CN105861024B - A kind of application process of Co based Fischer-Tropsch synthesis catalyst - Google Patents

A kind of application process of Co based Fischer-Tropsch synthesis catalyst Download PDF

Info

Publication number
CN105861024B
CN105861024B CN201610246442.3A CN201610246442A CN105861024B CN 105861024 B CN105861024 B CN 105861024B CN 201610246442 A CN201610246442 A CN 201610246442A CN 105861024 B CN105861024 B CN 105861024B
Authority
CN
China
Prior art keywords
ghsv
catalyst
constant temperature
cobalt
fixed bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610246442.3A
Other languages
Chinese (zh)
Other versions
CN105861024A (en
Inventor
李德宝
刘岩
侯博
贾丽涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongke Lu'an Energy Technology Co., Ltd.
Original Assignee
Shanxi Institute of Coal Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Institute of Coal Chemistry of CAS filed Critical Shanxi Institute of Coal Chemistry of CAS
Priority to CN201610246442.3A priority Critical patent/CN105861024B/en
Publication of CN105861024A publication Critical patent/CN105861024A/en
Application granted granted Critical
Publication of CN105861024B publication Critical patent/CN105861024B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G2/333—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 platinum-group
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products

Landscapes

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

Abstract

A kind of application process of Co based Fischer-Tropsch synthesis catalyst is that cobalt-base catalyst is loaded in fixed bed or paste state bed reactor once to be reduced, once reduction is carbonized after terminating, secondary reduction is carried out again, treats that temperature is down to less than 120 DEG C switching and merging gas and carries out Fischer-Tropsch synthesis.The present invention has the advantages of greatly improving cobalt-base catalyst F- T synthesis catalytic activity.

Description

A kind of application process of Co based Fischer-Tropsch synthesis catalyst
Technical field
The present invention relates to a kind of application process of Co based Fischer-Tropsch synthesis catalyst.
Background technology
Coal in China main body energy general layout can be changed by oily (CTL) technology of Material synthesis of coal by greatly developing, and can be achieved The optimization deep exploitation of coal clean utilization.CTL techniques have Reasonable Utilizing Its Coal Resources, alleviate world energy sources demand and structure shape The advantages such as contradiction, the ultra-clean liquid motor fuels of production and the senior lubricant of condition, oneself is through widely being paid close attention to.At present, generation Various countries of boundary successfully develop synthesis oil tech, such as fixed fluidized bed (SAS) and slurry bed system (SSPD) work of South Africa Sasol companies Skill, in addition with the fixed bed SMDS techniques of Dutch Shell companies, the GTL techniques of Syntrolem companies, Exxon companies The iron-based slurry of AGC-21 techniques, the GasCat techniques of EnergeInternational companies and Zhong Ke artificial oils company of China State bed process etc..
The hydrogenation activity for being mainly characterized by CO of cobalt-base catalyst is high, chain growing ability is strong, be not easy carbon distribution poisoning, generate it is low Carbon olefin and oxygenatedchemicals are few, the selectivity of methane generation is low, reaction condition is gentle etc..Cobalt-base catalyst is to H2/ CO ratios, temperature Degree and the remolding sensitivity ferrum-based catalyst of pressure are high, the narrow range of operation, and the requirement of device is high；Co catalysts must be at low temperature Operation could obtain suitable selectivity, and so as to cause reaction rate to decline, space-time yield is lower than ferrum-based catalyst, limits it Production application.Therefore, effective means must be taken to improve catalytic performance so that cobalt-base catalyst significantly carries in operating temperature range Its high CO hydrogenation activity, the production efficiency of cobalt-base catalyst can be just greatly improved, so as to realize commercial Application.
The content of the invention
It is an object of the invention to provide a kind of application side that can greatly improve cobalt-base catalyst F- T synthesis catalytic activity Method.
The present invention introduces " carbonization " process in the applying step " reduction-F- T synthesis " of conventional cobalt-base catalyst, should It is " reduction-carbonization-reduction-F- T synthesis " with step improvement.So, reduce rear catalyst in simple substance cobalt crystalline phase from mainly by Face-centred cubic structure (FCC) composition is changed into mainly being made up of the close pile structure of six sides (HCP), such as XRD (X-ray Diffraction) Shown in Fig. 1.The simple substance cobalt of the close pile structure of six sides has higher F- T synthesis catalytic activity than face-centred cubic structure simple substance cobalt.
The present invention be directed to cobalt in final finished catalyst with made by oneself existing for oxidation states or patent, article etc. its His form discloses the improved application of the cobalt-base catalyst of report.
The application process of the present invention is realized by following steps：
(1) cobalt-base catalyst is loaded in fixed bed or paste state bed reactor；
(2) cobalt-base catalyst is once reduced in fixed bed or paste state bed reactor, fixed bed reducing condition is： 280~500 DEG C, 0.1~1.5MPa, GHSV=500~1500h-1, 6~48h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume Content is 5%~100%；Slurry bed system reducing condition is：250~380 DEG C, 0.1~1.0MPa, GHSV=500~1500h-1, it is permanent 6~48h of temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content is 5%~100%, and rotating speed is 400~1500rpm；
(3) once reduction is carbonized after terminating, and fixed bed Carbonization Conditions are：180~350 DEG C, 0.1~2.0MPa, GHSV=500~2000h-1, 2~12h of constant temperature, using CO gas or CO and H2Gaseous mixture；Slurry bed system Carbonization Conditions are：180 ~350 DEG C, 0.1~2.0MPa, GHSV=500~2000h-1, 2~12h of constant temperature, using CO gas or CO and H2Gaseous mixture, Rotating speed is 400~1500rpm；
(4) carbonization carries out secondary reduction after terminating, and fixed bed reducing condition is：250~450 DEG C, 0.1~1.0MPa, GHSV=500~1500h-1, 6~36h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content is 5%~100%；Slurry bed system Reducing condition is：250~350 DEG C, 0.1~1.0MPa, GHSV=500~1500h-1, 6~36h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content is 5%~100%, and rotating speed is 400~1500rpm.
(5) after secondary reduction terminates, treat that temperature is down to less than 120 DEG C switching and merging gas and carries out Fischer-Tropsch synthesis, it is fixed Bed reaction condition be：170~250 DEG C, 1.0~5.0Mpa, GHSV=500~3000h-1, H2/ CO (v/v)=1.8~3.0；Slurry State bed reaction condition is：180~240 DEG C, 1.0~5.0MPa, GHSV=500~3000h-1, H2/ CO (v/v)=2.0~3.0, Rotating speed is 400~1500rpm.
Cobalt-base catalyst as described above is self-control or the method system for disclosing report according to other forms such as patent, articles Standby.
Step (3) CO and H as described above2Gaseous mixture be CO volume contents be 50%-95% gaseous mixture.
The application process of catalyst of the present invention has the following advantages that：
(1) application process of the present invention can greatly improve the F- T synthesis catalytic activity of cobalt-base catalyst；
(2) application process of the present invention is simple to operate, without increasing equipment investment, is very easy to realize.
Brief description of the drawings
Fig. 1 is the XRD of catalyst before and after present invention improvement.
Embodiment
Embodiment 1：
Method according to the embodiments 7 of patent ZL 201210160020.6 prepares cobalt-base catalyst：Account for by aluminum oxide and finally urge 89 (wt) % of agent measure boehmite, while prepare 4.5mol/L Na2CO3Solution, both mix regulation and intend thin water aluminium Stone slurries pH is 8.5.1.0 (wt) % of final catalyst are accounted for by barium monoxide, prepare 1.0mol/L Ba (NO3)2Solution, it is and upper State alkali lye under agitation while be added drop-wise in boehmite alkali lye, kept for 55 DEG C, after controlling endpoint pH 8.5, precipitation to terminate Static burn in 5h, washing, filter to free from admixture.Filter cake is dried into 8h at 80 DEG C, is then calcined 9h at 450 DEG C, is made and urges Agent carrier.9.9 (wt) % and 0.1 (wt) % for accounting for final catalyst respectively by cobalt oxide and palladium oxide weigh Co (NO3)2· 6H2O and PdCl2, deionized water is measured according to equi-volume impregnating, mixing salt solution is prepared and is simultaneously impregnated in above-mentioned carrier, during dipping Between be 9h, then at 85 DEG C dry 6h, finally 300 DEG C be calcined 10h, be made catalyst.Final catalyst quality percentage For Co3O4：BaO：PdO2：Al2O3=9.9：1.0：0.1：89.
Take above-mentioned catalyst 20g to be loaded in fixed bed reactors once to be reduced, reducing condition is：400 DEG C, 1.5MPa, GHSV=1500h-1, constant temperature 6h, using hydrogen reduction gas, H in nitrogen2Content is 10% (v/v)；After the completion of once reducing It is carbonized, Carbonization Conditions are：350 DEG C, 0.1MPa, GHSV=500h-1, constant temperature 12h, using CO atmosphere；After carbonization terminates, enter Row secondary reduction, secondary reduction condition are：450 DEG C, 0.1MPa, GHSV=500h-1, constant temperature 36h, using hydrogen reduction gas in nitrogen, H2Content is 35% (v/v)；After secondary reduction terminates, treat that temperature is down to less than 120 DEG C, it is anti-that switching and merging gas carries out F- T synthesis Should, reaction condition is：220 DEG C, 3.0Mpa, GHSV=800h-1, H2/ CO (v/v)=3.0.Reaction result is shown in Table 1, and and patent The Comparative result of ZL201210160020.6 embodiments 7.
Embodiment 2：
Method according to the embodiments 5 of patent ZL 201010539363.4 prepares cobalt-base catalyst：By Co：W：Zn=16： 43：39 ratio prepares modified zinc oxide-loaded cobalt catalyst.1.0M nitric acid zinc salt ethanol solutions are prepared, it is molten to prepare 1.2M ammoniacal liquor Liquid precipitates zinc salt as precipitating reagent under the conditions of pH=7.5,50 DEG C, after Washing of Filter Cake to neutrality, in 110 DEG C of dryings, and 400 It is calcined 5 hours at DEG C, gained sample broke is into stand-by after the powder below 200 mesh.By setting ratio, it is water-soluble to prepare ammonium paratungstate Liquid, using equi-volume process to gained sample load tungsten, through 115 DEG C of dryings, be calcined 2 hours at 480 DEG C, gained sample broke into It is stand-by after powder below 200 mesh.Amount and the cobalt that 7wt%, Cr account for 8% are accounted for by Ni in final catalyst, prepares nickel nitrate, nitric acid The mixed solution of chromium and cobalt nitrate, using equi-volume process Supported Co, sample is calcined 5 hours at 360 DEG C and produced through 100 DEG C of dryings Final catalyst.Catalyst composition is 13.88wt%Co/37.30wt%W/33.83wt%Zn/7.0wt%Ni/8.0wt% Cr。
Take above-mentioned catalyst 20g to be loaded in fixed bed reactors once to be reduced, reducing condition is：450 DEG C, 1.2MPa, GHSV=1200h-1, constant temperature 12h, using hydrogen reduction gas, H in nitrogen2Content is 30% (v/v)；After the completion of once reducing It is carbonized, Carbonization Conditions are：330 DEG C, 0.2MPa, GHSV=700h-1, constant temperature 10h, using CO atmosphere；After carbonization terminates, enter Row secondary reduction, secondary reduction condition are：400 DEG C, 0.3MPa, GHSV=700h-1, constant temperature 30h, using hydrogen reduction gas in nitrogen, H2Content is 50% (v/v)；After secondary reduction terminates, treat that temperature is down to less than 120 DEG C, it is anti-that switching and merging gas carries out F- T synthesis Should, reaction condition is：230 DEG C, 2.0Mpa, GHSV=1000h-1, H2/ CO (v/v)=2.0.Reaction result is shown in Table 1, and with it is special The Comparative result of sharp ZL201010539363.4 embodiments 5.
Embodiment 3：
Method according to the embodiments 1 of patent ZL 201210050261.5 prepares cobalt-base catalyst：Added in reactor A 4500g deionized waters, 500g γ-Al are added after opening stirring motor2O3Powder stirs, and adds hydrochloric acid and continues mixing until slurries pH It is worth for 5.0.5500g deionized waters are added in reactor B, and add 500g γ-Al2O3Powder, after being uniformly mixed, by AB The slurry of two kettles is well mixed, and is stood 1 hour after being heated to 80 DEG C, is continued to stir, and is added alkaline silica sol, is made sial mass ratio For SiO2：Al2O3=20：80, continue to be uniformly mixed.The 0.1mol/L prepared zirconyl chloride solution is slowly added to Into above-mentioned slurry, slurry temperature is controlled at 25 DEG C, and spray drying device spray shaping is used after well mixed, and zirconium oxychloride adds Enter amount for SiO in slurry2、Al2O3And the 0.5% of zirconium oxychloride gross mass.Obtained granular powder material is calcined 6 at 650 DEG C Hour, it is standby after cooling.Configure 1mol/L cobalt nitrate solution, 0.5mol/L lanthanum nitrate hexahydrate, 0.1mol/L nitre Sour ruthenium solution and 0.1mol/L rhodium nitrate solution, the carrier prepared using impregnation, by the catalyst after dipping at 150 DEG C Under conditions of dry 4 hours, after be calcined 5 hours under the conditions of 500 DEG C and obtain most catalyst.The quality of cobalt is catalysis in catalyst The 20% of agent gross mass, the quality of lanthanum are the 0.91% of catalyst gross mass, and the quality of ruthenium is the 0.05% of catalyst gross mass, The quality of rhodium is the 0.04% of catalyst gross mass, and the quality of zirconium is the 0.2% of catalyst gross mass.
Take above-mentioned catalyst 20g to be loaded in paste state bed reactor once to be reduced, reducing condition is：350 DEG C, 1.0MPa, GHSV=1000h-1, constant temperature 18h, 400rpm, using hydrogen reduction gas, H in nitrogen2Content is 40% (v/v)；Once also It is carbonized after the completion of original, Carbonization Conditions are：300 DEG C, 0.5MPa, GHSV=800h-1, constant temperature 8h, 600rpm, using CO gas Atmosphere；After carbonization terminates, secondary reduction is carried out, secondary reduction condition is：350 DEG C, 0.5MPa, GHSV=800h-1, constant temperature 24h, 800rpm, using hydrogen reduction gas, H in nitrogen2Content is 60% (v/v)；After secondary reduction terminates, treat that temperature is down to less than 120 DEG C, Switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition：Reaction condition：215 DEG C, 2.5Mpa, GHSV=2500h-1, H2/CO (v/v)=2.0,1000rpm.Reaction result is shown in Table 1, and with the Comparative result of patent ZL201210050261.5 embodiments 1.
Embodiment 4：
Method according to patent ZL 201110184014.X embodiments 4 prepares cobalt-base catalyst：Commercial silica gel 30g is weighed, Distilled water is added dropwise to first profit, the volume for consuming water is 48ml.Silica gel is put into tube furnace, nitrogen is passed through and enters line replacement, then Volume ratio is passed through as 3：1 ethene and the gaseous mixture of helium, the volume space velocity of ethene is 800h-1, it is passed through the time 10 hours, tubular type Furnace temperature is 800 DEG C, and cooling is made by the modified silica gel carrier that final catalyst nano carbon fiber content is 10.3%.By final Catalyst zirconium content 2wt% is counted, and is weighed nitrate trihydrate zirconium 2.82g, is added distilled water to wait to be completely dissolved, add above-mentioned modification to 48g Impregnate, aging 3 hours, 80 DEG C of dryings 12 hours, be calcined 4 hours in 350 DEG C in carrier silica gel afterwards.By final catalyst molybdenum Content 1wt%, ammonium molybdate 0.55g is weighed, adds distilled water to wait to be completely dissolved, add in the sample after above-mentioned load zirconium to 48g, Aging 3 hours, 80 DEG C of dryings 12 hours, it is calcined 4 hours at 350 DEG C under vacuum or in inert atmosphere.By final catalysis Agent cobalt content 20wt%, cobalt nitrate hexahydrate 29.64g, distilled water is added to wait to be completely dissolved, after adding above-mentioned dipping zirconium and molybdenum to 48g Sample in, aging 3 hours, 80 DEG C of dryings 12 hours, 350 DEG C are calcined 4 hours under vacuum or in inert atmosphere, and sieve takes 60-80 mesh scopes, required catalyst is made.
Take above-mentioned catalyst 20g to be loaded in fixed bed reactors once to be reduced, reducing condition is：500 DEG C, 1.0MPa, GHSV=1000h-1, constant temperature 24h, using hydrogen reduction gas, H in nitrogen2Content is 50% (v/v)；After the completion of once reducing It is carbonized, Carbonization Conditions are：270 DEG C, 0.7MPa, GHSV=1000h-1, constant temperature 6h, using CO atmosphere；After carbonization terminates, enter Row secondary reduction, secondary reduction condition are：350 DEG C, 0.7MPa, GHSV=800h-1, constant temperature 16h, using hydrogen reduction gas in nitrogen, H2Content is 90% (v/v)；After secondary reduction terminates, treat that temperature is down to less than 120 DEG C, it is anti-that switching and merging gas carries out F- T synthesis Should, reaction condition：215 DEG C, 2.0Mpa, GHSV=2500h-1, H2/ CO (v/v)=2.0.Reaction result is shown in Table 1, and and patent The Comparative result of ZL201110184014.X embodiments 4.
Embodiment 5：
Method according to patent ZL201110393919.8 embodiments 2 prepares cobalt-base catalyst：1g CTAB are dissolved in 30ml In the 0.05mol/L NaOH aqueous solution, then the speed addition 6.74mlTEOS with 2ml/min, continue after stirring 60min, stand 8h, then 100 DEG C of aging 72h.After cleaning filtering with deionized water and ethanol, 30h is dried at 90 DEG C, with 3 DEG C/min in 650 DEG C of roastings 10h is burnt, obtains mesopore-macropore diplopore distribution carrier.Configure a certain amount of zeolite precursor liquid solution.By 0.8g sodium aluminates (NaAlO2) and 1g sodium hydroxides (NaOH) be dissolved in 50mL tetraethyl ammonium hydroxides (aqueous solution of TEAOH 25%), add Simultaneously 6h is stirred at room temperature in homogeneously in 10g White Carbon blacks, obtains the precursor solution of zeolite nano-cluster.The zeolite precursor that will have been configured Liquid solution takes 3ml to be added in 3g mesopore-macropores carrier obtained above, then adds 20ml glycerine, then turns at 200 DEG C Enter from crystallization 12 days in pressure kettle.Most after drying 30h at 90 DEG C, 10h are calcined at 650 DEG C with 3 DEG C/min, obtain micropore-mesopore-big Hole multi-stage porous silicon carrier.3g carriers are subjected to incipient impregnation with being dissolved in the solution of 9ml cobalt nitrates containing 2.91g.Will be isometric The catalyst of non-drying is put into autoclave after dipping 20h, then 10% ammonia spirit is placed in the outer and inner lining of beaker Between, be placed in after sealing in 60 DEG C of baking ovens and react 0.5h, naturally cool to room temperature, then in an oven 60 DEG C baking 12h, finally in horse Not 650 DEG C of roasting 10h in stove, produce required catalyst.
Take above-mentioned catalyst 15ml more than 100 mesh to be put into 1L slurry stirred tank, then add 1000ml liquid stones Wax, once reduced first, reducing condition is：280 DEG C, 0.7MPa, GHSV=800h-1, 1000rpm, constant temperature 30h, use Hydrogen reduction gas in nitrogen, H2Content is 70% (v/v)；It is carbonized after the completion of once reducing, Carbonization Conditions are：250 DEG C, 1.0MPa, GHSV=1200h-1, 1000rpm, constant temperature 5h, using CO atmosphere；After carbonization terminates, secondary reduction is carried out, it is secondary to go back Old terms is：320 DEG C, 0.7MPa, GHSV=1000h-1, 1200rpm, constant temperature 18h, using hydrogen reduction gas, H in nitrogen2Content is 10% (v/v)；After secondary reduction terminates, treat that temperature is down to less than 120 DEG C, switching and merging gas carries out Fischer-Tropsch synthesis, reaction Condition：210 DEG C, 1.2Mpa, GHSV=2000h-1, H2/ CO (v/v)=3.0,1400rpm.Reaction result is shown in Table 1, and and patent The Comparative result of the embodiments 2 of ZL 201110393919.8.
Embodiment 6：
Method according to the embodiments 2 of patent ZL 201210486283.6 prepares cobalt-base catalyst：Prepare a certain amount of The 0.1mol/L aluminium isopropoxide aqueous solution, and hydrolytic reagent HCl is added in the solution by 0.01mol/L, microwave power 20W Lower keeping temperature is 75 DEG C, retention time 90min, is then 0.05 by glue and silicon source mol ratio：1 adds peptizing agent HNO3, microwave power is to be stirred at reflux under 200W to transparent colloidal sol, keeps 3h, then gel is made in aging 12h at room temperature. Gel is put in drying box in 100 DEG C of dry 6h, then xerogel is placed in temperature programming stove, 1 DEG C/min of heating rate, 10h is calcined at 350 DEG C, catalyst carrier is made.The 18 of final catalyst are accounted for respectively by cobaltosic oxide, cupric oxide and ruthenium-oxide (wt) %, 10 (wt) % and 2% weigh Co (NO3)2·6H2O、Cu(NO3)2·3H2O and RuCl3·3H2O, according to isometric leaching Stain method measures deionized water, is configured to mixing salt solution and is impregnated in above-mentioned carrier, dip time 5h, then at 100 DEG C 6h is dried, is finally calcined 5h, 3.5 DEG C/min of heating rate at 340 DEG C, catalyst is made.Final catalyst weight is Co3O4： CuO：RuO2：Al2O3=18：10：2：70.
Take above-mentioned catalyst 20g once to be reduced in the 1L slurry bed system stirred tanks equipped with 500ml atoleines, reduce Condition is：300 DEG C, 0.5MPa, GHSV=700h-1, constant temperature 42h, 1000rpm, using hydrogen reduction gas, H in nitrogen2Content is 80% (v/v)；It is carbonized after the completion of once reducing, Carbonization Conditions are：200 DEG C, 1.5MPa, GHSV=1500h-1, constant temperature 4h, 600rpm, using CO atmosphere；After carbonization terminates, secondary reduction is carried out, secondary reduction condition is：300 DEG C, 0.8MPa, GHSV= 1200h-1, constant temperature 12h, 800rpm, using hydrogen reduction gas, H in nitrogen2Content is 30% (v/v)；After secondary reduction terminates, temperature is treated Degree is down to less than 120 DEG C, and switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition：220 DEG C, 3.0Mpa, GHSV=2000h-1, H2/ CO (v/v)=3.0,1000rpm.Reaction result is shown in Table 1, and with the knot of the embodiments 2 of patent ZL 201210486283.6 Fruit contrasts.
Embodiment 7：
Method according to the embodiments 1 of patent ZL 201210486282.1 prepares cobalt-base catalyst：Prepare a certain amount of Lmol/L aluminum sulfate aqueous solution, and hydrolytic reagent NaOH is added in the solution by 0.05mol/L, it is 40 to keep bath temperature DEG C, retention time 180min, 0.1 (wt) % that final catalyst is accounted for by aoxidized nail weighs RuC13·3H2O is added to the solution In, it is then 1 by glue and silicon source mol ratio：1 adds peptizing agent H2SO4, microwave power is to be stirred at reflux under 50W in saturating Bright colloidal sol, 6h is kept, then gel is made in aging 24h at room temperature.Gel is put in drying box in 50 DEG C of dry 2h, then will Xerogel is placed in temperature programming micro-wave oven, heating rate 2 DEG C/min, and 12h is calcined at 550 DEG C, and catalyst carrier is made.By four 16.8 (wt) % that the brill of oxidation three accounts for final catalyst weigh Co (NO3)2·6H2O, deionization is measured according to equi-volume impregnating Water, it is configured to mixing salt solution and is impregnated in above-mentioned carrier, dip time 10h, 24h is then dried at 120 DEG C, is finally existed 450 DEG C of roasting l0h, are made catalyst.Final catalyst weight is Co3O4：RuO2：A12O3=16.8：0.2：83.
Take above-mentioned catalyst 20g once to be reduced in the 1L slurry bed system stirred tanks equipped with 500ml atoleines, reduce Condition is：330 DEG C, 0.1MPa, GHSV=500h-1, constant temperature 48h, 400rpm, using hydrogen reduction gas, H in nitrogen2Content is 90% (v/v)；It is carbonized after the completion of once reducing, Carbonization Conditions are：180 DEG C, 2.0MPa, GHSV=2000h-1, constant temperature 2h, 1500rpm, using CO atmosphere；After carbonization terminates, secondary reduction is carried out, secondary reduction condition is：250 DEG C, 1.0MPa, GHSV= 1500h-1, constant temperature 6h, 600rpm, using hydrogen reduction gas, H in nitrogen2Content is 70% (v/v)；After secondary reduction terminates, temperature is treated Less than 120 DEG C are down to, switching and merging gas carries out Fischer-Tropsch synthesis, reaction condition：220 DEG C, 3.0Mpa, GHSV=2000h-1, H2/ CO (v/v)=2.0,800rpm.Reaction result is shown in Table 1, and with the result pair of the embodiments 1 of patent ZL 201210486282.1 Than.
The catalyst reaction result of table 1

Claims (1)

1. a kind of application process of Co based Fischer-Tropsch synthesis catalyst, it is characterised in that comprise the following steps：
（1）Cobalt-base catalyst is loaded in fixed bed or paste state bed reactor；
（2）Cobalt-base catalyst is once reduced in fixed bed or paste state bed reactor, fixed bed reducing condition is：280~ 500 DEG C, 0.1 ~ 1.5MPa, GHSV=500 ~ 1500h-1, 6 ~ 48h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content be 5% ~ 100%；Slurry bed system reducing condition is：250 ~ 380 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, 6 ~ 48h of constant temperature, using in nitrogen Hydrogen is to go back Primordial Qi, H2Volume content is 5% ~ 100%, and rotating speed is 400 ~ 1500rpm；
（3）Once reduction is carbonized after terminating, and fixed bed Carbonization Conditions are：180 ~ 350 DEG C, 0.1 ~ 2.0MPa, GHSV=500 ~ 2000h-1, 2 ~ 12h of constant temperature, using CO gas or CO and H2Gaseous mixture；Slurry bed system Carbonization Conditions are：180 ~ 350 DEG C, 0.1 ~ 2.0MPa, GHSV=500 ~ 2000h-1, 2 ~ 12h of constant temperature, using CO gas or CO and H2Gaseous mixture, rotating speed be 400 ~ 1500rpm；
（4）Carbonization carries out secondary reduction after terminating, and fixed bed reducing condition is：250 ~ 450 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, 6 ~ 36h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content is 5% ~ 100%；Slurry bed system reducing condition is：250~ 350 DEG C, 0.1 ~ 1.0MPa, GHSV=500 ~ 1500h-1, 6 ~ 36h of constant temperature, hydrogen is used in nitrogen as also Primordial Qi, H2Volume content be 5% ~ 100%, rotating speed is 400 ~ 1500rpm；
（5）After secondary reduction terminates, treat that temperature is down to less than 120 DEG C switching and merging gas and carries out Fischer-Tropsch synthesis, fixed bed is anti- The condition is answered to be：170 ~ 250 DEG C, 1.0 ~ 5.0Mpa, GHSV=500 ~ 3000h-1, H2/ CO volume=1.8 ~ 3.0；Slurry reactor bar Part is：180 ~ 240 DEG C, 1.0 ~ 5.0MPa, GHSV=500 ~ 3000h-1, H2/ CO volume ratio=2.0 ~ 3.0, rotating speed be 400 ~ 1500rpm；
The step（3）CO and H2Gaseous mixture be CO volume contents be 50%-95% gaseous mixture.
CN201610246442.3A 2016-04-20 2016-04-20 A kind of application process of Co based Fischer-Tropsch synthesis catalyst Active CN105861024B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610246442.3A CN105861024B (en) 2016-04-20 2016-04-20 A kind of application process of Co based Fischer-Tropsch synthesis catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610246442.3A CN105861024B (en) 2016-04-20 2016-04-20 A kind of application process of Co based Fischer-Tropsch synthesis catalyst

Publications (2)

Publication Number Publication Date
CN105861024A CN105861024A (en) 2016-08-17
CN105861024B true CN105861024B (en) 2017-11-17

Family

ID=56632510

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610246442.3A Active CN105861024B (en) 2016-04-20 2016-04-20 A kind of application process of Co based Fischer-Tropsch synthesis catalyst

Country Status (1)

Country Link
CN (1) CN105861024B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107020154A (en) * 2017-05-02 2017-08-08 江南大学 A kind of preprocess method of the cobalt-base catalyst activity of raising CO Hydrogenation alkene
CN108246313B (en) * 2018-02-01 2021-03-02 中科合成油内蒙古有限公司 High-dispersion heavy hydrocarbon Fischer-Tropsch synthesis catalyst based on carbonization treatment method and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1583274A (en) * 2004-06-11 2005-02-23 中国科学院山西煤炭化学研究所 Reductive method for iron/mangan catalyst for fischer-tropsch synlhesis
EP2530125A1 (en) * 2011-05-30 2012-12-05 Total SA Core-shell particles with catalytic activity
CN104815701A (en) * 2015-04-10 2015-08-05 中国科学院上海高等研究院 Cobalt-based catalyst reduction processing method used for Fischer-Tropsch synthesis
CN105344356B (en) * 2015-11-19 2019-01-04 中科潞安能源技术有限公司 A kind of alumina load Co catalysts and preparation method and the application in F- T synthesis

Also Published As

Publication number Publication date
CN105861024A (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN105195156B (en) A kind of preparation method and application of high dispersive copper-based catalysts
CN110327933A (en) Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application
CN111229303B (en) Composite catalyst for directly preparing high-value aromatic hydrocarbon from carbon dioxide, preparation method and application
CN107774263B (en) A kind of preparation method of catalst for synthesis of methanol
CN107890870A (en) A kind of carbon dioxide and water methanation catalyst and its preparation method and application
CN102000575A (en) Cobalt-based Fischertropsch synthesis catalyst for slurry-bed reactor, and preparation method and application thereof
CN113209958B (en) Zn-doped solid solution catalyst, preparation and application thereof
CN112517012B (en) CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation
CN105861024B (en) A kind of application process of Co based Fischer-Tropsch synthesis catalyst
CN107774262B (en) The preparation method of copper zinc catalyst
CN113713804B (en) Metal oxide with high specific surface area, and preparation method and application thereof
CN110560153B (en) Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof
CN106890650A (en) A kind of catalyst for F- T synthesis and preparation method thereof
CN104591960B (en) Heterogeneous catalytic method and device for synthesis of aldehyde by hydroformylation of olefins and alcohol
CN106732620A (en) A kind of nickel series hydrogenating catalyst and preparation method thereof
CN108262047A (en) A kind of nickel-molybdenum series hydrocatalyst and preparation method thereof
CN105170156B (en) The preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure
CN108264586A (en) A kind of method of hydrotreating of C 5 petroleum resin
CN111054384B (en) Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof
CN105521775B (en) A kind of carrier S iO2And preparation method thereof and copper-based catalysts and its preparation method and application
CN107790138B (en) A kind of copper zinc catalyst and preparation method thereof
CN102049259A (en) Preparation method of cobalt-based catalyst for Fischer-Tropsch synthesis
CN105602603B (en) The Fischer-Tropsch synthesis method of hydrogen synchronization roasting reduction improvement Fischer-Tropsch synthesis cobalt-based catalyst is faced in original position
CN105713657A (en) Hydrocracking method
CN101966461B (en) Superfine cobalt-based catalyst for slurry bed reactor and preparation and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20180611

Address after: 030001 78 building, 27 Taoyuan South Road, Yingze District, Taiyuan, Shanxi.

Patentee after: Zhongke Lu'an Energy Technology Co., Ltd.

Address before: No. 27, Taoyuan South Road, Yingze District, Taiyuan, Shanxi

Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences