CN105498798A - Catalyst for directly converting synthesis gas into long-chain alkene by one-step method - Google Patents

Catalyst for directly converting synthesis gas into long-chain alkene by one-step method Download PDF

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CN105498798A
CN105498798A CN201510925821.0A CN201510925821A CN105498798A CN 105498798 A CN105498798 A CN 105498798A CN 201510925821 A CN201510925821 A CN 201510925821A CN 105498798 A CN105498798 A CN 105498798A
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catalyst
temperature
cobalt
carrier
solution
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安芸蕾
钟良枢
孙予罕
沈群
于飞
杨彦章
李正甲
李晋平
肖亚宁
刘斌
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Shanghai Advanced Research Institute of CAS
Shanxi Luan Mining Group Co Ltd
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Shanghai Advanced Research Institute of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
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    • 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
    • B01J23/8892—Manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • C07—ORGANIC CHEMISTRY
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium

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Abstract

The invention discloses a catalyst for directly converting synthesis gas into long-chain alkene by a one-step method. The catalyst comprises metallic cobalt, auxiliary agents and carriers, wherein the auxiliary agents are selected from one or a plurality of materials of potassium, manganese, iron, copper, zinc and zirconium; the mol ratio of the auxiliary agents to the cobalt is 10 to the maximum degree; the carriers are selected from one or a plurality of materials of Al2O3, SiO2, TiO2, MgO, BaO, active carbon and molecular sieves; through being metered by the total quality of the catalyst as the reference, the mass percentage of the carriers is 0 to 99 weight percent. The catalyst has the advantages that the catalyst has high activity and high long-chain alkene selectivity; the cost is low; the operation can be performed at low temperature and low pressure; the preparation is simple and convenient; the industrial amplification can be easily realized, and the like.

Description

A kind of catalyst directly changing into long-chain olefin for the synthesis of gas one-step method
Technical field
The invention belongs to catalyst field, be specifically related to a kind of catalyst directly changing into long-chain olefin for the synthesis of gas one-step method.
Background technology
The key component of synthesis gas is CO and H 2, can be used as the basic material of chemical industry.Current synthesis gas obtains mainly through coal, oil, natural gas.Synthesis gas is of many uses, is a kind of clean energy, is the important foundation realizing green chemical industry.The preparation technology of synthesis gas mainly contains: the synthesis gas preparation technology taking natural gas as raw material; Coal gasifying process; Natural gas & coal is gasifying process altogether.On the whole, China is the country of a scarcity of resources per capita, and the development of the preparation and application of synthesis gas is to the protection of china natural resources, and the improvement of environment has extremely important meaning.
F-T synthesis is the main path that Synthetic holography utilizes, and current fischer-tropsch synthesis process divides two classes: high temperature fischer-tropsch synthesis and Low Temperature Fischer Tropsch synthesis.The high temperature fischer-tropsch synthesis technique of South Africa rope Sa (Sasol) company uses Fe catalyst based, adopts fluidized-bed reactor, and temperature, between 300 ~ 350 DEG C, mainly produces gasoline and linear low molecular weight alkane.Low Temperature Fischer Tropsch synthesis use Fe base or Co catalyst based, temperature, between 200 ~ 240 DEG C, main produces high amylose hydrocarbon.Affect the multiple because have of F-T synthesis, as catalyst structure, reactor and reaction condition etc.With regard to reaction condition, reaction temperature, reaction pressure, air speed and the gas composition catalytic performance that all possibility extreme influence is final.From thermodynamics, reaction temperature major effect be reactive chemistry balance, temperature is higher, not necessarily favourable to F-T synthetic reaction.Temperature raises, and CO conversion rate is accelerated, but carbon deposit reaction is the endothermic reaction, and raised temperature is conducive to the generation of carbon deposit reaction, in addition, if temperature is too high, easily makes catalyst overtemperature sinter, shortens service life, even can damage device time serious.And consider from aerodynamic point, temperature raises, and reaction speed is accelerated, and the speed of side reaction simultaneously is also accelerated thereupon.Therefore, the seeking of suitable reaction temperature is extremely necessary, and operating temperature depends on used catalyst.For the impact of pressure on fischer-tropsch reaction, researcher finds, increase pressure and generally can accelerate the quickening of F-T synthesising reacting speed, but side reaction speed is also accelerated.Simultaneously excessive pressure needs high-pressure bottle, and the high and energy consumption of the investment cost of equipment increases thereupon.In a word, for obtaining best Fischer-Tropsch catalytic performance, the various influence factor of complex optimum is needed.
Long-chain olefin or higher olefins refer to that molecule contains the aliphatic hydrocarbon of more than 5 carbon atoms and a carbon-to-carbon double bond, and its general formula is C nh 2n.Be divided into end alkene and internal olefin according to position of double bond difference, wherein terminal olefine is also called alpha-olefin.Long-chain olefin is widely used in petrochemical industry, light industry, weaving, metallurgy and the aspect such as medicine and agricultural chemicals.Long-chain olefin can be used for the high valuable chemicals such as synthesizing bigh carbon alcohol, long chain mercaptans, lubricating oil.Therefore, the application prospect of long-chain olefin is very considerable, if it is of great value for directly preparing long-chain olefin from synthesis gas.The preparation of current long-chain olefin is mainly by petroleum cracking and low-carbon alkene polymerization gained.Undoubtedly, adopt Fischer-tropsch process, by synthesis gas directly long-chain olefin processed have that flow process is short, low power consumption and other advantages, and the dependence to petroleum resources can be avoided.But long-chain olefin content is general all lower in current F-T synthesis products therefrom, its main cause is to lack suitable catalyst.Therefore, directly long-chain olefin catalyst processed is most important to research and develop efficient synthesis gas.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of catalyst being converted into long-chain olefin for the synthesis of gas, low to overcome catalyst choice in prior art, the defect of severe reaction conditions.
In order to reach foregoing invention object and other objects, the present invention is achieved by the following technical solutions:
The invention provides a kind of catalyst for synthesis gas directly being changed into long-chain olefin, described catalyst comprises metallic cobalt, auxiliary agent and carrier: described auxiliary agent be selected from potassium, manganese, iron, copper, zinc and zirconium one or more, the mol ratio of described auxiliary agent and cobalt is 10 to the maximum; Described carrier is selected from Al 2o 3, SiO 2, TiO 2, MgO, BaO, one or more in active carbon and molecular sieve, in the gross mass of described catalyst for benchmark, the mass percentage of described carrier is 0 ~ 99wt%.
Preferably, described auxiliary agent is one or more in potassium, manganese, iron and zinc.
Preferably, the mass percentage of described carrier is 10 ~ 99wt%.More preferably, the mass percentage of described carrier is 20 ~ 30wt%.
More preferably, described carrier is active carbon, Al 2o 3, SiO 2and TiO 2in one or more.
Preferably, the mol ratio of described auxiliary agent and cobalt is 0.1 ~ 10.
More preferably, the mol ratio of described auxiliary agent and cobalt is 0.1 ~ 5.
More preferably, the mol ratio of described auxiliary agent and cobalt is 0.5 ~ 2.1.
Preferably, described auxiliary agent is at least containing manganese.
More preferably, the mol ratio of described manganese and cobalt is 0.5 ~ 2.
The invention also discloses a kind of method preparing catalyst as described above, for adopting infusion process or coprecipitation.
Preferably, described infusion process comprises the steps:
1) be dissolved in the water cobalt and the corresponding salt of auxiliary agent formation mixing salt solution;
2) by step 1) in mixing salt solution progressively impregnated on carrier;
3) dry at 50 ~ 150 DEG C, then roasting at 200 ~ 500 DEG C.
Preferably, step 1) in mixing salt solution total slaine molar concentration be 6mol/L to the maximum.
Preferably, step 3) in baking temperature be 80 ~ 120 DEG C.Drying time is 2 ~ 50h.More preferably, drying time is 8 ~ 30h.More preferably, sintering temperature is 300 ~ 450 DEG C.Roasting time is 1 ~ 20h.More preferably, roasting time is 2 ~ 10h.
Described step 3) in, drying can be carried out under vacuum condition, air atmosphere and inert atmosphere, prioritizing selection air atmosphere.Roasting is carried out in vacuum condition, air atmosphere or nitrogen atmosphere, prioritizing selection vacuum condition and air atmosphere.
Preferably, described coprecipitation comprises the steps:
1) by the corresponding salt formation mixing salt solution soluble in water of cobalt and auxiliary agent, using support dispersion in water as mother liquor;
2) by formation precipitant solution soluble in water for precipitating reagent, described precipitating reagent be selected from sodium carbonate, sodium acid carbonate, NaOH, potash or potassium hydroxide one or more;
3) in described mother liquor, add mixing salt solution and precipitant solution carry out co-precipitation and form co-precipitation solution simultaneously;
4) carry out aging to described co-precipitation solution, carry out after aging washing, dry and roasting obtains catalyst.
Preferably, in described mixing salt solution, the total mol concentration of slaine is 6mol/L to the maximum; The molar concentration of described precipitant solution is 3mol/L to the maximum.More preferably, the molar concentration of described precipitant solution is 2 ~ 3mol/L.
Preferably, the corresponding salt of cobalt described in the present invention and auxiliary agent is the nitrate of cobalt, potassium, manganese, iron, copper, zinc and zirconium.
Preferably, described mixing salt solution and precipitant solution volume ratio are 1:3 ~ 4.
Preferably, described aging temperature is 20 ~ 100 DEG C.
Preferably, the pH of co-precipitation is 5 ~ 10.More preferably, the pH of co-precipitation is 5 ~ 9.More preferably, the pH of co-precipitation is 7.5 ~ 9.Preferably, the temperature of co-precipitation is 50 ~ 90 DEG C.
Aging is standing.Preferably, in described step (4), aging temperature is 20 ~ 100 DEG C, and prioritizing selection is 50 ~ 90 DEG C; Ageing time is 0 ~ 100h, and prioritizing selection is 1 ~ 10h.
Preferably, step 4) in baking temperature at 50 ~ 150 DEG C.More preferably, baking temperature is 80 ~ 120 DEG C.Preferably, drying time is at 2 ~ 50h.Preferably, sintering temperature is at 200 ~ 500 DEG C.Preferably, roasting time is at 1 ~ 20h.
Preferably, described step 4) in, drying can be carried out under vacuum condition, air atmosphere and inert atmosphere.Roasting is carried out in vacuum condition, air atmosphere or nitrogen atmosphere.
The invention also discloses method as described above one-step method from syngas directly change into long-chain olefin reaction in purposes.
Long-chain olefin described in the present invention refers to that molecule contains the aliphatic hydrocarbon of more than 5 carbon atoms and a carbon-to-carbon double bond, and its general formula is C nh 2n.
Preferably, described purposes is reduced to catalyst described above before comprising use.Method of reducing is adopt the method passing into reducing gases to reduce, and reduction temperature is at 150 ~ 400 DEG C; Recovery time 1 ~ 50h.Described reducing gases comprises hydrogen and synthesis gas, and described synthesis gas is CO and H 2gaseous mixture.Described reducing gases also comprises inert gas.Described inert gas comprises nitrogen, argon gas or helium.
Preferably, described purposes for react in fixed bed; Reaction adopts H in synthesis gas 2with CO than being 1:10 ~ 10:1; Reaction temperature can at 150 DEG C ~ 400 DEG C; Reaction pressure can at 0bar ~ 60bar.Preferably, reaction adopts H in synthesis gas 2with CO than being 1:3 ~ 3:1.Preferably, reaction temperature can at 200 DEG C ~ 300 DEG C.Preferably, reaction pressure can at 0bar ~ 10bar.
The beneficial effect of the present invention's technical scheme described above is: gained catalyst of the present invention has high activity and high long-chain olefin is selective, with low cost, and it can operate under low-temp low-pressure, prepares easy, is easy to the advantages such as industry amplification.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the catalyst of preparation in the embodiment of the present invention 8.
Fig. 2 is the XRD photo of the catalyst of preparation in the embodiment of the present invention 8.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Embodiment 1
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is dissolved in a certain amount of deionized water by Co/Mn/Fe=2/1/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then by anhydrous Na 2cO 3be dissolved in a certain amount of deionized water, forming concentration is that 2mol/L alkali lye precipitates.
Carrier selects Ludox, Ludox quality choice accounts for 20% of catalyst total amount, and carry out dispersion stirring formation mother liquor by a certain amount of deionized water, above-mentioned Co/Mn/Fe=2/1/1 (atomic ratio) mixed solution and natrium carbonicum calcinatum aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, be down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 350 DEG C, be down to room temperature, obtain silicon dioxide carried cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 2
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=2/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then is dissolved in by NaOH in a certain amount of deionized water, and forming concentration is that 2mol/L alkali lye precipitates.
Carrier selective oxidation aluminium, carrier quality is selected to account for 25% of catalyst total amount, and carries out dispersion stirring by a certain amount of deionized water, and the mixed solution being 2:1 by above-mentioned cobalt manganese atom ratio and NaOH aqueous slkali carry out co-precipitation in the middle of the mother liquor stirred.It is 8.5 that co-precipitation pH controls, and titration temperature controls at 60 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, be down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 350 DEG C, be down to room temperature, obtain the catalyst of the cobalt manganese 2:1 of alundum (Al2O3) load.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 3
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr/Zn=2/1/0.1/0.05 (atomic ratio), and forming concentration is the mixed solution of 3mol/L, then by anhydrous Na 2cO 3be dissolved in a certain amount of deionized water, forming concentration is that 2mol/L alkali lye precipitates.
Carrier selects titanium dioxide, its quality choice accounts for 30% of catalyst total amount, and carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn/Zr/Zn=2/1/0.1/0.05 (atomic ratio) mixed solution and natrium carbonicum calcinatum aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 70 DEG C.After titration terminates, aging 4h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, be down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 350 DEG C, be down to room temperature, obtain the cobalt-base catalyst of titanium dichloride load.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 4
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2 (atomic ratio), and forming concentration is the mixed solution of 3mol/L, then by NaHCO 3be dissolved in a certain amount of deionized water, forming concentration is that 3mol/L alkali lye precipitates.
Carrier selects Ludox, and Ludox quality choice accounts for 25% of catalyst total amount, and carries out dispersion stirring by a certain amount of deionized water, and the mixed solution being 1:2 by above-mentioned cobalt manganese atom ratio and sodium acid carbonate aqueous slkali carry out co-precipitation in the middle of the mother liquor stirred.It is 7.5 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, dry atmosphere selects nitrogen, is down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 350 DEG C, is down to room temperature, obtains the catalyst of silicon dioxide carried cobalt manganese 1:2.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 320 DEG C, and reducing gases selects pure H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 210 DEG C, and pressure back pressure is 20bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 5
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr/Zn=2/1/0.1/0.05 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then by NaHCO 3be dissolved in a certain amount of deionized water, forming concentration is that 2mol/L alkali lye precipitates.
Catalyst choice gas-phase silicon colloidal sol, Ludox quality choice accounts for 20% of catalyst total amount, and carry out dispersion stirring by a certain amount of deionized water, the mixed solution of above-mentioned Co/Mn/Zr/Zn=2/1/0.1/0.05 and sodium acid carbonate aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 80 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, dry atmosphere selects vacuum, be down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 350 DEG C, calcination atmosphere selects nitrogen, is down to room temperature, obtains silicon dioxide carried cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects pure H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 220 DEG C, and pressure back pressure is 10bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 6
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr=1/1/0.05 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as ZSM-5 molecular sieve.Above-mentioned gained mixing salt solution is slowly instilled in molecular sieve under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 35%.Be placed on dry 10h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 3h under the nitrogen environment of 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 7
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zn=2/1/0.05 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as ZSM-5 molecular sieve.Above-mentioned gained mixing salt solution is slowly instilled in molecular sieve under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 25%.Be placed on dry 10h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 3h under the nitrogen environment of 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 280 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 3.Evaluation temperature is set to 220 DEG C, and pressure back pressure is to 10bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 8
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Using active carbon as carrier.Above-mentioned gained mixing salt solution is slowly instilled in active carbon under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 10h in 120 DEG C of baking ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 4h under the vacuum environment of 300 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 310 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 3.Evaluation temperature is set to 240 DEG C, and pressure back pressure is to 4bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
As shown in Figure 1, as seen from Figure 1, the granular size of the catalyst prepared in the present embodiment is 5 ~ 20nm to the projection electromicroscopic photograph of the catalyst obtained in the present embodiment.
The catalyst obtained in the present embodiment XRD figure as shown in Figure 2, as seen from Figure 2: calcined catalyst mainly consist of cobalt manganese composite oxide.
Embodiment 9
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=3/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then is dissolved in by sodium acid carbonate in a certain amount of deionized water, and forming concentration is that 2mol/L alkali lye precipitates.
Using active carbon as carrier.Above-mentioned gained mixing salt solution is slowly instilled in active carbon under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 10h in 120 DEG C of baking ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 4h under the vacuum environment of 300 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 320 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 7bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 10
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then by anhydrous K 2cO 3be dissolved in a certain amount of deionized water, forming concentration is that 2mol/L alkali lye precipitates.
Using magnesia as carrier, under dispersion stirring by above-mentioned cobalt manganese atom than carrying out co-precipitation for the mixed solution of 1:2 and Anhydrous potassium carbonate aqueous slkali in wherein.It is 8 that co-precipitation pH controls, and titration temperature controls at 60 DEG C.After titration terminates, aging 4h at 60 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 3h under the environment of 330 DEG C, be down to room temperature, obtain the catalyst of cobalt manganese 1:2.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 1.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 10bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 11
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr/Zn=2/1/0.05/0.05 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then is dissolved in by KOH in a certain amount of deionized water, and forming concentration is that 2mol/L alkali lye precipitates.
Using magnesia as carrier, above-mentioned Co/Mn/Zr/Zn=2/1/0.05/0.05 (atomic ratio) mixed solution and potassium hydroxide aqueous slkali carried out co-precipitation under dispersion stirring in wherein.It is 8 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 6h at 40 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, dry atmosphere selects nitrogen, is down to room temperature, after grinding evenly, to catalyst roasting 3h under the environment of 330 DEG C, is down to room temperature, obtains cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 1.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 10bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 12
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o and KNO 3, be dissolved in a certain amount of deionized water by Co/Mn/Zr/K=1/1/0.1/0.05 (atomic ratio), forming concentration is the mixed solution of 2mol/L, then is dissolved in by sodium acid carbonate in a certain amount of deionized water, and forming concentration is that 2mol/L alkali lye precipitates.
Using Ludox as carrier, above-mentioned Co/Mn/Zr/K=1/1/0.1/0.05 mixed solution and sodium acid carbonate aqueous slkali carried out co-precipitation under dispersion stirring in wherein.It is 9 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of baking oven, be down to room temperature, after grinding evenly, to catalyst roasting 4h under the environment of 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 310 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 1.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 11bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 13
By Co (NO 3) 26H 2o and Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Zn=2/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then is dissolved in by NaOH in a certain amount of deionized water, and forming concentration is that 2mol/L alkali lye precipitates.
Carrier selects Ludox, Ludox quality choice accounts for 30% of catalyst total amount, and carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Zn=2/1 (atomic ratio) mixed solution and NaOH aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 12h of baking oven, be down to room temperature, after grinding evenly, to catalyst roasting 3h under the vacuum environment of 330 DEG C, be down to room temperature, obtain silicon dioxide carried cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 280 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 14
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zn=1/1/0.1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as barium monoxide.Above-mentioned gained mixing salt solution is slowly instilled in barium monoxide under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 10h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 3h at 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 3.Evaluation temperature is set to 220 DEG C, and pressure back pressure is 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 15
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2 (atomic ratio), and forming concentration is the mixed solution of 3mol/L.
Carrier is chosen as magnesia.Above-mentioned gained mixing salt solution is slowly instilled in magnesia under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 10h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 3h at 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 330 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 8bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 16
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L, then by K 2cO 3be dissolved in a certain amount of deionized water, forming concentration is that 2mol/L alkali lye precipitates.
Carrier selects Al 2o 3, alundum (Al2O3) quality choice accounts for 20% of catalyst total amount, and carries out dispersion stirring by a certain amount of deionized water, and the mixed solution being 1:1 by above-mentioned cobalt manganese atom ratio and potash aqueous slkali carry out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 10h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 3h under the environment of 310 DEG C, be down to room temperature, obtain the catalyst of the cobalt manganese 1:1 of alundum (Al2O3) load.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 12bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 17
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Cu (NO 3) 23H 2o is dissolved in a certain amount of deionized water by Co/Mn/Cu=1/2/0.1 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as active carbon.Above-mentioned gained mixing salt solution is slowly instilled in active carbon under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 10h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 3h at 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 330 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 8bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 18
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zn=1/1/0.1, and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as Ludox (60%).And carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn/Zn=1/1/0.1 mixed solution and sodium acid carbonate aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 5 that co-precipitation pH controls, and titration temperature controls at 30 DEG C.After titration terminates, aging 4h at 30 DEG C.Aging end, centrifuge washing 7 times, then be placed in 120 DEG C of dry 10h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the environment of 310 DEG C, be down to room temperature, obtain the catalyst of silicasol-supported Co/Mn/Zn=1/1/0.1.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 12bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 19
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2, and forming concentration is the mixed solution of 3mol/L.
Carrier is chosen as magnesia (vector contg is 30%_).And carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn/Zn=1/2 mixed solution and sodium carbonate aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 6 that co-precipitation pH controls, and titration temperature controls at 60 DEG C.After titration terminates, aging 4h at 80 DEG C.Aging end, centrifuge washing 7 times, then be placed in 80 DEG C of dry 50h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the environment of 380 DEG C, be down to room temperature, obtain the catalyst of the Co/Mn=1/2 of MgO-Supported.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 20
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2, and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as Al 2o 3(40%).And carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn=1/2 mixed solution and potash aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 8 that co-precipitation pH controls, and titration temperature controls at 65 DEG C.After titration terminates, aging 2h at 65 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 30h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 5h under the environment of 420 DEG C, be down to room temperature, obtain Al 2o 3the catalyst of the Co/Mn=1/2 of load.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 21
By 50%Mn (NO 3) 2the aqueous solution, Cu (NO 3) 23H 2o solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Cu=1/2/0.1, and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as active carbon 50%.And carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn/Cu=1/2/0.1 mixed solution and potash aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 7 that co-precipitation pH controls, and titration temperature controls at 70 DEG C.After titration terminates, aging 2h at 80 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 20h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the environment of 420 DEG C, be down to room temperature, obtain the catalyst of activated carbon supported Co/Mn/Cu=1/2/0.1.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 22
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr/Zn=2/1/0.1/0.05 (atomic ratio), and forming concentration is the mixed solution of 3mol/L.
Carrier is chosen as ZSM-5 molecular sieve.Above-mentioned gained mixing salt solution is slowly instilled in molecular sieve under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 35%.Be placed on dry 10h in 120 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the nitrogen environment of 330 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 23
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn=1/2 (atomic ratio), and forming concentration is the mixed solution of 3mol/L.
Carrier is chosen as ZSM-5 molecular sieve.Above-mentioned gained mixing salt solution is slowly instilled in molecular sieve under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 25%.Be placed on dry 50h in 80 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the nitrogen environment of 380 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 24
By 50%Mn (NO 3) 2the aqueous solution and Co (NO 3) 26H 2o, Zr (NO 3) 45H 2o, Zn (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Zr/Zn=2/1/0.1/0.05 (atomic ratio), and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as active carbon.Above-mentioned gained mixing salt solution is slowly instilled in molecular sieve under continuous stirring, after tentatively soaking carrier, evaporate to dryness is revolved to gained material dry, after revolving evaporate to dryness constipation bundle, carry out double-steeping in the same way, three dippings etc., until catalyst carrier content is 20%.Be placed on dry 30h in 100 DEG C of vacuum drying ovens again after dipping terminates, be down to room temperature, after grinding evenly, to catalyst roasting 50h under the nitrogen environment of 420 DEG C, be down to room temperature, obtain cobalt-base catalyst.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects the H of 10% 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is to 5bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Embodiment 25
By 50%Mn (NO 3) 2the aqueous solution, Cu (NO 3) 23H 2o solution and Co (NO 3) 26H 2o is dissolved in a certain amount of deionized water by Co/Mn/Cu=1/2/0.1, and forming concentration is the mixed solution of 2mol/L.
Carrier is chosen as active carbon 50%.And carry out dispersion stirring by a certain amount of deionized water, above-mentioned Co/Mn/Cu=1/2/0.1 mixed solution and 1mol/L potash aqueous slkali are carried out co-precipitation in the middle of the mother liquor stirred.It is 7 that co-precipitation pH controls, and titration temperature controls at 70 DEG C.After titration terminates, aging 2h at 100 DEG C.Aging end, centrifuge washing 7 times, then be placed in 100 DEG C of dry 20h of vacuum drying oven, be down to room temperature, after grinding evenly, to catalyst roasting 10h under the environment of 420 DEG C, be down to room temperature, obtain the catalyst of activated carbon supported Co/Mn/Cu=1/2/0.1.
Evaluate catalyst, reaction unit is fixed bed reactors.Take 1.5g granular size be 40 ~ 60 object Catalyst packings in pipe, dilute with 1.5g40 ~ 60 object quartz sand.Arranging reduction temperature is 300 DEG C, and reducing gases selects H 2, air speed is 8000mlg -1h -1, after reduction terminates, switch to H 2/ CO is the synthesis gas of 2.Evaluation temperature is set to 230 DEG C, and pressure back pressure is 6bar, and air speed is set to 2000mlg -1h -1, reaction result is in table 1.
Table 1 embodiment evaluating catalyst result
As can be seen from Table 1, this catalyst is in course of reaction, and can operate under lower temperature lower pressure, Synthetic holography ability is higher, and long-chain olefin is selective higher simultaneously.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.

Claims (10)

1. one kind for directly changing into the catalyst of long-chain olefin by synthesis gas, it is characterized in that: described catalyst comprises metallic cobalt, auxiliary agent and carrier: described auxiliary agent be selected from potassium, manganese, iron, copper, zinc and zirconium one or more, the mol ratio of described auxiliary agent and cobalt is 10 to the maximum; Described carrier is selected from Al 2o 3, SiO 2, TiO 2, MgO, BaO, one or more in active carbon and molecular sieve, in the gross mass of described catalyst for benchmark, the mass percentage of described carrier is 0 ~ 99wt%.
2. catalyst as claimed in claim 1, is characterized in that: the mol ratio of described auxiliary agent and cobalt is 1 ~ 10.
3. prepare as arbitrary in claim 1 ~ 2 as described in the method for catalyst, be adopt infusion process or coprecipitation.
4. method as claimed in claim 3, is characterized in that: described infusion process comprises the steps:
1) be dissolved in the water cobalt and the corresponding salt of auxiliary agent formation mixing salt solution;
2) by step 1) in mixing salt solution progressively impregnated on carrier;
3) dry at 50 ~ 150 DEG C, then roasting at 200 ~ 500 DEG C.
5. method as claimed in claim 4, is characterized in that: step 1) in mixing salt solution total slaine molar concentration be 6mol/L to the maximum.
6. method as claimed in claim 3, is characterized in that: described coprecipitation comprises the steps:
1) by the corresponding salt formation mixing salt solution soluble in water of cobalt and auxiliary agent, using support dispersion in water as mother liquor;
2) by formation precipitant solution soluble in water for precipitating reagent, described precipitating reagent be selected from sodium carbonate, sodium acid carbonate, NaOH, potash or potassium hydroxide one or more;
3) in described mother liquor, add mixing salt solution and precipitant solution carry out co-precipitation and form co-precipitation solution simultaneously;
4) carry out aging to described co-precipitation solution, carry out after aging washing, dry and roasting obtains catalyst.
7. method as claimed in claim 6, is characterized in that: in described mixing salt solution, the total mol concentration of slaine is 6mol/L to the maximum; The molar concentration of described precipitant solution is 3mol/L to the maximum.
8. method as claimed in claim 6, is characterized in that: described mixing salt solution and precipitant solution volume ratio are 1:3 ~ 4.
9. method as claimed in claim 6, is characterized in that: described aging temperature is 20 ~ 100 DEG C.
10. method as described in as arbitrary in claim 1 ~ 2 directly changes into the purposes in long-chain olefin reaction in one-step method from syngas.
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