CN110368983A - A kind of preparation method of synthesis gas synthesis aviation kerosine catalyst and thus obtained catalyst and its application - Google Patents
A kind of preparation method of synthesis gas synthesis aviation kerosine catalyst and thus obtained catalyst and its application Download PDFInfo
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- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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Abstract
The present invention relates to the methods for preparing synthesis gas aviation kerosine catalyst, the catalyst is comprising carrier and loads catalytic active component thereon and catalyst aid, include: (A) 1-50 weight % is selected from the element of Ru, Fe, Ni, Co, Pt and Pd as catalytic active component, (B) element in the first Main Group Metal Elements of the periodic table of elements, transition elements and lanthanide series different from catalytic active component of 1-20 weight % is as catalyst aid, and (C) carrier.Catalyst of the present invention is by being heat-treated carrier with weak acid and highly basic before supporting catalytic active metal, the catalyst so prepared is when being used for synthesis gas aviation kerosine, the ASF distribution of traditional Fischer-Tropsch reaction is broken, high aviation kerosine selectivity is obtained, additionally can get acceptable or higher CO conversion ratio.The invention further relates to the purposes of the catalyst prepared by the method for the invention and the catalyst in synthesis gas synthesis aviation kerosine.
Description
Technical field
The present invention relates to it is a kind of for synthesis gas synthesis aviation kerosine catalyst preparation method, the invention further relates to by
The application of catalyst and the catalyst that this method obtains.
Background technique
Aviation kerosine is also known as jet fuel, is mainly used as the fuel of jet-propelled spacecraft engine, is to need in the world at present
The very big liquid fuel of the amount of asking, the usually hydrocarbon mixture by carbon number between 8-16 are formed.Due to for aviation kerosine demand
The increasingly growth of amount, holds at high price, extensive concern of the synthesis of aviation kerosine by countries in the world.Expect 2020
Year, the demand of China's aviation kerosine will be more than 40,000,000 tons.Currently, aviation kerosine production is mainly just like under type: 1) by original
Oil distillation.The increasingly depleted petroleum resources of this method heavy dependence, and equipment material is required high；2) biomass high temperature pyrolysis is raw
Upgrade at bio-oil, then through deoxidation into liquid fuel.The process is complicated, and bio-oil inferior quality obtained, Wu Fazhi
It connects and is used as engine fuel, need to further refine；3) biomass passes through chemistry and biological treatment (including hydrolysis, fermentation, selectivity
Add hydrogen etc.) small molecule platform object is obtained, then had using these small molecule platform chemicals as raw material by C-C coupling reaction
There is aviation kerosine chain length (C8-C16) oxygen-containing organic compound.The process is complicated, and technology is immature, invests excessive.Synthesis gas is made
For the bridge of energy conversion, clear gusoline can be converted by coal, natural gas, biomass, it is considered to be most potential stone
One of oily alternative route.It is that raw material is being catalyzed that last century the '20s, Fischer and Tropsch, which develop one kind by synthesis gas,
The synthetic route that hydrocarbon (liquid fuel) is synthesized under agent and felicity condition, is referred to as F- T synthesis.The route is first
Synthesis gas is prepared by non-oil resource, then liquid fuel is generated by CO catalytic hydrogenation.One synthetic route of carbon not only has green
Environmental protection, the advantage that reaction condition is mild, Atom economy is high, and for adjustment world energy sources structure, improvement to petroleum resources
Interdependency have important strategic importance.However, traditional Fischer-Tropsch synthetic distribution meets Anderson-Schulz-
Flory (ASF) distribution, it means that the selective theoretical value of aviation kerosine causes anti-by Fischer-Tropsch less than 40% in ASF distribution
Industrialized production aviation kerosine is answered to be obstructed.As it can be seen that the ASF distribution for how breaking traditional Fischer-Tropsch reaction is to realize industrialization synthesis gas
The key of aviation kerosine processed, wherein traditional Fischer-Tropsch reaction is broken in the exploitation of synthesis gas aviation kerosine reacting middle catalyst
The key of ASF distribution.
It is distributed studies have shown that synthesis gas aviation kerosine directly processed needs to break traditional ASF and product is concentrated on into C8-C16Area
Between.For example, Fushan Mountain university just makes ASF distribution curve to aviation kerosine distributed area using the method for injecting alkene into reactor
Between move (J.Li, G.Yang, Y.Yoneyama, T.Vitidsant, N.Tsubaki, Fuel, 2016,171:159-166) with
Improve the selectivity of aviation kerosine.But the method needs additional alkene to inject process matched therewith, and it is anti-not to be suitable for fixed bed
Device is answered, application is low.
It is well known that synthesis gas aviation kerosine is strong exothermal reaction and has by-product water generation, the catalysis of cobalt-based monometallic
Agent leads to its easy to reunite, sintering, inactivation in the reaction because oxidizable；Common Fischer-Tropsch reaction meets ASF distribution, target product selection
Property it is low, limit the route synthesis aviation kerosine in large-scale application.
Summary of the invention
In view of the above-mentioned condition of the prior art, the present inventor in terms of synthesis gas aviation kerosine catalyst into
It has gone extensively and in-depth study is led to find a kind of preparation method of new synthesis gas aviation kerosine catalyst
The catalyst of this method preparation is crossed when for synthesis gas aviation kerosine, the ASF distribution of traditional Fischer-Tropsch reaction can be broken, obtained
The highly selective of aviation kerosine is obtained, additionally can get acceptable or higher CO conversion ratio.The inventors discovered that preparing
When synthesis gas aviation kerosine catalyst, if be first heat-treated then supported catalyst again to carrier using weak acid and highly basic
Auxiliary agent and catalytically-active metals, the catalyst so prepared can break traditional Fischer-Tropsch when being used for synthesis gas aviation kerosine
The ASF of reaction is distributed, and is obtained the highly selective of aviation kerosine, additionally be can get acceptable or higher CO conversion ratio.This
Invention is based on aforementioned discovery and is achieved.
Therefore, it is an object of the present invention to provide a kind of methods for preparing synthesis gas aviation kerosine catalyst.It should
Method first uses weak acid and highly basic be heat-treated then supported catalyst auxiliary agent and catalytically-active metals again to carrier, so prepares
Catalyst be used for synthesis gas aviation kerosine when, can break traditional Fischer-Tropsch reaction ASF distribution, obtain aviation kerosine
It is highly selective, it additionally can get acceptable or higher CO conversion ratio.
It is a further object to provide the synthesis gas aviation kerosine catalyst prepared by the method for the invention.
The catalyst can break the ASF distribution of traditional Fischer-Tropsch reaction, obtain aviation kerosine when being used for synthesis gas aviation kerosine
It is highly selective, it additionally can get acceptable or higher CO conversion ratio.
Final object of the present invention is to provide the catalyst prepared by the method for the invention in synthesis gas aviation coal
As the purposes of catalyst in oil.The catalyst can break traditional Fischer-Tropsch reaction when being used for synthesis gas aviation kerosine
ASF distribution, obtains the highly selective of aviation kerosine, additionally can get acceptable or higher CO conversion ratio.
Realize that the technical solution of above-mentioned purpose of the present invention can be summarized as follows:
1. a kind of method for preparing synthesis gas aviation kerosine catalyst, which is loaded catalyst, includes
Carrier and the catalytic active component being carried on the carrier and catalyst aid, the total weight based on the catalyst, the catalyst packet
Contain:
It (A) is based on the element one or more element conducts in Ru, Fe, Ni, Co, Pt and Pd of 1-50 weight %
Catalytic active component,
(B) periodic table of elements is selected from for the one or more of catalytic active component that are different from of 1-20 weight % based on the element
Element in first Main Group Metal Elements, transition elements and lanthanide series as catalyst aid, and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps:
(1) by carrier dissociation constant KaIt is 1.0 × 10-3-1.0×10-1Weakly acidic aqueous solution heat treatment；
(2) carrier obtained through step (1) processing is heat-treated under alkaline condition with alkali metal hydroxide aqueous solution；
(3) product obtained in step (2) is directly water-soluble with the water soluble salt of the metallic element as catalyst aid
Liquid is contacted, or is filtered by product obtained in step (2), washing, first with the metal as catalyst aid after dry
The aqueous solution of the water soluble salt of element is contacted, using the metallic element on loading as catalyst aid；
(4) product obtained in step (3) is filtered, is washed, it is dry, and after roasting, then with as catalytic active component
The water-soluble metal salt of metallic element itself or its solution contact, using load on as catalytic active component metallic element；
And
(5) product for obtaining step (4) roasts, and obtains catalyst.
2., wherein the total weight based on the catalyst, which includes according to the 1st method:
It (A) is based on the element 5-30 weight %, the catalytic active component of more preferable 12-18 weight %, and (B) is based on the element
For 1-15 weight %, the catalyst aid of more preferable 8-12 weight %；And
(C) 60-94 weight %, the carrier of more preferable 70-80 weight %.
3. wherein catalytic active component is selected from one of Ni, Co and Fe or a variety of members according to the 1st or 2 method
Element, especially Co, Fe or combinations thereof；And/or catalyst aid is selected from one of Na, K, La, Ce and Mn or multiple element, especially
It is La, Ce or combinations thereof；And/or carrier is selected from carbon nanotube, graphene, active carbon, SiO2、Al2O3、ZrO2, carbonization
Silicon, TiO2With one of molecular sieve or a variety of, preferably one or more molecular sieves, especially Y type molecular sieve, tiltedly hair boiling
One of stone, modenite and ZSM-5 or a variety of, on condition that: when catalyst aid is Ti, carrier is not TiO2, work as catalysis
When auxiliary agent is Zr, carrier is not ZrO2。
4. wherein the water-soluble metal salt of catalytic active component is nitrate, vinegar according to any one of 1-3 methods
Hydrochlorate, chloride salt, their hydrate or its any mixture, preferably nitrate or its hydrate；And/or catalyst aid
Water soluble salt be nitrate, acetate, chloride salt, their hydrate or its any mixture, preferably nitrate or its
Hydrate.
5. wherein weak acid described in step (1) is organic monoacid according to any one of 1-4 methods, preferably select
From one of oxalic acid, phenyl pregnancy acid, maleic acid, salicylic acid and EDTA or a variety of, especially EDTA；And/or in step (1)
Weakly acidic aqueous solution concentration be 0.04-0.5mol/L, preferably 0.04-0.1mol/L；And/or the heat treatment in step (1)
Be no more than reflux temperature under conditions of carry out, preferably 40-100 DEG C, it is more preferable 70-100 DEG C at a temperature of carry out；And/or
Heat treatment in step (1) carries out 1-10 hours, preferably 4-10 hours.
6. wherein alkali metal hydroxide is sodium hydroxide, hydrogen in step (2) according to any one of 1-5 methods
Potassium oxide or combinations thereof, preferably sodium hydroxide；And/or alkali metal hydroxide aqueous solution concentration is 0.1-1mol/L, preferably
0.1-0.5mol/L；And/or the heat treatment in step (2) carries out at 40-100 DEG C, preferably 40-80 DEG C；And/or step
(2) time being heat-treated in is 0.1-2h, preferably 0.1-1h.
7. according to any one of 1-6 methods, wherein before the heat treatment for carrying out step (2), it will be through step (1)
Obtained carrier is handled to be filtered, washed and dried；And/or in step (3), product obtained in step (2) is filtered, is washed
It washs, is contacted again with the aqueous solution of the water soluble salt of the metallic element as catalyst aid after dry using in load as catalysis
The metallic element of auxiliary agent.
8. according to any one of 1-7 methods, wherein in step (3), metallic element as catalyst aid
The concentration of the aqueous solution of water soluble salt is 0.1-4mol/L, preferably 0.5-2mol/L；In step (3), carrier with as catalysis
The contact of the aqueous solution of the water soluble salt of the metallic element of auxiliary agent carries out at preferably 40-80 DEG C at 40-100 DEG C；And/or carrier
The contact with the aqueous solution of the water soluble salt of the metallic element as catalyst aid carries out 2-24 hours, preferably 4-12 hours.
9. according to any one of 1-8 methods, wherein in step (4), the metallic element as catalytic active component
Water-soluble metal salt contacted with molten state with product obtained in step (3), it is preferred that will be as catalytic active component
The water-soluble metal salt of metallic element melts in closed container again after mixing with product obtained in step (3).
10. wherein the drying in step (2), (3) and (4) exists each independently according to any one of 1-9 methods
It is carried out under the conditions of 60-120 DEG C；And/or the roasting in step (4) and step (5) carries out at 350-650 DEG C each independently,
Preferably, the roasting in step (4) carries out at 450-650 DEG C, and the roasting in step (5) carries out at 350-500 DEG C.
11. the catalyst as made from the method according to any one of 1-10.
12. use of the catalyst as made from the method according to any one of 1-10 in synthesis gas aviation kerosine
On the way.
13. according to the 12nd purposes, wherein in the reaction of synthesis gas aviation kerosine, H2/ CO molar ratio is 1-5,
Preferably 1-3, more preferably 1 to less than 2.
14. according to the 12nd or 13 purposes, wherein in the reaction of synthesis gas aviation kerosine, reaction pressure 1-
5MPa (gauge pressure), it is 5-20gh mol that reaction temperature, which is 150-350 DEG C and W/F,-1；It is preferred that reaction pressure is 1-3MPa (gauge pressure),
It is 8-15gh mol that reaction temperature, which is 200-300 DEG C and W/F,-1。
These and other purposes, features and advantages of the present invention are readily able to be common after combining the hereafter consideration present invention
Technical staff understands.
Specific embodiment
According to an aspect of the invention, there is provided a kind of method for preparing synthesis gas aviation kerosine catalyst, it should
Catalyst is loaded catalyst, comprising carrier and the catalytic active component being carried on carrier and catalyst aid, is urged based on this
The total weight of agent, which includes:
It (A) is based on the element one or more element conducts in Ru, Fe, Ni, Co, Pt and Pd of 1-50 weight %
Catalytic active component,
(B) periodic table of elements is selected from for the one or more of catalytic active component that are different from of 1-20 weight % based on the element
Element in first Main Group Metal Elements, transition elements and lanthanide series as catalyst aid, and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps:
(1) by carrier dissociation constant KaIt is 1.0 × 10-3-1.0×10-1Weakly acidic aqueous solution heat treatment；
(2) carrier obtained through step (1) processing is heat-treated under alkaline condition with alkali metal hydroxide aqueous solution；
(3) product obtained in step (2) is directly water-soluble with the water soluble salt of the metallic element as catalyst aid
Liquid is contacted, or is filtered by product obtained in step (2), washing, it is dry after again with the metal as catalyst aid
The aqueous solution of the water soluble salt of element is contacted, using the metallic element on loading as catalyst aid；
(4) product obtained in step (3) is filtered, is washed, it is dry, and after roasting, then with as catalytic active component
The water-soluble metal salt of metallic element itself or its solution contact, using load on as catalytic active component metallic element；
And
(5) product for obtaining step (4) roasts, and obtains catalyst.
Catalyst of the present invention is loaded catalyst, includes catalytic active component, catalyst aid and carrier, and the catalysis is lived
Property component and catalyst aid are carried on carrier.As catalytic active component, it be usually it is one or more selected from Ru, Fe, Ni,
Element in Co, Pt and Pd, preferably one or more elements in Co, Ni and Fe, especially Co and/or Fe.Catalysis
Active component can be used as simple substance and be present in catalyst, and the form that also can be used as compound such as oxide is present in catalyst
In, then be present in catalyst as a mixture of both.Based on the element, catalyst of the present invention generally comprises 1-50 weight
The catalytic active component of %, preferably 5-30 weight % are measured, the catalytic active component of more preferable 12-18 weight % is based on catalyst
Total weight.
Catalyst of the present invention also includes catalyst aid.The presence of catalyst aid can be further improved synthesis gas aviation coal
Aviation kerosine selectivity when oily, also can be improved CO conversion ratio sometimes.As catalyst aid, it is usually one or more differences
In the element in the first Main Group Metal Elements of the periodic table of elements, transition elements and lanthanide series of catalytic active component.The
One Main Group Metal Elements include Li, Na and K.When the first major element is as catalyst aid, preferably Na and/or K.Transition member
Element refers to a series of metallic elements in the area d in the periodic table of elements, this region includes the element that 3-12 has ten races altogether, but is not wrapped
The inner transition element in the area f is included, that is, does not include lanthanide series and actinides.As transition elements can be mentioned that Sc, Y, Ti,
Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Os, Rh, Ir, Zn, Cd and Hg.It is excellent when transition metal is as catalyst aid
It is selected as selected from one of Mo, Mn and Zn or a variety of, particularly preferred Mo and/or Mn.As lanthanide series can be mentioned that La, Ce, Pr,
Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.When lanthanide series is as catalyst aid, be preferably selected from La,
One of Ce, Pr and Tb or a variety of, particularly preferred La and/or Ce.In a preferred embodiment of the invention, catalysis helps
Agent is selected from one of Na, K, La, Ce and Mn or multiple element, especially La, Ce or combinations thereof.Catalyst aid can be used as
Simple substance is present in catalyst, and the form that also can be used as compound such as oxide is present in catalyst, then with the two
Form of mixtures is present in catalyst.Based on the element, catalyst of the present invention generally comprises the catalyst aid of 1-20 weight %, excellent
Select 1-15 weight %, the catalyst aid of more preferable 8-12 weight %, the total weight based on catalyst.
Catalyst of the present invention is loaded catalyst, and catalytic active component and catalyst aid are carried on carrier.As load
Body, it can be any carrier that aviation kerosine catalyst is catalyzed and synthesized suitable for synthesis gas.Carrier is preferably one or more
Selected from carbon nanotube, graphene, active carbon, SiO2、Al2O3、ZrO2, SiC and molecular sieve carrier, it is more preferably a kind of or more
Kind molecular sieve carrier, especially a kind of and a variety of carriers in Y type molecular sieve, clinoptilolite, modenite and ZSM-5,
On condition that: when catalyst aid is Ti, carrier is not TiO2, when catalyst aid is Zr, carrier is not ZrO2.Present invention catalysis
Agent generally comprises the carrier of 40-98 weight %, preferably 60-94 weight %, the carrier of more preferable 70-80 weight %, based on catalysis
The total weight of agent.
Catalyst of the present invention by first use weak acid and highly basic to carrier be heat-treated then supported catalyst auxiliary agent again and
Catalytically-active metals, the catalyst so prepared can break traditional Fischer-Tropsch reaction when being used for synthesis gas aviation kerosine
ASF distribution, obtains the highly selective of aviation kerosine, additionally can get acceptable or higher CO conversion ratio.For this purpose, usually
Catalyst of the present invention is prepared by the method included the following steps:
(1) by carrier dissociation constant KaIt is 1.0 × 10-3-1.0×10-1Weakly acidic aqueous solution heat treatment；
(2) carrier obtained through step (1) processing is heat-treated under alkaline condition with alkali metal hydroxide aqueous solution；
(3) product obtained in step (2) is directly water-soluble with the water soluble salt of the metallic element as catalyst aid
Liquid is contacted, or is filtered by product obtained in step (2), washing, it is dry after again with the metal as catalyst aid
The aqueous solution of the water soluble salt of element is contacted, using the metallic element on loading as catalyst aid；
(4) product obtained in step (3) is filtered, is washed, it is dry, and after roasting, then with as catalytic active component
The water-soluble metal salt of metallic element itself or its solution contact, using load on as catalytic active component metallic element；
And
(5) product for obtaining step (4) roasts, and obtains catalyst.
Firstly, needing in step (1) with dissociation constant KaIt (at 25 DEG C, is put down when weak electrolyte reaches ionization in the solution
When weighing apparatus, the product of various ion concentrations is with the ratio between molecular concentration unionized in solution in solution) it is 1.0 × 10-3-1.0×10-1Weakly acidic aqueous solution carrier is heat-treated.As weak acid here, organic monoacid is advantageously used, especially can be used
Selected from one of oxalic acid, phenyl pregnancy acid, maleic acid, salicylic acid and EDTA (ethylenediamine tetra-acetic acid) or a variety of, especially
EDTA.In the heat treatment, the concentration of weakly acidic aqueous solution is usually 0.04-0.5mol/L, preferably 0.04-0.1mol/L.This
In heat treatment usually require that and carry out at temperatures greater than room temperature or at elevated temperatures.But the temperature is usually not more than
Reflux temperature is crossed, such as heat treatment temperature is 40-100 DEG C, preferably 70-100 DEG C.Heat treatment time is usually 1-10 hours, excellent
It selects 4-10 hours.
After the heat treatment of step (1) is completed, directly obtained carrier alkali metal hydrogen will can be handled through step (1)
Oxide water solution is heat-treated under alkaline condition, the carrier obtained through step (1) processing can also be filtered, washed and dried
It is heat-treated under alkaline condition with alkali metal hydroxide aqueous solution again afterwards, preferably the latter.Here " direct " refers to step
(1) product obtained in just uses alkali without separation (such as without selected from any one of be filtered, washed and dried process)
Metal hydroxides aqueous solution is heat-treated under alkaline condition.For washing here, deionized water etc. can be used and washed,
Washing can carry out once, can also carry out repeatedly.Advantageously, washing carries out under reduced pressure, such as carried out under the conditions of suction filtration.It is right
At a temperature of dry 10-48h, preferably 10-24h in drying here, usually by the solid after washing at 60-120 DEG C.
In step (2), obtained carrier alkali metal hydroxide aqueous solution will be handled through step (1) in alkaline condition
Lower heat treatment.As alkali metal hydroxide here, sodium hydroxide, potassium hydroxide or combinations thereof usually can be used, preferably
Sodium hydroxide.Alkali metal hydroxide aqueous solution concentration is usually 0.1-1mol/L, preferably 0.1-0.5mol/L.The heat treatment
It can usually be carried out at 40-100 DEG C, preferably 40-80 DEG C.The time of the heat treatment is usually 0.1-2h, preferably 0.1-1h.
In step (3), by water solubility of the product directly with the metallic element as catalyst aid obtained in step (2)
The aqueous solution of salt is contacted, or is filtered by product obtained in step (2), and washing is helped with as catalysis again after dry
The aqueous solution of the water soluble salt of the metallic element of agent is contacted, using the metallic element on loading as catalyst aid.Here
" direct " refers to product obtained in step (2) without separation (such as without any in being filtered, washed and dried
One process) just contacted with the aqueous solution of the water soluble salt of the metallic element as catalyst aid.For washing here,
Deionized water etc. can be used to be washed, washing can carry out once, can also carry out repeatedly.Advantageously, washing under reduced pressure into
Row, such as carried out under the conditions of suction filtration.For drying here, usually by the solid after washing 60-120 DEG C at a temperature of it is dry
Dry 10-48h, preferably 10-24h.In step (3), provide the water-soluble metal salt of the metal as catalyst aid in water, preferably
Aqueous solution in deionized water.The concentration of the water-soluble metal saline solution is usually 0.1-4mol/L, preferably 0.5-2mol/L.
The water-soluble metal salt of catalyst aid can be nitrate, acetate, chloride salt, their hydrate or its any mixing
Object, preferably nitrate, acetate, their hydrate or its any mixture, especially nitrate or its hydrate.Step
(3) carrier is handled in the contact of the aqueous solution of the water soluble salt of the metallic element as catalyst aid usually in 40-100
DEG C, it is carried out at preferably 40-80 DEG C.The time of contact is usually 2-24 hours, preferably 4-12 hours.
In step (4), product obtained in step (3) is filtered, is washed, it is dry, and after roasting, then with as catalysis
Water-soluble metal salt of metallic element of active component itself or the contact of its solution, using the gold on loading as catalytic active component
Belong to element.For washing here, deionized water etc. can be used and washed, washing can carry out once, can also carry out repeatedly.Have
Benefit, washing carry out under reduced pressure, such as by carrying out under the conditions of suction filtration.For drying here, after usually washing
At a temperature of dry 10-48h, preferably 10-24h of the solid at 60-120 DEG C.For roasting here, maturing temperature is usually
350-650 DEG C, preferably 450-650 DEG C.Calcining time is usually 2-8h, preferably 4-8h.Metal member as catalytic active component
Element water-soluble metal salt, can be nitrate, acetate, chloride salt, their hydrate or its any mixture, preferably
For nitrate, acetate, their hydrate or its any mixture, especially nitrate or its hydrate.When with as urging
When the water-soluble metal salt of metallic element of change active component itself contacts, usually by the water-soluble metal salt with molten state (example
As being heated to its fusing point or more) contact or mix with product obtained in step (3), it is advantageous that by the water-soluble metal salt with
It is melted in closed container again after the mixing of product obtained in step (3).When with the metallic element as catalytic active component
When the aqueous solution contact of water-soluble metal salt, the water-soluble metal salt as the metallic element of catalytic active component is made into water-soluble
Product obtained in step (3) is then impregnated or is immersed in the aqueous solution of the water-soluble metal salt by liquid, or this is water-soluble
The aqueous solution of property metal salt is sprayed on product obtained in step (3).When the metallic element for being employed as catalytic active component
Water-soluble metal salt aqueous solution when, concentration is not particularly limited, as long as can be by the gold as catalytic active component
Belong to element to load on carrier, typically 5-50 weight %, preferably 5-30 weight %.It contacts as an aqueous solution
Temperature is also not particularly limited, and typically 20-40 DEG C.
In step (5), the product that step (4) is obtained is roasted, and obtains catalyst.The roasting is usually at 350-650 DEG C
Lower progress carries out at preferably 350-500 DEG C.Calcining time is usually 2-8h, preferably 4-8h.Calcination atmosphere is usually air or lazy
Property atmosphere.
Herein, inert atmosphere refers to the atmosphere for being not involved in chemical reaction under the roasting condition, such as nitrogen, argon
Gas.
Then catalyst of the present invention supported catalyst auxiliary agent and is urged again by being first heat-treated with weak acid and highly basic to carrier
Change active component, the catalyst so prepared can break the ASF of traditional Fischer-Tropsch reaction when being used for synthesis gas aviation kerosine
Distribution, obtains the highly selective of aviation kerosine, additionally can get acceptable or higher CO conversion ratio.
Therefore, according to another aspect of the present invention, it is obtained to provide a kind of method for preparing catalyst through the invention
Catalyst.All features that the catalyst is related to above described in catalyst preparation it is identical.
The last one aspect according to the present invention provides catalyst obtained by the method for the invention and navigates in synthesis gas system
Purposes in empty kerosene.
Catalyst of the invention needs to restore the catalyst before for synthesis gas aviation kerosine, so that
The catalytic active component in catalyst and the catalyst aid being optionally present are obtained in simple substance form.For this purpose, usually by catalyst with containing
The atmosphere of hydrogen restores.Reduction temperature is usually 200-400 DEG C, and preferably 250-350 DEG C.Restoring pressure is usually 0-
4.0MPa, the preferably gauge pressure of 0-1.0MPa.Recovery time is usually 3-12h, preferably 6-12h.Pure hydrogen can be used in reducing atmosphere
The gaseous mixture of hydrogen also can be used in gas.After reduction, catalytic active component and catalyst aid in catalyst are in simple substance shape
Formula shows catalytic activity.
In using reaction of the catalyst of the present invention by synthesis gas aviation kerosine, H2/ CO molar ratio is usually 1-5, excellent
It is selected as 1-3.When the molar ratio is lower than 2, the situation that can be more than or equal to 2 compared to molar ratio further increases the boat of the reaction
The selectivity of empty kerosene.Therefore, in a preferred embodiment of the invention, H2/ CO molar ratio is 1 to less than 2.The synthesis
The reaction pressure of reaction is usually 1-5MPa (gauge pressure), preferably 1-3MPa (gauge pressure).The temperature of the synthetic reaction is usually 150-
350 DEG C, preferably 200-300 DEG C.The W/F (gas hourly space velocity) of the synthetic reaction is usually 5-20gh mol-1, preferably 8-15gh
mol-1.In a preferred embodiment, in the reaction of synthesis gas aviation kerosine, reaction pressure is 1-5MPa (gauge pressure),
It is 5-20gh mol that reaction temperature, which is 150-350 DEG C and W/F,-1.In a further preferred embodiment, navigate in synthesis gas system
In the reaction of empty kerosene, reaction pressure is 1-3MPa (gauge pressure), and it is 8-15gh mol that reaction temperature, which is 200-300 DEG C and W/F,-1。
Relative to prior art, the invention has the benefit that
Synthesis gas aviation kerosine is strong exothermal reaction and has by-product water generation, and cobalt-based single-metal reforming catalyst is because oxidizable
Lead to its easy to reunite in the reaction, sintering, inactivation；Common Fischer-Tropsch reaction meets ASF distribution, target product (i.e. aviation kerosine) choosing
Selecting property is low, and theoretical value is no more than 40%.In the present invention, by being first heat-treated with weak acid and highly basic to carrier, then bear again
Catalytic active component (Ru, Fe, Ni, Co, Pt, Pd or any combination thereof) and catalyst aid are carried, can get the synthesis of polymolecularity
Gas aviation kerosine catalyst advantageously accounts for the problem of catalyst stability difference during the reaction, improves catalyst
Stability, and the ASF distribution of traditional Fischer-Tropsch reaction can be broken, the highly selective of aviation kerosine can be especially obtained, additionally
It can get acceptable or higher CO conversion ratio.Embodiment
Below with reference to specific embodiment, the invention will be further described, but should not be construed as protecting the present invention
The limitation of range.
Embodiment 1
The preparation of catalyst
EDTA is made into the solution I that concentration is 0.07mol/L with deionized water, weighs (eastern ソ ー plants of 6.7gY type molecular sieve
Formula commercial firm, HSZ-320NAA) it is put into solution I and is filtered after return stirring 6h, it is washed with deionized, is then done at 120 DEG C
It is dry.NaOH is made into the solution II that concentration is 0.4mol/L with deionized water, is put into 3.4g through aforementioned treated Y type molecule
Sieve is filtered after 30min is mixed at 40 DEG C, is washed with deionized, and then obtains presoma a after drying at 120 DEG C.
Manganese nitrate is made into the solution III that concentration is 1mol/L with deionized water.1g presoma a is added into solution III, is protected at 80 DEG C
12h is held, is filtered later, is washed with deionized, then obtains presoma b after drying at 120 DEG C.By presoma b in air
The lower 650 DEG C of roastings 6h of atmosphere.Then 1g gains are weighed and 1.72g cobalt nitrate hexahydrate is put into mortar, grind 30min.Will
To product be placed in closed glass jar, melt 48h under the conditions of 60 DEG C.Then 400 DEG C of roastings under nitrogen atmosphere in tube furnace
4h is burnt, catalyst A is obtained, based on the element includes the Mn of 15 weight %Co and 10% weight.
Catalyst reduction and reaction
Gained catalyst A is fitted into the tubular reactor that the diameter erect is 9 millimeters for 0.5 gram totally, catalyst A is with fixation
Bed setting.It is passed through hydrogen from the upper inlet of tubular reactor, holds catalyst A at 400 DEG C of temperature and the gauge pressure of 0MPa
Continuous reduction 8h.After catalyst A reduction, temperature is reduced to 250 DEG C, is passed through synthesis gas, H2/ CO molar ratio is 1, and reaction pressure is
2MPa (gauge pressure), it is 10gh mol that reaction temperature, which is 250 DEG C and W/F,-1Continuously reacted.Reaction result is shown in Table 1.
Embodiment 2
The preparation of the catalyst in embodiment 1 is repeated, the difference is that: solution III replaces with the sodium nitrate of 1mol/L
Aqueous solution.Catalyst B is finally obtained, based on the element includes 15 weight %Co and 10 weight %Na.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst B.
Reaction result is shown in Table 1.
Embodiment 3
The preparation of the catalyst in embodiment 1 is repeated, the difference is that: solution III replaces with the cerous nitrate of 1mol/L
Aqueous solution.Catalyst C is finally obtained, based on the element includes 15 weight %Co and 10 weight %Ce.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C.
Reaction result is shown in Table 1.
Embodiment 4
The preparation of the catalyst in embodiment 1 is repeated, the difference is that: solution III replaces with the lanthanum nitrate of 1mol/L
Aqueous solution.Catalyst D is finally obtained, based on the element includes 15 weight %Co and 10 weight %La.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst D.
Reaction result is shown in Table 1.
Embodiment 5
The preparation of the catalyst in embodiment 1 is repeated, the difference is that: solution III replaces with the lithium nitrate of 1mol/L
Aqueous solution.Catalyst E is finally obtained, based on the element includes 15 weight %Co and 10 weight %Li.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst E.
Reaction result is shown in Table 1.
Embodiment 6
The preparation of the catalyst in embodiment 1 is repeated, the difference is that: solution III replaces with the potassium nitrate of 1mol/L
Aqueous solution.Catalyst F is finally obtained, based on the element includes 15 weight %Co and 10 weight %K.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst F.
Reaction result is shown in Table 1.
Comparative example 1
Weigh 1g Y type molecular sieve (Dong ソ ー Co., Ltd., HSZ-320NAA) mortar is put into 1.72g cobalt nitrate hexahydrate
In, grind 30min.Obtained product is placed in closed glass jar, melts 48h under the conditions of 60 DEG C.Then in tube furnace
The lower 400 DEG C of roastings 4h of nitrogen atmosphere, obtains catalyst C-A, based on the element includes 15 weight %Co.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C-
A.Reaction result is shown in Table 1.
Comparative example 2
EDTA is made into the solution I that concentration is 0.07mol/L with deionized water, weighs (eastern ソ ー plants of 3.4gY type molecular sieve
Formula commercial firm, HSZ-320NAA) it is put into solution I and is filtered after return stirring 6h, it is washed with deionized, is then done at 120 DEG C
Presoma a is obtained after dry.Sodium nitrate is made into the solution II that concentration is 1mol/L with deionized water.Before 1g is added into solution II
Body a is driven, 12h is kept at 80 DEG C, is filtered later, is washed with deionized, then obtains presoma b after drying at 120 DEG C.
By presoma b 650 DEG C of roasting 6h in air atmosphere.Then 1g gains are weighed and 1.72g cobalt nitrate hexahydrate is put into mortar,
Grind 30min.Obtained product is placed in closed glass jar, melts 48h under the conditions of 60 DEG C.Then the nitrogen in tube furnace
The lower 400 DEG C of roastings 4h of atmosphere, obtains catalyst C-B, based on the element includes 15 weight %Co and 10 weight %Na.Catalyst is also
Former and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C-
B.Reaction result is shown in Table 1.
Comparative example 3
NaOH is made into the solution I that concentration is 0.4mol/L with deionized water, weighs (eastern ソ ー plants of 6.7gY type molecular sieve
Formula commercial firm, HSZ-320NAA) it is put into solution I and is filtered after mixing 30min at 40 DEG C, it is washed with deionized, then
Presoma a is obtained after drying at 120 DEG C.Sodium nitrate is made into the solution II that concentration is 1mol/L with deionized water.To solution
1g presoma a is added in II, 12h is kept at 80 DEG C, is filtered later, is washed with deionized, then at 120 DEG C after drying
Obtain presoma b.By presoma b 650 DEG C of roasting 6h in air atmosphere.Then 1g gains and six water nitric acid of 1.72g are weighed
Cobalt is put into mortar, grinds 30min.Obtained product is placed in closed glass jar, melts 48h under the conditions of 60 DEG C.Then
400 DEG C of roasting 4h under nitrogen atmosphere, obtain catalyst C-C in tube furnace, based on the element include 15 weight %Co and 10 weights
Measure %Na.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C-
C.Reaction result is shown in Table 1.
Comparative example 4
Weigh 1g Y type molecular sieve (Dong ソ ー Co., Ltd., HSZ-320NAA) with the saturated water of 1.72g cobalt nitrate hexahydrate
It is dry after solution dipping.Then 400 DEG C of roasting 4h under nitrogen atmosphere in tube furnace, obtain catalyst C-D, wrap based on the element
Containing 15 weight %Co.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C-
D.Reaction result is shown in Table 1.
Comparative example 5
Sodium nitrate is made into the solution I that concentration is 1mol/L with deionized water.1g Y type molecular sieve is added into solution I
(Dong ソ ー Co., Ltd., HSZ-320NAA), 12h is kept at 80 DEG C, is filtered later, is washed with deionized, then in 120
Presoma a is obtained after drying at DEG C.By presoma a 650 DEG C of roasting 6h in air atmosphere.Then weigh 1g gains with
1.72g cobalt nitrate hexahydrate is put into mortar, grinds 30min.Obtained product is placed in closed glass jar, under the conditions of 60 DEG C
Melt 48h.Then 400 DEG C of roasting 4h under nitrogen atmosphere in tube furnace, obtain catalyst C-E, based on the element include 15 weights
Measure %Co and 10 weight %Na.
Catalyst reduction and reaction
The catalyst reduction and reaction process in embodiment 1 are repeated, unlike: catalyst A is replaced with into catalyst C-
E.Reaction result is shown in Table 1.
Table 1
A: for different/direct ratio in aviation kerosine component, i.e. product component is C8-C16Hydro carbons in isomery hydro carbons and normal hydrocarbon
The molar ratio of class, the higher oil product freezing point of different/direct ratio the low more is conducive to the use of aircraft.
Claims (14)
1. a kind of method for preparing synthesis gas aviation kerosine catalyst, which is loaded catalyst, includes carrier
With the catalytic active component and catalyst aid that are carried on the carrier, the total weight based on the catalyst, which includes:
It (A) is based on the element one or more elements in Ru, Fe, Ni, Co, Pt and Pd of 1-50 weight % as catalysis
Active component,
(B) periodic table of elements first is selected from for the one or more of catalytic active component that are different from of 1-20 weight % based on the element
Element in Main Group Metal Elements, transition elements and lanthanide series as catalyst aid, and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps:
(1) by carrier dissociation constant KaIt is 1.0 × 10-3-1.0×10-1Weakly acidic aqueous solution heat treatment；
(2) carrier obtained through step (1) processing is heat-treated under alkaline condition with alkali metal hydroxide aqueous solution；
(3) by product obtained in step (2) directly with the aqueous solution of the water soluble salt of the metallic element as catalyst aid into
Row contact, or filtered by product obtained in step (2), washing, it is dry after with the metallic element as catalyst aid
The aqueous solution of water soluble salt is contacted, using the metallic element on loading as catalyst aid；
(4) product obtained in step (3) is filtered, is washed, it is dry, and after roasting, then with the gold as catalytic active component
Water-soluble metal salt itself or the contact of its solution for belonging to element, using the metallic element on loading as catalytic active component；And
(5) product for obtaining step (4) roasts, and obtains catalyst.
2. the method according to claim 1, wherein the total weight based on the catalyst, which includes:
It (A) is based on the element 5-30 weight %, the catalytic active component of more preferable 12-18 weight %, and
It (B) is based on the element 1-15 weight %, the catalyst aid of more preferable 8-12 weight %；And
(C) carrier of 60-94 weight %, more preferable 70-80 weight %.
3. method according to claim 1 or 2, wherein catalytic active component is selected from one of Ni, Co and Fe or a variety of members
Element, especially Co, Fe or combinations thereof；And/or catalyst aid is selected from one of Na, K, La, Ce and Mn or multiple element, especially
It is La, Ce or combinations thereof；And/or carrier is selected from carbon nanotube, graphene, active carbon, SiO2、Al2O3、ZrO2, carbonization
Silicon, TiO2With one of molecular sieve or a variety of, preferably one or more molecular sieves, especially Y type molecular sieve, tiltedly hair boiling
One of stone, modenite and ZSM-5 or a variety of, on condition that: when catalyst aid is Ti, carrier is not TiO2, work as catalysis
When auxiliary agent is Zr, carrier is not ZrO2。
4. method as claimed in one of claims 1-3, wherein the water-soluble metal salt of catalytic active component is nitrate, vinegar
Hydrochlorate, chloride salt, their hydrate or its any mixture, preferably nitrate or its hydrate；And/or catalyst aid
Water soluble salt be nitrate, acetate, chloride salt, their hydrate or its any mixture, preferably nitrate or its
Hydrate.
5. method as claimed in one of claims 1-4, wherein weak acid described in step (1) is organic monoacid, preferably select
From one of oxalic acid, phenyl pregnancy acid, maleic acid, salicylic acid and EDTA or a variety of, especially EDTA；And/or in step (1)
Weakly acidic aqueous solution concentration be 0.04-0.5mol/L, preferably 0.04-0.1mol/L；And/or the heat treatment in step (1)
Be no more than reflux temperature under conditions of carry out, preferably 40-100 DEG C, it is more preferable 70-100 DEG C at a temperature of carry out；And/or
Heat treatment in step (1) carries out 1-10 hours, preferably 4-10 hours.
6. method as claimed in one of claims 1-5, wherein alkali metal hydroxide is sodium hydroxide, hydrogen in step (2)
Potassium oxide or combinations thereof, preferably sodium hydroxide；And/or alkali metal hydroxide aqueous solution concentration is 0.1-1mol/L, preferably
0.1-0.5mol/L；And/or the heat treatment in step (2) carries out at 40-100 DEG C, preferably 40-80 DEG C；And/or step
(2) time being heat-treated in is 0.1-2h, preferably 0.1-1h.
7. method as claimed in one of claims 1-6, wherein before the heat treatment for carrying out step (2), it will be through step (1)
Obtained carrier is handled to be filtered, washed and dried；And/or in step (3), product obtained in step (2) is filtered, is washed
It washs, is contacted again with the aqueous solution of the water soluble salt of the metallic element as catalyst aid after dry using in load as catalysis
The metallic element of auxiliary agent.
8. method as claimed in one of claims 1-7, wherein in step (3), metallic element as catalyst aid
The concentration of the aqueous solution of water soluble salt is 0.1-4mol/L, preferably 0.5-2mol/L；In step (3), carrier with as catalysis
The contact of the aqueous solution of the water soluble salt of the metallic element of auxiliary agent carries out at preferably 40-80 DEG C at 40-100 DEG C；And/or carrier
The contact with the aqueous solution of the water soluble salt of the metallic element as catalyst aid carries out 2-24 hours, preferably 4-12 hours.
9. method as claimed in one of claims 1-8, wherein in step (4), the metallic element as catalytic active component
Water-soluble metal salt contacted with molten state with product obtained in step (3), it is preferred that will be as catalytic active component
The water-soluble metal salt of metallic element melts in closed container again after mixing with product obtained in step (3).
10. method as claimed in one of claims 1-9, wherein the drying in step (2), (3) and (4) exists each independently
It is carried out under the conditions of 60-120 DEG C；And/or the roasting in step (4) and step (5) carries out at 350-650 DEG C each independently,
Preferably, the roasting in step (4) carries out at 450-650 DEG C, and the roasting in step (5) carries out at 350-500 DEG C.
11. the catalyst as made from method as claimed in one of claims 1-10.
12. use of the catalyst as made from method as claimed in one of claims 1-10 in synthesis gas aviation kerosine
On the way.
13. purposes according to claim 12, wherein in the reaction of synthesis gas aviation kerosine, H2/ CO molar ratio is 1-5, excellent
It is selected as 1-3, more preferably 1 to less than 2.
14. 2 or 13 purposes according to claim 1, wherein in the reaction of synthesis gas aviation kerosine, reaction pressure 1-
5MPa (gauge pressure), it is 5-20gh mol that reaction temperature, which is 150-350 DEG C and W/F,-1；It is preferred that reaction pressure is 1-3MPa (gauge pressure),
It is 8-15gh mol that reaction temperature, which is 200-300 DEG C and W/F,-1。
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| CN201810331053.XA CN110368983A (en) | 2018-04-13 | 2018-04-13 | A kind of preparation method of synthesis gas synthesis aviation kerosine catalyst and thus obtained catalyst and its application |
| JP2020555431A JP7320532B2 (en) | 2018-04-13 | 2019-04-02 | Method for producing catalyst used in synthesizing aviation kerosene from synthesis gas, catalyst obtained by the method, and use thereof |
| PCT/CN2019/080955 WO2019196703A1 (en) | 2018-04-13 | 2019-04-02 | Preparation method for catalyst for use in synthesizing aviation fuel from synthesis gas, catalyst |
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| CN114425411B (en) * | 2020-10-14 | 2023-08-29 | 中国石油化工股份有限公司 | Supported Fe-based catalyst and preparation and application thereof |
| CN115663215B (en) * | 2022-12-12 | 2024-03-12 | 华北电力大学 | Preparation method of supported electrocatalyst |
| CN115920954B (en) * | 2022-12-20 | 2023-10-24 | 江苏润普食品科技股份有限公司 | Solid base catalyst for catalyzing depolymerization of sorbic acid polyester to prepare sorbic acid, preparation method and application thereof |
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| JP7320532B2 (en) | 2023-08-03 |
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