas distributor,
It is possible to prevente effectively from there is the area Si Chuan because bottom bulkhead shape (generally taper or elliposoidal) radian is too big.False bottom and nozzle
Distance is 0.1~0.5m between outlet, and eroding velocity is 30~80m/s.
In order to guarantee false bottom and its with the deformation quantity of the sealing structure (such as weld seam) of shell connecting place within allowed band,
Under the vacation just in addition to supporting element is arranged, being provided with balance pipeline makes the pressure of false bottom two sides be in equilibrium state.Support
One or two kinds of combinations of crossbeam and pillar may be selected in part, are fixed on reactor shell or bottom bulkhead, and it is false to play support
The effect of bottom stress vertically downward.Balancing pipeline is usually to connect reactor inlet gas, and making false bottom, gas pressure is kept up and down
It is identical, prevent false bottom two sides pressure difference is excessive from causing the excessive deformation in false bottom.
The gas distributor may be selected circular concentric or branch shape multitube distributor, supervisor using feed pipe as the center of circle to
Wall Radiation extends, and branch pipe equably covers sagittal plane.Distributor pipe lower part configuration nozzle vertically downward, between adjacent respective nozzles
It is closely located or equal.Specifically, nozzle bore be 5~25mm, pressure drop be 0.02~0.1MPa, outlet linear speed be 50~
100m/s.Slurries flow backwards and enter gas distributor, catalyst in bottom deposit under dead ship condition in order to prevent,
The urgent nitrogen pipeline being connected with feeding line or gas distributor is configured, imports reaction at once when feed synthesis gas interrupts
Device keeps sinking speed of the superficial gas velocity not less than maximum particle diameter catalyst granules, typically no less than 0.1m/s in reactor.
The heat-transfering device is made of the shifting hot coil of import and export collection general pipeline and multiple groups parallel connection, along reactor axial arrangement 2
~3 layers.One heat-transfering device contains 2~4 couples of import and export collection general pipeline, form may be selected close to reactor wall surface curved pipe or
Radially go deep into the straight tube of reactor center.It moves hot coil to be made up of by 2~60 180 ° of concatenated straight tubes of elbow, import and export
It is connect respectively with import and export collection general pipeline.Straight tube form can also use the special pipes such as bellows, finned tube to enhance in addition to light pipe
The wall surface of slurries side exchanges heat, and length is 6~10m.The straight tube quantity of every group of shifting hot coil is equal to guarantee each group boiler water flow
It is evenly distributed.If the tube side pressure drop for collecting general pipeline is greater than the pressure drop of single cooling tube, the shifting heat of collection general pipeline distal end connection should be reduced
The cooling tube quantity of coil pipe.The boiler feed temperature of heat-transfering device import leads to lower than 20~80 DEG C of reaction zone temperature in reactor
Convection current-wall surface heat exchange absorbing reaction heat is crossed, is partially converted to saturated vapor, outlet rate of gasification is 0.05~0.25.
The downspout is a kind of special inner member of enhancing gas-liquid-solid three-phase mixing, its working principle is that: gas-liquid-solid three
Mutually stream is being streamed into the sedimentation pipe being relatively large in diameter, and air pocket continues up under the action of buoyancy, and slurries are made in gravity
It is settled in pipe under, to form low gas holdup, highdensity region in sedimentation pipe；The slurries of air pocket are removed in weight
It is moved downward under the action of power, flows to bed lower zone by delivery pipe.It is moved downward in downspout in slurries and reaction zone
The three-phase flow moved upwards forms the circulation loop of fluid, plays the role of stirring.In general, the sedimentation pipe diameter of downspout
For 0.2~1.5m, internal diameter of delivery hose is 0.1~0.7m, and every layer of sedimentation pipe area accounts for the 10%~30% of reaction zone cross-sectional area.
In order to enhance the mixing of slurries around cooler, the heat convection efficiency of slurries side, downspout and shifting hot charging are improved
It sets and matches, to form stirring area around heat-transfering device.Due under shearing force of the wall surface to three-phase flow, reaction zone
There is the phenomenon that center is high, nearly wall is low in interior bubble diameter and speed, in order to keep the radial distribution of three-phase flow more uniform, drop
Liquid pipe should be arranged equably in the heart and nearly wall position in the reactor.Specifically, axle center pair is arranged or surrounded to downspout in axle center
Claim arrangement, the center spacing of adjacent downspout is 0.5~2m.
The liquid-solid separation device is made of 5~30 groups of filter assemblies, every group of filter assemblies by 5~30 filter elements and
Filtering collection general pipeline, the flushing collection general pipeline composition being attached thereto.Sintering metal, porous ceramics etc. may be selected in the form of filter element,
Allow by catalyst maximum particle diameter be 10~40 μm, catalyst is less than 100ppm containing rate in filtered slurries.Filtering
Fischer-Tropsch wax can carry a large amount of gas products and synthesis gas secretly, in order to prevent vent plug, and filtrate exports to filtering above filter element
Collect in general pipeline, correspondingly, collection general pipeline is rinsed in lower section connection.
When cooler is two layers, liquid-solid separation device is mounted between two layers of heat-transfering device；When heat-transfering device is three layers
When, liquid-solid separation device is preferably mounted between top layer and middle layer heat-transfering device, with reduce the carbon monoxide in gas-entrained and
The content of hydrogen.Filtration yield and flushing dose in order to guarantee every group of filter assemblies is equal, and the quantity of filter element should be equal as far as possible.
The gas-solid washing separation device is by reflux wax spray thrower, refluxer spray thrower, liquid distribution trough and gas-liquid
Separator group at；The reflux wax spray thrower is located at the lower section of the refluxer spray thrower, the refluxer spray thrower
Lower section be equipped with the liquid distribution trough, the gas-liquid separator is located at the upper of refluxer spray thrower and liquid distribution trough
Side, is connected with the gas vent of reactor head.
The gas-solid washing separation device uses the lower medium washing gas product of catalyst content, then removes wherein
The fine droplet containing solid particle, with have the function that reduce gas products in catalyst content, device include be uniformly distributed
The spray thrower of Quench liquid strengthens the liquid distribution trough and separation drop/product gas gas-liquid separator of gas-liquid contact.It leaves anti-
The gas products in area are answered to contain the Fischer-Tropsch of rate lower (< 100ppm) with catalyst on the liquid distribution trough below reflux wax spray thrower
Wax inversely contacts, and after the mist containing catalyst of entrainment is largely refluxed wax absorption, is brought back reaction zone.Subsequent gas produces
Product continue inversely to contact with the refluxer for being practically free of catalyst (< 5ppm), and catalyst is by further supplementary set.In addition,
Refluxer causes gas-liquid mass transfer to the condensation of gas products, can further strengthen washing effect.After Quench
The mist for being practically free of catalyst carried secretly with it of gas products enter gas-liquid separator, mist collides and is attached to baffle plate
After upper, flowed back on liquid distribution trough along baffle plate, gas products then pass through baffle plate outflow reactor.
Reaction system provided by the invention includes reactor and the filtering-rinsing module connecting with the reactor and washing
Component.
Filtering-the rinsing module is by Fischer-Tropsch wax collecting tank, Fischer-Tropsch wax dashpot, filter, flushing wax collecting tank, flushing
Pump rinses wax pan, strainer valve and flushing valve composition, and the import of Fischer-Tropsch wax collecting tank is filled by the pipeline and solid-liquor separation for being equipped with strainer valve
The filtering collection general pipeline set is connected, and liquid-phase outlet is connected with Fischer-Tropsch wax dashpot, Fischer-Tropsch wax dashpot liquid-phase outlet and filter phase
Even, the filtrate (liquid of filter is connected with wax collecting tank is rinsed, and rinses wax collecting tank liquid-phase outlet and is connected with flushing pump, flushing pump
Outlet is connected with wax pan is rinsed, and rinses wax pan liquid-phase outlet by the flushing lump of pipeline and liquid-solid separation device equipped with flushing valve
Pipe is connected.
Rinsing module can also be gas bleed component, and the flushing wax collecting tank and flushing wax pan store up for high pressure gas
Tank, the flushing gas in high pressure gas storage tank are synthesis gas or inert gas.
The purpose of the filtering-rinsing module be Fischer-Tropsch wax is filtered in reactor and liquid-solid separation device carry out
It rinses.Filtering-flushing operation program includes filtering, flushing and selectable wait state, is filled by control and solid-liquor separation
Connected strainer valve and flushing valve is set to complete.Specifically, flushing shape is switched to from filtration condition when one group or several groups of filter assemblies
State, a kind of scheme are that the filter assemblies of identical group of number switch to wait state, switch to filtration condition after wait state, according to
It is secondary repeatedly；Another scheme is to be directly switch into flushing state after filtration condition, successively repeatedly.Under filtration condition, filtering
Valve is opened, and flushing valve is closed, 10~30min of duration；Under wait state, strainer valve is closed, and flushing valve is closed, the duration
5~20min；Under flushing state, strainer valve is closed, and flushing valve is opened, 2~20s of duration.
The essence of Fischer-Tropsch wax is filtered through following scheme realization: the Fischer-Tropsch wax that liquid-solid separation device is isolated enters Fischer-Tropsch wax receipts
Collect slot, the gas products carried secretly and synthesis gas removing.Fischer-Tropsch wax after degassing enters after entering the decompression of Fischer-Tropsch wax dashpot
Filter.Vane type or plate and frame filter may be selected in filter form.After essence filtering, catalyst maximum particle diameter is small in Fischer-Tropsch wax
In 1 μm, content is less than 5ppm.The filtered Fischer-Tropsch wax a part of essence is produced as product, and a part, which imports, rinses wax collecting tank.
It rinses wax and is delivered to flushing wax pan through flushing pump, be then returned to reactor and liquid-solid separation device is rinsed.Wherein, Fischer-Tropsch wax
Collecting tank pressure is lower than 0.1~1.0MPa of reactor, and Fischer-Tropsch wax dashpot pressure is lower than the permission pressure of filter, rinses wax pan
Pressure is higher than 0.1~1.0MPa of reactor.
The wash is by product Gas Cooler, condensate liquid separating tank, condensate reflux pump and Fischer-Tropsch wax reflux pump group
At product gas cooler inlet is connected with gas reactor outlet, and outlet is connected with condensate liquid separating tank, condensate liquid separating tank
Oily mutually outlet is connected with condensate reflux pump, and condensate reflux pump exports the condensate liquid spray thrower phase with gas-solid washing separation device
Even, the import of Fischer-Tropsch wax reflux pump is connected with Fischer-Tropsch wax collecting tank, and outlet is connected with reflux wax spray thrower.
Wash condenses and separates gas products, and the expense that oily phase condensate liquid and liquid-solid separation device are isolated
Support wax is delivered to washing separation device.The gas of reactor outlet, which enters after cooler, is cooled to 20~150 DEG C, water therein and
Heavy hydrocarbon is from being condensed into liquid.One or more combinations of following cooler can be used according to process requirement cooler: using
The forecooler of import synthesis gas or the lower process fluid of other temperature as cooling medium；Using recirculated water as cooling medium
Water cooler；Use air as the air cooler of cooling medium.Gas after cooling enters condensate liquid separating tank and carries out gas and oil
Water three phase separation.Oily phase condensate liquid a part is produced as product, and a part is delivered to condensate liquid spray through condensate reflux pump
Device.Fischer-Tropsch wax in Fischer-Tropsch wax collecting tank is delivered to reflux wax spray thrower by reflux wax pump.Wherein, condensate liquid and gas products
Liquid-gas ratio is 2~4L/m3, the liquid-gas ratio of flow back wax and gas products is 0.4~1L/m3, the temperature of gas products is lower than after Quench
10~60 DEG C of reaction zone temperature.
Compared with prior art, the invention has the following advantages that
(1) inlet gas distributor is mixed with false bottom with the use of the gas-liquid-solid that can be effectively improved reaction zone bottom, is kept away
Exempt from the appearance in the bottom area Si Chuan.Even if pressurising and balance pipeline make the pressure difference of false bottom two sides under extreme conditions also in a small range
Fluctuation, has ensured the safety of false bottom and its sealing element.
(2) heat-transfering device structure is simple, and stringing density is big, it is ensured that the heat exchange area of surplus abundance adapts to various multiple
General labourer's condition and biggish load variations.
(3) reasonable descending liquid pipe size and arrangement can significantly improve gas-liquid-solid three-phase mixing, match with heat-transfering device
Covering use can be with enhanced heat transfer effect.
(4) easy to operate efficiently using liquid-solid separation device and filtering-rinsing module, extraction Fischer-Tropsch wax can be effectively reduced
Catalyst contain rate, make its meet rinse and product quality requirement.
(5) catalyst in gas products can be effectively removed using gas-solid washing separation device and wash, reduced
The loss of catalyst reduces the risk of upstream device blocking.
(6) disclosed in the CN1233451C compared with technical solution, the present invention is enhanced in bed by configuring downspout
Three mix, and use more reasonable distributor and configure, it is suppressed that the generation of bed bottom dead and hot spot, and then reduce bed
Temperature difference in layer, improves the yield of target product.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of reactor；
Fig. 2 is the structural schematic diagram of filtering-rinsing module matched with reactor；
Fig. 3 is the structural schematic diagram with the matched wash of reactor.
In figure, 1 is reactor body, and 2 be gas distributor, and 3 be false bottom, and 4 be heat-transfering device, and 4a is to move hot coil, 4b
It is outlet collection general pipeline for inlet header general pipeline, 4c, 5 be downspout, and 5a is sedimentation pipe, and 5b is delivery pipe, and 6 be liquid-solid separation device,
6a is that filtering collects general pipeline, and 6b is that flushing collection general pipeline, 6c is filter element, and 7 be gas-solid washing separation device, and 7a sprays for reflux wax
Device is drenched, 7b is refluxer spray thrower, and 7c is liquid distribution trough, and 7d is gas-liquid separator, and 8 be reaction zone, and 9 be the area Jia Di,
S1 is unstripped gas, and S2 is gas products, and S3 is boiler feedwater, and S4 is byproduct steam, and S5 is extraction Fischer-Tropsch wax, and S6 is to rinse wax,
S7 is reflux wax, and S8 is refluxer, and S9 is pressure charging pipe, and S10 is balance pipe, and S11 is reflux Fischer-Tropsch wax, and V1 is Fischer-Tropsch wax
Collecting tank, V2 are Fischer-Tropsch wax dashpot, and V3 is to rinse wax collecting tank, and V4 is to rinse wax pan, and V5 is condensate liquid separating tank, and VLV1 is
Strainer valve, VLV2 are flushing valve, and F1 is fine filter, and P1 is to rinse wax pump, and P2 is Fischer-Tropsch wax reflux pump, and P3 returns for condensate liquid
Stream pump, C1 are product Gas Cooler.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
In the description of the present invention, it is to be understood that, term, " top ", " bottom ", " parallel ", " centre " etc. indicate
Orientation or positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the component of indication or suggestion meaning or
Element must have a particular orientation, and be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
Embodiment 1
A kind of paste state bed reactor for F- T synthesis, structure is as shown in Figure 1, include reactor body 1, setting exists
Several groups heat-transfering device 4 and and heat-transfering device in reactor body 1 is arranged in the gas distributor 2 of 1 bottom of reactor body
4 matched downspouts 5 are equipped with liquid-solid separation device 6 between two groups of heat-transfering devices 4, and the top of reactor body 1 is provided with gas-solid
Washing separation device 7.
Reactor body 1 is vertical pressure vessel, the bottom bulkhead and gas distributor 2 of the connection of 1 bottom of reactor body
Between be equipped with false bottom 3, which is circular bulkheads, constitute the area Jia Di 9 being isolated with reaction zone with bottom bulkhead, the area Jia Di 9 and
Pressure charging pipe S9 and balance pipe S10 is set between reactor outlet.
The gas distributor 2 used is multitube distributor, is connected with raw material gas inlet, gas vent is vertically downward.It moves
Thermal 4 is made of the shifting hot coil 4a of inlet header general pipeline 4b, outlet collection general pipeline 4c and multiple groups parallel connection, moves the disengaging of hot coil 4a
Mouth is connected with inlet header general pipeline 4b, outlet collection general pipeline 4c respectively.Downspout 5 is connected by funnelform sedimentation pipe 5a and with its bottom
Delivery pipe 5b composition, the top of sedimentation pipe 5a heat-transfering device 4 above, delivery pipe 5b with shifting hot coil 4a it is parallel, sedimentation pipe
The lower section of heat-transfering device 4 is arranged in the bottom end of 5a.
Liquid-solid separation device 6 is made of multiple groups filter assemblies, and every group of filter assemblies are collected by multiple filter element 6c and two
Collection general pipeline 6b is rinsed in general pipeline composition, the lower end connection filtering collection general pipeline 6a of filter element 6c, upper end connection.Gas-solid washing separation dress
7 are set to be made of reflux wax spray thrower 7a, refluxer spray thrower 7b, liquid distribution trough 7c and gas-liquid separator 7d；Flow back wax
Spray thrower 7a is located at the lower section of refluxer spray thrower 7b, and the lower section of the refluxer spray thrower is equipped with liquid distribution trough
7c, gas-liquid separator 7d are located at the top of refluxer spray thrower 7b Yu liquid distribution trough 7c, the gas with reactor head
Outlet is connected.
Unstripped gas S1 enters in reactor body 1 from the area Jia Di 9.It is reacted in reaction zone 8, final gas products S2
It is produced at the top of reactor body 1, boiler feedwater S3 is entered in heat-transfering device 4 through inlet header general pipeline 4b, is obtained by heat exchange
Byproduct steam S4 from outlet collection general pipeline 4c discharge.In reaction zone 8, wax S6 is rinsed through flushing collection general pipeline 6b and enters solid-liquor separation
Device 6, extraction Fischer-Tropsch wax S5 is through filtering lump pipe 6a extraction.In gas-solid washing separation device 7, reflux wax S7 is sprayed from reflux wax
It drenches device 7a to enter, refluxer S8 enters from refluxer spray thrower 7b.
For the slurry reactor system of F- T synthesis, including reactor and the filtering-flushing being connect with the reactor
Component and wash.
Filtering-rinsing module structure is as shown in Fig. 2, by Fischer-Tropsch wax collecting tank V1, Fischer-Tropsch wax dashpot V2, rinse wax receipts
Collect slot V3, rinse wax pan V4, fine filter F1 and matching used strainer valve VLV1, flushing valve VLV2, rinse wax pump P1 etc.
Component is constituted.The import of Fischer-Tropsch wax collecting tank V1 has the filtering of the pipeline and liquid-solid separation device 6 of strainer valve VLV1 by being equipped with
Collect general pipeline 6a to be connected, receive extraction Fischer-Tropsch wax S5, in addition it can produce reflux Fischer-Tropsch wax S11.The liquid of Fischer-Tropsch wax collecting tank V1
Mutually outlet is connected with Fischer-Tropsch wax dashpot V2, and the liquid-phase outlet of Fischer-Tropsch wax dashpot V2 is connected with fine filter F1, fine filter
The filtrate (liquid of F1 is connected with wax collecting tank V3 is rinsed, and the liquid-phase outlet for rinsing wax collecting tank V3 is connected with flushing pump P1, rinses
The outlet pump P1 is connected with wax pan V4 is rinsed, and rinses wax pan V4 liquid-phase outlet by pipeline and solid-liquor separation equipped with flushing valve VLV2
The flushing collection general pipeline 6b of device 6 is connected.
The structure of wash is as shown in figure 3, by product Gas Cooler C1, condensate liquid separating tank V5, condensate reflux pump
The components such as P3 and Fischer-Tropsch wax reflux pump P2 are constituted.The import of product Gas Cooler C1 is connected with gas reactor outlet, imports gas
Body product S2, outlet are connected with condensate liquid separating tank V5, and the oil of condensate liquid separating tank V5 mutually exports and condensate reflux pump P3 phase
Even, the outlet of condensate reflux pump P3 is connected with the refluxer spray thrower 7b of gas-solid washing separation device 7, and Fischer-Tropsch wax returns
The import of stream pump P2 is connected with Fischer-Tropsch wax collecting tank V1, receives reflux Fischer-Tropsch wax S11, and outlet is connected with reflux wax spray thrower 7a,
Output reflux wax S7.
Embodiment 2
It is roughly the same with embodiment 1 for the slurry reactor system of F- T synthesis, the difference is that, the present embodiment
Middle rinsing module is gas bleed component, and the flushing wax collecting tank used and flushing wax pan are high pressure gas storage tank, high pressure gas storage
Flushing gas in tank is synthesis gas or inert gas.
Embodiment 3
Technical solution in the embodiment includes paste state bed reactor shown in FIG. 1, filtering-rinsing module shown in Fig. 2
And wash shown in Fig. 3.Reactor tangent line height is 45m, internal diameter 0.52m.Filling Fischer-Tropsch precipitating in reaction zone 8
Iron catalyst, feed synthesis gas S1 tolerance 320000Nm3/ h, wherein being 2:1 to make hydrogen-carbon ratio in the synthesis gas of gas unit by oneself.Instead
Answer 8 operating pressure 2.3MPaG of area, 240 DEG C of operation temperature.Fischer-Tropsch wax yield 4.8t/h produces catalyst in Fischer-Tropsch wax S5 and contains rate
80ppm, filter F1 filter out catalyst in Fischer-Tropsch wax and contain rate < 5ppm.Gas products condensate 7.0t/h, wherein catalyst contains rate
<5ppm。
Embodiment 4
Using reactor described in embodiment 1 and corollary system.Fischer-Tropsch cobalt-base catalyst, charging synthesis are loaded in reaction zone 8
Gas S1 tolerance 328000Nm3/ h, wherein being 2:1 to make hydrogen-carbon ratio in the synthesis gas of gas unit by oneself.8 operating pressure of reaction zone
2.3MPaG, 240 DEG C of operation temperature.Fischer-Tropsch wax yield 4.8t/h produces catalyst 80ppm containing rate, filter F1 in Fischer-Tropsch wax S5
It filters out catalyst in Fischer-Tropsch wax and contains rate < 5ppm.Gas products condensate 6.7t/h, wherein catalyst contains rate < 5ppm.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of paste state bed reactor for F- T synthesis, which is characterized in that including
Reactor body,
The gas distributor of reactor body bottom is set,
Several groups heat-transfering device in reactor body and downspout matched with the heat-transfering device, two groups of shifting hot chargings are set
Liquid-solid separation device is equipped between setting,
The gas-solid washing separation device of reactor head is set.
2. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the reactor
Main body is vertical pressure vessel, and false bottom is equipped between the bottom bulkhead and the gas distributor of the connection of reactor body bottom,
The vacation bottom is circular bulkheads, constitutes the area Jia Di being isolated with reaction zone with bottom bulkhead, sets between the area Jia Di and reactor outlet
Set balance pipe.
3. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the gas point
Cloth device is multitube distributor, is connected with raw material gas inlet, gas vent is vertically downward.
4. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the shifting hot charging
Set and be made of inlet header general pipeline, outlet collection general pipeline and the shifting hot coil of multiple groups parallel connection, the inlet and outlet of the shifting hot coil respectively with
Inlet header general pipeline, outlet collection general pipeline are connected.
5. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the downspout
It is made of funnelform sedimentation pipe and the delivery pipe being connected with its bottom, the sedimentation pipe top is described above heat-transfering device
Delivery pipe is parallel with hot coil is moved, and sedimentation pipe bottom end is arranged below the heat-transfering device.
6. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the liquid divides admittedly
It is made of from device multiple groups filter assemblies, every group of filter assemblies are made of multiple filter elements and two collection general pipeline, the filtering
Collection general pipeline is rinsed in the lower end connection filtering collection general pipeline of element, upper end connection.
7. a kind of paste state bed reactor for F- T synthesis according to claim 1, which is characterized in that the gas-solid is washed
Separator is washed to be made of reflux wax spray thrower, refluxer spray thrower, liquid distribution trough and gas-liquid separator；The reflux
Wax spray thrower is located at the lower section of the refluxer spray thrower, and the lower section of the refluxer spray thrower is equipped with the liquid point
Cloth device, the gas-liquid separator are located at the top of refluxer spray thrower and liquid distribution trough, the gas with reactor head
Outlet is connected.
8. a kind of slurry reactor system for F- T synthesis, which is characterized in that including any one of such as claim 1-7 institute
The reactor stated and the filtering-rinsing module and wash that are connect with the reactor.
9. a kind of slurry reactor system for F- T synthesis according to claim 8, which is characterized in that
Filtering-the rinsing module by Fischer-Tropsch wax collecting tank, Fischer-Tropsch wax dashpot, filter, rinse wax collecting tank, flushing pump,
Wax pan, strainer valve and flushing valve composition are rinsed, the import of Fischer-Tropsch wax collecting tank is by pipeline and liquid-solid separation device equipped with strainer valve
Filtering collection general pipeline be connected, liquid-phase outlet is connected with Fischer-Tropsch wax dashpot, and Fischer-Tropsch wax dashpot liquid-phase outlet is connected with filter,
The filtrate (liquid of filter is connected with wax collecting tank is rinsed, and rinses wax collecting tank liquid-phase outlet and is connected with flushing pump, flushing pumps out
Mouth is connected with wax pan is rinsed, and rinses wax pan liquid-phase outlet by being equipped with the pipeline of flushing valve and the flushing collection general pipeline of liquid-solid separation device
It is connected；
The wash is made of product Gas Cooler, condensate liquid separating tank, condensate reflux pump and Fischer-Tropsch wax reflux pump, is produced
The import of product Gas Cooler is connected with gas reactor outlet, and outlet is connected with condensate liquid separating tank, the oily phase of condensate liquid separating tank
Outlet is connected with condensate reflux pump, and condensate reflux pump outlet is connected with the condensate liquid spray thrower of gas-solid washing separation device,
The import of Fischer-Tropsch wax reflux pump is connected with Fischer-Tropsch wax collecting tank, and outlet is connected with reflux wax spray thrower.
10. a kind of slurry reactor system for F- T synthesis according to claim 9, which is characterized in that flushing group
Part can also be gas bleed component, the flushing wax collecting tank and to rinse wax pan be high pressure gas storage tank, in high pressure gas storage tank
Flushing gas be synthesis gas or inert gas.
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