CN109201074A - A kind of regeneration method of micro passage reaction fischer-tropsch synthetic catalyst - Google Patents
A kind of regeneration method of micro passage reaction fischer-tropsch synthetic catalyst Download PDFInfo
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- CN109201074A CN109201074A CN201710532763.4A CN201710532763A CN109201074A CN 109201074 A CN109201074 A CN 109201074A CN 201710532763 A CN201710532763 A CN 201710532763A CN 109201074 A CN109201074 A CN 109201074A
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/16—Oxidation gas comprising essentially steam and oxygen
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- 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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
A kind of regeneration method of micro passage reaction fischer-tropsch synthetic catalyst, first with synthesis gas in inert gas replacement reactor, then under the conditions of cracking reaction, cracking reaction occurs for the macromolecule hydrocarbon of fischer-tropsch synthetic catalyst absorption, methane and lighter hydrocarbons are obtained, is then aoxidized and is restored again.The present invention regenerates the Co based Fischer-Tropsch synthesis catalyst of micro passage reaction, and the physicochemical properties and catalytic performance of regenerated catalyst are close with fresh catalyst, and regenerative process energy consumption is small low with material consumption.
Description
Technical field
The present invention relates to a kind of regeneration methods of fischer-tropsch synthetic catalyst, are a kind of based on microchannel plate more specifically
Answer the regeneration method of the Co based Fischer-Tropsch synthesis catalyst of device.
Background technique
Microchannel reaction technology is one of the new technology of 21st century Chemical waste-water, has conventional reactor can not
The advantage of analogy, such as: reaction channel is micron level, and surface area is big, and reactor has very high mass transfer and rate of heat transfer, single
Position volume reactor reaction load is high, and engineering amplification is simple.And some strongly exothermic catalysis are reacted, such as F- T synthesis is anti-
It answers, hydrocracking reaction, reinforces the heat transfer of catalyst layer, the temperature plateau for controlling reaction is the premise of the reaction effect obtained
And guarantee.Using microchannel reaction technology, high activated catalyst may be implemented and reacted in isothermy, both overcome traditional reaction
Device mass transfer extends influence big, heat-transfer effect difference disadvantage.
After Fischer-Tropsch synthesis carries out a period of time, since catalyst surface forms carbon distribution, active metal is oxidized, greatly
Molecule covers the factors such as activated centre, declines catalyst performance, needs to regenerate catalyst to restore its performance.Especially
It is for micro passage reaction, the filling and coating of catalyst are complex, compared with traditional fixed bed and slurry bed system, need
Longer operation cycle and catalyst life, catalyst regeneration not only reduce catalyst cost and operating cost, additionally it is possible to reduce
Because of catalyst recovery processing bring consumption and environmental pollution.
For different fischer-tropsch synthesis process, researcher has developed a variety of regeneration methods.For syrup state bed Fischer Tropsch
Synthetic catalyst regeneration, since reaction condition limits, regenerated offline is the mode generallyd use, generally comprises dewaxing, oxidation takes off
Carbon and reduction, such as: it is proposed in Chinese patent CN101844093B, CN101688125B a kind of for slurry bed system
The processes such as the regeneration method of the pellet type catalyst of reaction, including dewaxing treatment, oxidation processes and reduction treatment, dewaxing process
The technique that re-dry after solvent washing is carried out using dimethylbenzene.Chinese patent CN101703937B proposes a kind of syrup state bed Fischer Tropsch
The regeneration method of synthetic catalyst, catalyst need to undergo extraction, air lift, oxidation and reduction process.Catalyst dewaxing uses C7
~C12Alkane extracted, then air lift is dry.Chinese patent CN102791377B discloses a kind of fischer-tropsch synthetic catalyst
Regeneration method, catalyst first passes around the washing de-oiling of alkane, then the steam treatment through 5MPa, it is available it is preferable again
It comes into force fruit.United States Patent (USP) US4399234 discloses a kind of regeneration method of catalyst, main process be by catalyst at high temperature
It is contacted with oxygen-containing gas or steam, the catalyst after regeneration passes through hydrogen-containing gas reduction activation at high temperature again.United States Patent (USP)
US2369956 discloses a kind of regeneration method of fischer-tropsch synthetic catalyst, uses acid by catalyst activity dissolving metal, then
By reprecipitation catalyst metals to restore catalyst.This method is effective for the catalyst inactivation of a variety of causes, but
Catalyst structure can be destroyed, the interaction between active metal and carrier and active metal and auxiliary agent is influenced, and is operated multiple
Miscellaneous, catalyst regeneration needs carry out in other special equipments.Chinese patent CN102259036B discloses a kind of on-line regeneration
The method of catalyst is regenerated for fixed bed FischerTropsch synthesis catalyst, and catalyst reactor is by purging, solvent washing, oxygen
Change and reduction obtains performance recovery.
From the prior art as can be seen that dewaxing in fischer-tropsch synthetic catalyst regenerative process, on fischer-tropsch synthetic catalyst
Step is mainly to be washed using solvent, but solvent washing process is on the one hand very high to the requirement of solvent, such as to sulphur in solvent, nitrogen,
Oxygen, metal impurities content have strict demand, to prevent pollution catalyst.On the other hand, solvent washing process and washing after
Content of wax solvent reprocessing process be all energy consumption and the higher process of material consumption.
Summary of the invention
The object of the present invention is to provide a kind of regeneration methods of fischer-tropsch synthetic catalyst for micro passage reaction.With solution
Certainly in the prior art, energy consumption is high and the high technical problem of material consumption for regenerative process.
Regeneration method provided by the present invention, comprising:
(1) synthesis gas in inert gas replacement reactor is used,
(2) it is passed through hydrogen in reactor, in hydrogen atmosphere, under the conditions of cracking reaction, fischer-tropsch synthetic catalyst absorption
Macromolecule hydrocarbon occur cracking reaction, obtain methane and lighter hydrocarbons,
(3) step (2) treated fischer-tropsch synthetic catalyst contacts oxygen-containing gas, is aoxidized under oxidative conditions,
(4) the fischer-tropsch synthetic catalyst contact hydrogen-containing gas after step (3) oxidation is restored, and Fischer-Tropsch closes after being regenerated
At catalyst,
The fischer-tropsch synthetic catalyst is cobalt-based support type fischer-tropsch synthetic catalyst, in micro passage reaction, filling
Or the cobalt-based support type fischer-tropsch synthetic catalyst that coating is described.
The micro passage reaction refers to the reactor with multiple row channel design, channel in layer structure in parallel and/
Or it is staggered, channel for loading, coat catalyst or circulation heat-conducting medium, microchannel of the present invention for width or
For depth dimensions in 1000 microns of ducts below, passage length is more than 1 centimetre.
In one of embodiment of the invention, two kinds of channels are set, i.e. reaction is logical in the micro passage reaction
Road and heat-conducting medium channel.The cobalt-based support type fischer-tropsch synthetic catalyst is filled or coated in reaction channel, and Fischer-Tropsch occurs
Synthetic reaction；The heat-conducting medium of heat-conducting medium passage flow gas phase perhaps liquid phase is for exporting reaction heat or heating response device.
Reaction channel and heat-conducting medium channel are arranged alternately, mutually isolated, and material circulating direction can cocurrent, cross-flow or angled
(such as 90 degree).
The Fischer-Tropsch synthesis in micro passage reaction, reaction condition are as follows: pressure is 1~5MPa, and temperature is
150~300 DEG C, gas hourly space velocity is 1000~100000h-1, H in unstripped gas2It is 1~3 with CO volume ratio, circulating air and fresh original
Material-gas ratio example be 0.1~10, preferably are as follows: reaction pressure be 2~4MPa, temperature be 180~250 DEG C, gas hourly space velocity be 2000~
40000h-1, H in unstripped gas2It is 1.8~2.5 with CO ratio, circulating air and fresh feed gas ratio are 0.5~6.Reaction process
Middle to need to be passed through medium export heat in the heat-conducting medium channel of micro passage reaction, heat-conducting medium can be gas phase, as air,
N2、H2、CO2, water vapour etc., be also possible to liquid phase, such as water, conduction oil.
The cobalt-based support type fischer-tropsch synthetic catalyst includes active component cobalt, auxiliary agent and carrier, and auxiliary agent is selected from transition gold
One or more of category, rare earth metal and nonmetalloid, carrier are selected from Al2O3、SiO2、TiO2、ZrO2, in molecular sieve one
Kind is several, and by weight, the content of cobalt is 10%~50%.
The cobalt-based support type fischer-tropsch synthetic catalyst is as prepared by co-precipitation, dipping, spray method either method.
When the cobalt-based support type fischer-tropsch synthetic catalyst is powder, it is seated in the reaction channel of micro passage reaction, or adopt
Mode is carried with wall, cobalt-based support type fischer-tropsch synthetic catalyst is coated on the inner wall or supporter of reaction channel.Supporter
It can be any reactionlessness object that stainless (steel) wire, stainless steel plate, ceramic wafer etc. have some strength.
It is anti-with inert gas replacement in step (1) in regeneration method one of which embodiment provided by the present invention
Synthesis gas in device is answered, the inert gas is selected from N2, one or more of Ar, He, preferably N2, it is passed through inert gas
Air speed is 2000~20000h-1, preferably 5000~10000h-1.While being passed through inert gas, temperature of reactor is dropped
Down to 180 DEG C hereinafter, being preferably decreased to 150 DEG C.
In regeneration method one of which embodiment provided by the present invention, in step (2), the air speed for being passed through hydrogen is
2000h-1~8000h-1, preferably 3000h-1~5000h-1, reactor pressure be 0.5MPa~10MPa, preferably 1.0MPa~
8.0MPa.Reactor temperature control process in step (2) are as follows: be warming up to 200 DEG C~300 DEG C, constant temperature 2h~10h is warming up to
300 DEG C~450 DEG C, constant temperature to discharge gas in methane content be lower than 1 volume % when, reduce reactor temperature, be down to 50 DEG C.Into
One step is preferably warming up to 340 DEG C~400 DEG C, when methane content is lower than 1 volume % in constant temperature extremely discharge gas, reduces temperature in reactor
Degree.Heating rate is not more than 40 DEG C/h, preferably no greater than 30 DEG C/h.In the process, big point of fischer-tropsch synthetic catalyst absorption
Cracking reaction occurs for sub- hydro carbons, obtains methane and lighter hydrocarbons.
It is preferred that being passed through inert gas before step (2) treated fischer-tropsch synthetic catalyst contact oxygen-containing gas and being blown
It sweeps, the fischer-tropsch synthetic catalyst after purging is qualified contacts oxygen-containing gas, and the inert gas is selected from N2, one of Ar, He
Or it is several；As combustible gas (H in periodic off-gases2+ total hydrocarbon) volume fraction less than 0.1% when, it is qualified to be considered as purging.
In regeneration method one of which embodiment provided by the present invention, in step (3), it is lower than 50 in temperature of reactor
DEG C~80 DEG C, under pressure 0.5MPa~2.0MPa, fischer-tropsch synthetic catalyst contacts oxygen-containing gas, in reactor inlet oxygen-containing gas
Oxysome fraction is 0.5%~2%.After reactor is passed through oxygen-containing gas, after reactor does not have temperature change, step up anti-
Answer device temperature to 400 DEG C~450 DEG C, heating rate is not more than 40 DEG C/h, preferably no greater than 30 DEG C/h.To CO+CO in periodic off-gases2
After content is constant, improve oxysome fraction in oxygen-containing gas, in reactor inlet oxygen-containing gas oxysome fraction be 5%~
15%；To CO+CO in periodic off-gases2Oxidation terminates after volume content < 0.05%.
The purpose of the described fischer-tropsch synthetic catalyst oxidation be in controlled range by the metal of fischer-tropsch synthetic catalyst and
The organic matters such as surface carbon deposit are changed into metal oxide and oxycarbide, therefore in the premise for not damaging fischer-tropsch synthetic catalyst
Under, any mode of oxidizing all can be used.Currently preferred oxygen-containing gas is selected from oxygen and/or air and inert gas or water steams
The mixed gas of vapour.It, can also be with specifically, oxygen-containing gas can be the mixed gas of oxygen and/or air and inert gas
It is the mixed gas of oxygen and/or air and water vapour.The further preferably mixed gas of oxygen and inert gas.
Step (2) cracking process and step (3) oxidation process is exothermic process, preferably in micro passage reaction
Heat-conducting medium channel be passed through heat-conducting medium to export heat, the heat-conducting medium is gas phase: being selected from air, N2、H2、CO2、
One or more of water vapour, or be liquid phase: water or conduction oil.
It is preferred that being passed through inert gas before the fischer-tropsch synthetic catalyst after step (3) oxidation contacts hydrogen-containing gas and being blown
It sweeps, the fischer-tropsch synthetic catalyst after purging is qualified contacts hydrogen-containing gas, and the inert gas is selected from N2, one of Ar, He
Or it is several；When the volume fraction of oxygen in periodic off-gases is less than 0.1%, it is qualified to be considered as purging.
In regeneration method one of which embodiment provided by the present invention, in step (4), hydrogen is passed through in reactor
Body, the volume fraction of hydrogen is not more than 10%, preferably no greater than 5% in the hydrogen-containing gas, and the air speed for being passed through hydrogen-containing gas is
500~5000h-1, preferably 1500~3000h-1, temperature of reactor is 350 DEG C~500 DEG C, preferably 350 DEG C~450 DEG C, is heated up
Rate is not more than 60 DEG C/h, preferably no greater than 40 DEG C/h, and pressure is 0~2.0MPa, and preferably 0~1.0MPa, reactor each point is most
The big temperature difference is not more than 5 DEG C, preferably no greater than 3 DEG C.Water content in measurement discharge gas, wait be less than 5mg/L, preferably smaller than 2mg/L is mentioned
The volume fraction of hydrogen is 30%~60%, preferably 40%~50% in high hydrogen-containing gas, and 2~20h of constant temperature.
Catalyst regeneration process of the present invention can carry out in situ in F- T synthesis device, can also will have catalysis
It is carried out after the micro passage reaction unloading of agent in dedicated unit.
Compared with prior art, the present invention having the advantage that
(1) characteristic for utilizing cobalt-based support type fischer-tropsch synthetic catalyst, realizes in-situ regeneration, and combine microchannel plate
The cracking performance for answering device feature and cobalt-based support type fischer-tropsch synthetic catalyst makes strongly exothermic split under the regeneration condition of optimization
Change reaction controllably to occur in micro passage reaction, has both avoided destruction of the cracking reaction heat release to catalyst structure, also avoided
The generations of a large amount of carbon deposits of catalyst, while solvent wash step is omitted, effectively reduce the material consumption and energy consumption of regenerative process.
(2) regeneration method provided by the invention, it is small to the damage of cobalt-based support type fischer-tropsch synthetic catalyst, it is easy to operate to be easy to
It realizes, no newly added equipment, cobalt-based support type fischer-tropsch synthetic catalyst performance recovery is good after regeneration.
Detailed description of the invention
Fig. 1 is micro passage reaction one of which embodiment structure schematic diagram of the present invention.Number 11 is microchannel in figure
Reactor, 12 be reaction channel, and 13 be heat-conducting medium channel.
Fig. 2 is micro passage reaction another embodiment structural schematic diagram of the present invention.Number 21 is microchannel plate in figure
Device is answered, 22 be reaction channel, and 23 be heat-conducting medium channel.
Specific embodiment
The following examples are further described method provided by the invention, but not thereby limiting the invention.
Embodiment 1
As shown in Figure 1, micro passage reaction 11 is led comprising what 8 layers of reaction channel 12 and 9 layer being arranged side by side were arranged side by side
Hot media channel 13, the wide 10mm of every reaction channel, high 1mm, long 100mm, every layer has 4 reaction channels 12.Every thermally conductive Jie
Matter channel width 10mm, high 1mm, long 100mm, every layer has 6 heat-conducting medium channels 13.Reaction channel 12 and heat-conducting medium channel 13
Intersect in 90 °.Cobalt-based support type fischer-tropsch synthetic catalyst is loaded in reaction channel 12.
The preparation process of cobalt-based support type fischer-tropsch synthetic catalyst used in the present embodiment is as follows: taking alumina powder, drips
Add distilled water to first wetting, writes down the volume of consumption water, then calculated by 27 weight % of Co content (based on oxide), make nitre
Then sour cobalt maceration extract is calculated by 0.1 weight % of Re content (based on oxide), makes perrhenic acid maceration extract.Then molten with this
Liquid oxide impregnation aluminium is soaked to first, stands 8 hours, then 4 hours dry in 120 DEG C, is roasted 4 hours for 450 DEG C in muffle furnace,
Cobalt-based support type fischer-tropsch synthetic catalyst is made.The cobalt-based support type fischer-tropsch synthetic catalyst particle size range is 50 μm~200 μ
m。
The cobalt-based support type fischer-tropsch synthetic catalyst prepared is seated in reaction channel, at 0.1MPa, in nitrogen gas
In atmosphere, gas space velocity 1000h-1Under the conditions of, reactor is warming up to 120 DEG C with 30 DEG C/h heating rate, in temperature-rise period
Reactor each point maximum temperature difference is not more than 1 DEG C, constant temperature 8h；Hydrogen nitrogen mixed gas is passed through after constant temperature, and (hydrogen volume score is
5%), gas space velocity 3000mL/mLCatalyst/ h is warming up to 280 DEG C with 10 DEG C/h of assigned rate, the reactor in temperature-rise period
Each point maximum temperature difference is not more than 2 DEG C, and temperature is raised to rear constant temperature 12h.Hydrogen nitrogen mixed gas (hydrogen volume score is passed through after constant temperature
For 5%), gas space velocity 2000mL/mLCatalyst/ h is warming up to 400 DEG C with 20 DEG C/h of assigned rate, reacts in temperature-rise period
Device each point maximum temperature difference is not more than 3 DEG C, and it is 2mg/L that temperature, which is raised to after constant temperature 6h and detects moisture content in discharge gas, increases hydrogen
Nitrogen mixed gas hydrogen volume score detects moisture content in discharge gas after being 40%, 6h be 2mg/L, is changed to pure hydrogen charging,
Reduction terminates after when constant temperature 6h, starts with 30 DEG C/h cooling.
Cobalt-based support type fischer-tropsch synthetic catalyst after reduction is in reaction condition: pressure 3.0MPa, and 220 DEG C of temperature, synthesis
Gas (unstripped gas) group becomes H2Volume fraction 60%, CO volume fraction 30%, N2Volume fraction 10%, air speed 20000mL/
mLCatalyst/ h carries out Fischer-Tropsch synthesis, and product is analyzed by gas-chromatography, calculates the conversion ratio, methane selectively and C of CO5 +
Hydrocarbon selective.
After reacting a period of time, cobalt-based support type fischer-tropsch synthetic catalyst is regenerated.Synthesis gas original is cut out first
Material incision N2Metathesis reactor, gas hourly space velocity 6000mL/mLCatalyst/ h reduces catalyst bed after 12 hours with the rate of 20 DEG C/h
Layer temperature is to 160 DEG C.Cut hydrogen, gas hourly space velocity 3000mL/mLCatalyst/ h sets hydrogen partial pressure as 4.5MPa, with heating rate 10
DEG C/h is warming up to 280 DEG C, methane content in temperature-rise period detection discharge gas；After methane content starts reduction, with heating rate 20
DEG C/h is warming up to 400 DEG C；When methane content is lower than 1% in discharge gas, with the rate reduction temperature of reactor of 20 DEG C/h to 50 DEG C,
Hydrocracking process terminates.
Cut out hydrogen incision nitrogen, displacement combustible gas (H into periodic off-gases2+ total hydrocarbon) volume fraction is less than 0.1%；In nitrogen
It is incorporated a certain proportion of air in gas, makes the volume fraction 1% of oxygen in reactor inlet oxygen-containing gas, catalyst is because occurring oxygen
Change reaction temperature and rise to 85 DEG C, after reactor does not have temperature change, steps up temperature of reactor extremely with 25 DEG C per hour
400℃.After 400 DEG C of constant temperature 5h, it is 5% that the volume fraction of oxygen in reactor inlet oxygen-containing gas, which is increased, after constant temperature 5h, switching
For air constant temperature 10h, as CO in periodic off-gases2Oxidation terminates when volume fraction < 0.05%, with 30 DEG C of speed responsers drops per hour
Temperature is to 150 DEG C.
Oxygen-containing gas incision nitrogen is cut out, replaces after oxygen purity is less than 0.1% into periodic off-gases and cuts containing volume
The hydrogen nitrogen mixed gas of 2% hydrogen of score, gas space velocity 3000mL/mLCatalyst/ h reduces catalyst bed temperature with the rate of 20 DEG C/h
Degree is to 400 DEG C, and reactor each point maximum temperature difference is not more than 3 DEG C in temperature-rise period, and temperature is raised to detection discharge gas after constant temperature 6h
Moisture content is 2mg/L in body, increases hydrogen nitrogen mixed gas hydrogen volume score and contains to detect moisture in discharge gas after 40%, 6h
Amount is 2mg/L, is changed to pure hydrogen charging, when constant temperature 6h after restore and terminates, start with 30 DEG C/h cooling, the conjunction of cobalt-based support type Fischer-Tropsch
Terminate at catalyst regeneration process.
Cobalt-based support type fischer-tropsch synthetic catalyst after regeneration carries out F- T synthesis performance test under the same conditions, and new
Fresh catalyst, regeneration procatalyst performance comparison result are listed in table 1.
Embodiment 2
As shown in Fig. 2, micro passage reaction 21 is led comprising what 8 layers of reaction channel 22 and 9 layer being arranged side by side were arranged side by side
Hot media channel 23, every 22 width 20mm of reaction channel, high 1mm, long 100mm, every layer has 3 reaction channels 22.Every thermally conductive
23 width 10mm of medium channel, high 1mm, long 100mm, every layer has 6 heat-conducting medium channels 23.Reaction channel 22 and heat-conducting medium are logical
Road 23 is in 90 ° of intersections.Filling is coated with the catalyst support of cobalt-based support type fischer-tropsch synthetic catalyst in reaction channel 22.
Co based Fischer-Tropsch synthesis catalyst used in the present embodiment is coating type monolithic catalyst, and preparation process is as follows: cobalt
Base supported catalyst is coated on treated undaform stainless steel supporter, the wide 18mm of supporter, high 0.8mm, length
90mm.Supporter ultrasonic oscillation 30min in acetone soln removes surface smut.According to 8%Al powder, 5%Fe, 3%
NH4Cl, remaining is aluminium oxide, is made into aluminizing medium.Aluminizing medium and stainless steel supporter are mixed, roasted at 850 DEG C
120min.The stainless steel supporter that surface is rich in aluminium is made.The ultrasonic oscillation 45min in acetone soln removes surface smut,
It is warming up to 500 DEG C of roasting 120min with the heating rate of 2.0 DEG C/min, prepares the rich salic stainless steel substrates in surface.
By nitric acid and boehmite according to molar ratio H+/Al3+=0.12 is mixed, and after stirring 1.0 hours at 70 DEG C, is reacted old
Change 12 hours, the alumina sol after being aged；Colloidal sol and 20% polyethylene glycol mixing, homogeneous slurry is stirred into, is pressed
It is applied according to infusion process is added dropwise.It after the completion of coating, dries at room temperature 3 hours, then 3 hours dry at 120 DEG C, heating rate
0.5℃/min.Coating part can be put into Muffle kiln roasting after drying, and maturing temperature is 700 DEG C, and heating rate is 0.8 DEG C/
Min, time are 3 hours, and cooled to room temperature takes out sample.Coated carrier part is put into mixed containing cobalt nitrate and ammonium metatungstate
It closes solution and carries out saturation dipping, be dried and roast later.Wherein, drying temperature is 120 DEG C, and drying time is 3 hours, roasting
Burning temperature is 350 DEG C, calcining time 3 hours.The dosage of the cobalt nitrate makes cobalt oxide content in final fischer-tropsch synthetic catalyst
For 45 weight %, tungsten auxiliary agent content is about 2 weight %.
In the Co based Fischer-Tropsch synthesis catalyst supporter intercalation reaction channel prepared, at 0.1MPa, in nitrogen atmosphere
In, gas space velocity 1000mL/gCatalystUnder/h condition, 120 DEG C are warming up to 30 DEG C/h of assigned rate, is reacted in temperature-rise period
Device each point maximum temperature difference is not more than 1 DEG C, constant temperature 8h；Hydrogen nitrogen mixed gas (hydrogen volume score is 5%), gas are passed through after constant temperature
Body air speed is 3000mL/gCatalyst/ h is warming up to 280 DEG C with 10 DEG C/h of assigned rate, and reactor each point is maximum in temperature-rise period
The temperature difference is not more than 2 DEG C, and temperature is raised to rear constant temperature 12h.Be passed through after constant temperature hydrogen nitrogen mixed gas (hydrogen volume score be 5%),
Gas space velocity is 2000mL/gCatalyst/ h is warming up to 400 DEG C with 20 DEG C/h of assigned rate, and reactor each point is most in temperature-rise period
The big temperature difference is not more than 3 DEG C, and it is 2mg/L that temperature, which is raised to after constant temperature 6h and detects moisture content in discharge gas, increases hydrogen nitrogen mixed gas
Hydrogen volume score detects moisture content in discharge gas after being 40%, 6h be 2mg/L, is changed to pure hydrogen and feeds, when constant temperature 6h
Reduction terminates afterwards, starts with 30 DEG C/h cooling.
Cobalt-based support type fischer-tropsch synthetic catalyst after reduction is in reaction condition: pressure 3.0MPa, and 220 DEG C of temperature, synthesis
Gas (unstripped gas) group becomes H2Volume fraction 60%, CO volume fraction 30%, N2Volume fraction 10%, air speed 20000mL/gCatalyst/
H carries out Fischer-Tropsch synthesis, and product is analyzed by gas-chromatography, calculates the conversion ratio, methane selectively and C of CO5 +Hydro carbons choosing
Selecting property.
After reacting a period of time, cobalt-based support type fischer-tropsch synthetic catalyst is regenerated.Synthesis gas incision N is cut out first2
Metathesis reactor, gas hourly space velocity 6000mL/gCatalyst/ h reduced temperature of reactor to 160 DEG C with the rate of 20 DEG C/h after 12 hours.
Cut hydrogen, gas hourly space velocity 3000mL/gCatalyst/ h sets hydrogen partial pressure as 3.0MPa, is warming up to 265 with 10 DEG C/h of heating rate
DEG C, methane content in temperature-rise period detection discharge gas；After methane content starts reduction, 360 are warming up to 20 DEG C/h of heating rate
℃；When discharging that methane content is lower than 1% in gas, temperature of reactor is reduced to 50 DEG C with the rate of 20 DEG C/h, hydrocracking process
Terminate.
Cut out hydrogen incision nitrogen, displacement combustible gas (H into periodic off-gases2+ total hydrocarbon) volume fraction is less than 0.1%；In nitrogen
It is incorporated a certain proportion of air in gas, makes the volume fraction 1% of oxygen in reactor inlet oxygen-containing gas, cobalt-based support type Fischer-Tropsch
Synthetic catalyst because occur oxidizing reaction temperature rise to 85 DEG C, after reactor does not have temperature change, with 25 DEG C per hour by
Step improves temperature of reactor to 350 DEG C.After 350 DEG C of constant temperature 5h, the volume fraction of oxygen in reactor inlet oxygen-containing gas is increased
It is 5%, after constant temperature 5h, air constant temperature 10h is switched to, as CO in periodic off-gases2Oxidation terminates when volume fraction < 0.05%, with every
Hour, 30 DEG C of speed were cooled to 150 DEG C.
Oxygen-containing gas incision nitrogen is cut out, replaces after oxygen purity is less than 0.1% into periodic off-gases and cuts containing volume
The hydrogen nitrogen mixed gas of 2% hydrogen of score, gas space velocity 3000mL/gCatalyst/ h reduces temperature of reactor extremely with the rate of 20 DEG C/h
400 DEG C, reactor each point maximum temperature difference is not more than 3 DEG C in temperature-rise period, and temperature detects in discharge gas after being raised to constant temperature 6h
Moisture content is 2mg/L, increases hydrogen nitrogen mixed gas hydrogen volume score to detect moisture content in discharge gas after 40%, 6h and is
2mg/L is changed to pure hydrogen charging, when constant temperature 6h after restore and terminates, start to cool down with 30 DEG C/h, cobalt-based support type F- T synthesis is urged
Agent regenerative process terminates.
Cobalt-based support type fischer-tropsch synthetic catalyst after regeneration carries out F- T synthesis performance test under the same conditions, and new
Fresh catalyst, regeneration procatalyst performance comparison result are listed in table 2.
Table 1
Table 2
| Fresh catalyst | Before regeneration | Embodiment 2 | |
| Temperature of reactor, DEG C | 220 | 220 | 220 |
| Reaction pressure, MPa | 3.0 | 3.0 | 3.0 |
| Air speed, mL/gCatalyst/h | 20000 | 20000 | 20000 |
| CO conversion ratio, % | 90.6 | 80.7 | 89.8 |
| CH4Selectivity, % | 7.4 | 11.6 | 7.6 |
| C5 +Selectivity, % | 88.6 | 84.7 | 88.9 |
Claims (17)
1. a kind of regeneration method of micro passage reaction fischer-tropsch synthetic catalyst, comprising:
(1) synthesis gas in inert gas replacement reactor is used,
(2) it is passed through hydrogen in reactor, in hydrogen atmosphere, under the conditions of cracking reaction, fischer-tropsch synthetic catalyst is adsorbed big
Cracking reaction occurs for molecular hydrocarbon, obtains methane and lighter hydrocarbons,
(3) step (2) treated fischer-tropsch synthetic catalyst contacts oxygen-containing gas, is aoxidized under oxidative conditions,
(4) the fischer-tropsch synthetic catalyst contact hydrogen-containing gas after step (3) oxidation is restored, and F- T synthesis is urged after being regenerated
Agent,
The fischer-tropsch synthetic catalyst is cobalt-based support type fischer-tropsch synthetic catalyst, in micro passage reaction, filling or painting
Cover the cobalt-based support type fischer-tropsch synthetic catalyst.
2. according to the method for claim 1, which is characterized in that inert gas described in step (1) is selected from N2, in Ar, He
One or more, the air speed for being passed through inert gas is 2000h-1~20000h-1。
3. according to the method for claim 2, which is characterized in that inert gas described in step (1) is selected from N2, it is passed through inertia
The air speed of gas is 5000h-1~10000h-1。
4. according to the method for claim 1, which is characterized in that in step (1) while being passed through inert gas, will react
Device temperature is reduced to 180 DEG C or less.
5. according to the method for claim 1, which is characterized in that in step (2), the air speed for being passed through hydrogen is 2000h-1~
8000h-1, reactor pressure is 0.5MPa~10MPa.
6. according to the method for claim 5, which is characterized in that in step (2), the air speed for being passed through hydrogen is 3000h-1~
5000h-1, reactor pressure is 1.0MPa~8.0MPa.
7. according to the method for claim 1, which is characterized in that reactor temperature control process in step (2) are as follows: heating
To 200 DEG C~300 DEG C, constant temperature 2h~10h, 300 DEG C~450 DEG C are warming up to, constant temperature methane content into discharge gas is lower than 1 body
When product %, reactor temperature is reduced, is down to 50 DEG C.
8. according to the method for claim 7, which is characterized in that in step (2) in reactor temperature control process: heating
To 340 DEG C~400 DEG C, constant temperature reduces reactor temperature when methane content is lower than 1 volume % into discharge gas.
9. according to the method for claim 1, which is characterized in that step (2) treated fischer-tropsch synthetic catalyst contact contains
It before carrier of oxygen, is passed through inert gas and is purged, the fischer-tropsch synthetic catalyst after purging is qualified contacts oxygen-containing gas, and described is lazy
Property gas be selected from N2, one or more of Ar, He；As combustible gas (H in periodic off-gases2+ total hydrocarbon) volume fraction less than 0.1%
When, it is qualified to be considered as purging.
10. according to the method for claim 1, which is characterized in that in step (3), be lower than 50 DEG C~80 in temperature of reactor
DEG C, under pressure 0.5MPa~2.0MPa, fischer-tropsch synthetic catalyst contacts oxygen-containing gas, oxysome product in reactor inlet oxygen-containing gas
Score is 0.5%~2%.
11. according to the method for claim 10, which is characterized in that in step (3), after reactor is passed through oxygen-containing gas, by
Step improves temperature of reactor to 400 DEG C~450 DEG C；
To CO+CO in periodic off-gases2After content is constant, oxysome fraction in oxygen-containing gas, oxygen in reactor inlet oxygen-containing gas are improved
Volume fraction is 5%~15%；
To CO+CO in periodic off-gases2Oxidation terminates after volume content < 0.05%.
12. according to the method for claim 10, which is characterized in that oxygen-containing gas is selected from oxygen and/or air and indifferent gas
The mixed gas of body or water vapour.
13. according to the method for claim 1, which is characterized in that the fischer-tropsch synthetic catalyst contact after step (3) oxidation contains
It before hydrogen, is passed through inert gas and is purged, the fischer-tropsch synthetic catalyst after purging is qualified contacts hydrogen-containing gas, and described is lazy
Property gas be selected from N2, one or more of Ar, He；When the volume fraction of oxygen in periodic off-gases is less than 0.1%, it is considered as purging
It is qualified.
14. according to the method for claim 1, which is characterized in that in step (4), hydrogen-containing gas is passed through in reactor, it is described
The volume fraction of hydrogen is not more than 10% in hydrogen-containing gas, and the air speed for being passed through hydrogen-containing gas is 500~5000h-1, temperature of reactor
It is 350 DEG C~500 DEG C, pressure is 0~2.0MPa, and reactor each point maximum temperature difference is not more than 5 DEG C.
15. according to the method for claim 14, which is characterized in that in step (4), the air speed for being passed through hydrogen-containing gas is 1500
~3000h-1, temperature of reactor is 350 DEG C~450 DEG C, and pressure is 0~1.0MPa, and reactor each point maximum temperature difference is not more than 3
℃。
16. according to the method for claim 1, which is characterized in that in step (4), water content in measurement discharge gas, wait be less than
5mg/L, the volume fraction for improving hydrogen in hydrogen-containing gas is 30%~60%, and 2~20h of constant temperature.
17. according to the method for claim 1, which is characterized in that the cobalt-based support type fischer-tropsch synthetic catalyst includes to live
Property component cobalt, auxiliary agent and carrier, auxiliary agent is selected from one or more of transition metal, rare earth metal and nonmetalloid, carrier
Selected from Al2O3、SiO2、TiO2、ZrO2, one or more of molecular sieve, by weight, the content of cobalt is 10%~50%.
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| WO2020249529A1 (en) * | 2019-06-13 | 2020-12-17 | Velocys Technologies Limited | Regeneration of catalyst |
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| CN114832739A (en) * | 2022-03-29 | 2022-08-02 | 清华大学 | Coupling fluidized bed device and application thereof |
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