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CN105817222B - A kind of preparation method and application of hydro carbons catalyst for fischer-tropsch synthesis composition - Google Patents

A kind of preparation method and application of hydro carbons catalyst for fischer-tropsch synthesis composition Download PDF

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CN105817222B
CN105817222B CN201610238331.8A CN201610238331A CN105817222B CN 105817222 B CN105817222 B CN 105817222B CN 201610238331 A CN201610238331 A CN 201610238331A CN 105817222 B CN105817222 B CN 105817222B
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catalyst
roasting
carbon monoxide
hydro carbons
preparation
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CN105817222A (en
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李程伟
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SHANGHAI XINXIN CHEMICAL Co.,Ltd.
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Hangzhou Fuyang Hongxiang Technology Service Co Ltd
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Priority to CN201810282152.3A priority patent/CN108525652A/en
Priority to CN201610238331.8A priority patent/CN105817222B/en
Priority to CN201810281960.8A priority patent/CN108435204A/en
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • 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
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract

It the present invention relates to the use of Fischer-Tropsch（FT）The preparation method of the carbon monoxide-olefin polymeric used when reaction as the mixed gas of principal component using hydrogen and carbon monoxide by manufacturing hydro carbons and the method that hydro carbons is manufactured by above-mentioned synthesis gas using FT reactions.More particularly to by the manufacturing method for including the specific preparation process and the hydro carbons characterized by using above-mentioned FT synthetic catalysts for being carried on concave-convex stone and the carbon monoxide-olefin polymeric of spinel oxide complex carrier containing FT active metals and promoter metal.

Description

A kind of preparation method and application of hydro carbons catalyst for fischer-tropsch synthesis composition
Technical field
The present invention relates to the use of Fischer-Tropsch (FT) reaction by using hydrogen and carbon monoxide as the mixed gas of principal component (hereinafter referred to as For " synthesis gas ") it manufactures the carbon monoxide-olefin polymeric used when hydro carbons and hydro carbons is manufactured by above-mentioned synthesis gas using FT reactions Method.More specifically, it is related to carbon monoxide-olefin polymeric to be carried on complex carrier comprising active metal containing FT and to use The manufacturing method for the hydro carbons that above-mentioned FT synthetic catalysts are characterized.
Background technology
As the method by synthesis gas Synthin, Fischer-Tropsch (Fischer-Tropsch) reaction, methanol synthesis reaction etc. It is well-known.Synthetic technology in ICL for Indirect Coal Liquefaction is by Germany scientist Frans Fischer and Hans Tropsch In 1,923 first letter i.e. F-T names finding first and with their names, abbreviation F-T synthesis or Fiscber-Tropscb synthesis.By Indirect liquefaction technology, not only can from coal the common petroleums product such as extracting gasoline, diesel oil, kerosene, but also can refine Go out a variety of high value-added products such as the high quality oil product such as Aviation Fuel, lubricating oil and alkene, paraffin.
Since Fischer and Tropsch has found to produce hydrocarbon compound on the iron catalyst of alkalization, Fischer-Tropsch Synthetic technology just along with the fluctuation and political factor of world's crude oil price and prosperity and decline is indefinite.Fiscber-Tropscb synthesis takes the lead in Germany Starting industrial applications, Rule chemical company in 1934 has built up First indirect liquefaction process units, and yield is 70,000 tons/year, To nineteen forty-four, Germany shares 9 factories totally 57 ten thousand tons/year of production capacity.In the same period, Japan, France, China also have 6 Covering device is built up.FT reactions are the catalyst as active metal such as ruthenium of the iron using iron family element, cobalt, nickel, platinum family element.Separately On the one hand, it is known that methanol synthesis reaction is carried out by Cu-series catalyst, and C2 oxygenatedchemicals (ethyl alcohol, acetaldehyde etc.) synthesis passes through rhodium Series catalysts carry out.
Currently, Exxon-Mobil (Exxon-Mobil), British Petroleum (BP-Amoco), ConUS oil company (ConocoPhillips) and synthetic oil company (Syntroleum) etc. is also developing the Fiscber-Tropscb synthesis technique of oneself, transfers the possession of License technology, and plan to build Fischer-Tropsch synthetic natural gas liquefaction plant in the outlying region for possessing natural gas.F-T is closed At main chemical reactions：
The main reaction of F-T synthesis：
Generate alkane：nCO+(2n+1)H2=CnH2n+2+nH2O
Generate alkene：nCO+(2n)H2=CnH2n+nH2O
In addition there are some side reactions, such as：
Generate methane：CO+3H2=CH4+H2O
Generate methanol：CO+2H2=CH3OH
Generate ethyl alcohol：2CO+4H2=C2H5OH+H2O
Carbon deposit reacts：2CO=C+CO2
Other than above 6 are reacted, the oxygenatedchemicals such as alcohol and aldehyde, ketone, acid, the ester of higher carbon number are also generated Side reaction.
Fischer-Tropsch catalyst
Synthetic catalyst is mainly made of the periodic tables group VIII metal such as Co, Fe, Ni, Ru, in order to improve catalyst Activity, stability and selectivity, will also be added some auxiliary elements, such as metal oxide or salt in addition to principal component.It is most of Catalyst is required for carrier, such as aluminium oxide, silica, kaolin or diatomite.Only through CO+ after synthetic catalyst preparation It is just active after H2 or H2 reduction activations.Currently, in the world using more ripe indirect liquefaction catalyst mainly have iron system and Cobalt system two major classes, the mainly Fe-series catalyst that SASOL is used.It is used in SASOL fixed beds and paste state bed reactor Precipitated iron catalyst uses fused iron catalyst in a fluidized bed reactor.
Only Sasol (iron, cobalt), the Shell (cobalt) of Fiscber-Tropscb synthesis cobalt and iron catalyst industrial applications in the world Two, also there are this respect patent in some also other companies, but do not hear input large-scale industrial application, only in pilot scale It is used on device, these companies are broadly divided into following several：Big oil company such as Exxon Mobil (cobalt), Statoil (cobalt), BP (cobalt), Conoco (cobalt), Chevron (cobalt)；Profession is company such as Rentech (iron), the Syntroleum of synthetic oil (cobalt)；Also some professions are the company such as Johnson Matthey (iron, cobalt) of catalyst, Albemarle (iron, cobalt) etc..
But current fischer-tropsch synthetic catalyst there is a problem in that：Since FT reacts, CH4Etc. lower hydrocarbons, CO2In this way The generation of gas componant be promoted, gasoline yield reduces；Most suitable reaction problem or catalyst are not adapted to either The relatively low easy inactivation of activity, stability is poor, is under higher reaction temperatures, the more low stabilization of gasoline fraction yield.
Invention content
The object of the present invention is to provide the catalyst for producing compositions of hydro carbons, can pass through reaction by synthesis gas Obtain CO high conversion rates, gas componant generate less and aromatic series, cycloalkane, alkene, branched alkane as higher octane It is worth the gasoline fraction of the high selectivity of ingredient.At the same time, the stability of catalyst is good, long-term non-inactivation, can efficiently by The method that synthesis gas obtains above-mentioned gasoline fraction.
Present inventor is studied to reach above-mentioned purpose, as a result, it has been found that reacting active metal species by FT FT synthetic catalysts and complex carrier with special construction, can manufacture and gasoline is manufactured by synthesis gas with existing report The method of fraction is high compared to activity, gas componant generates less and the alkane rich in aromatic series, cycloalkane, alkene, branched High-knock rating gasoline fraction, so as to complete the present invention.
The present invention provides a kind of catalyst for fischer-tropsch synthesis composition, the active component in the Fischer-Tropsch catalyst For the one or more of Co, Fe, Ru, active component content is about 0.1~30 matter with amount of metal conversion relative to catalyst benchmark % is measured, metal promoter is about 0.1-5% with amount of metal conversion relative to catalyst benchmark.Active component is carried on compound with auxiliary agent Carrier.
The metal promoter is the one or more of Ni, Zn, Mn, Zr.
The complex carrier is concave-convex stone and spinel oxide complex carrier, concave-convex stone and spinel complex oxide Mass ratio is 1：2-5, preferably 1：4-5, complex carrier preparation process are：
(i) deionized water is added in a kettle, stirring is added attapulgite, is uniformly mixed, and slurry A is made；
(ii) using magnesium nitrate, aluminum nitrate as presoma, using citric acid or ethylene glycol as complexing agent, wiring solution-forming and mix stir It mixes uniformly, then carries out moisture evaporation, solution is transformed into sticky gel by transparent colloidal sol, finally dry, roasting, after roasting Magnesium aluminate spinel metal oxide MgAl is made2O4；
(iii) the magnesium aluminate spinel oxide is added in slurry A, control temperature continues to be uniformly mixed, ultrasound Slurry B is made in processing；
(iv) roasting after slurry B spray drying formings is obtained into the concave-convex stone and spinel oxide complex carrier of catalyst P-M。
Wherein, step (ii) drying condition is 100-150 DEG C 1-12 hours dry, and roasting condition is：200-400 DEG C of roasting 1-4 hours；Step (iii) described temperature is 100-200 DEG C；Step (iv) described roasting condition is that 350-800 DEG C of roasting 1-4 is small When, preferably 400-600 DEG C roasts 1-3 hours.
The preparation method of the carbon monoxide-olefin polymeric, which is characterized in that include the following steps：
(1) concave-convex stone and spinel oxide complex carrier are prepared according to above-mentioned steps；
(2) auxiliary agent introduces：By one or more soluble salt solutions incipient impregnations of Ni, Zn, Mn, Zr to step (1) on complex carrier, then dry, roasting；
(3) active component introduces：Active component is isometric for one or more soluble salt solutions of Co, Fe, Ru It is impregnated on step (2) obtained complex carrier containing auxiliary agent, then dries, roasting obtains carbon monoxide-olefin polymeric.Step (2) drying condition is：100-120 DEG C, time 10-20 hour, the condition of roasting is 250-500 DEG C and roasts 1-8 hours.Step Suddenly the aqueous solution of nickel salt and zinc salt is used in (2), and cobalt salt solution, preferably cobalt nitrate are used in step (3).In the step (3) Drying condition is：100-130 DEG C, time 12-20 hour, the condition of roasting is 400-800 DEG C and roasts 1-8 hours.
The present invention provides the manufacturing method of hydro carbons as shown below.
A kind of manufacturing method of hydro carbons, which is characterized in that have：Using containing showing active metal to Fischer-Tropsch reaction The Fischer-Tropsch catalyst of complex carrier is carried on by anti-as the FT of the gas synthesis hydro carbons of principal component using hydrogen and carbon monoxide It answers.
The manufacturing method of hydro carbons, wherein the FT reactions are carried out at 260~350 DEG C.
It, can be efficient by fischer-tropsch reaction by synthesis gas by using the catalyst for producing composition of the hydro carbons of the present invention Ground obtains that the CO high conversion rates of material synthesis gas, in addition gas componant generates less and aromatic series, cycloalkane, alkene, branched The mass percent of the gasoline fraction of the high selectivity of antiknock component as alkane, product gasoline fraction can reach 89% or more.Moreover, the selectivity of catalyst is good, active higher, continuous operations 12 months do not occur significantly inactivating mark As can be adapted for operating with full load for 10 ton day of scale or more.
The addition of concave-convex stone can reduce catalyst cost, and natural resources formation is efficiently used, and concave-convex stone with Complex carrier is formed with spinel-type ABxOy, on the one hand can play cohesive effect, it on the other hand can be with spinelle oxygen Compound forms complex carrier, can form mesopore-macropore distribution, larger specific surface area and pore volume, and can utilize point The special crystal form of spar is conducive to the load and dispersion of active component, improves F- T synthesis selectivity, forms mesopore-macropore and carries Body catalyst, the first aperture of catalyst carrier are 10-32nm, account for the 20-35% of catalyst pore structure；Second aperture is 60- 70nm accounts for the 40-60% of catalyst pore structure；
Further, further include the one or more of transition metal promoter Ni, Zn, Mn, Zr in carbon monoxide-olefin polymeric, relative to Catalyst benchmark is about 0.1-10% with amount of metal conversion, and the effect of preferably 0.1-5%, auxiliary agent contribute to carbon monoxide to dissociate, Increase the selectivity of long chain hydrocarbons, reduces methane selectively.
In order to efficiently use spinel carrier oxide, therefore, the calcination temperature of control catalyst is had to, it is excessively high to be more than 1000 DEG C can cause peroxide breaks down, crystal form to destroy, and can not play catalytic action.Compared with conventionally known method, pass through this The manufacturing method of the carbon monoxide-olefin polymeric of embodiment or the hydro carbons of present embodiment can effectively manufacture high-octane rating Gasoline fraction.In the reaction using the carbon monoxide-olefin polymeric involved by present embodiment, by FT synthetic catalysts by closing At gas synthesize hydro carbons contacted with carbon monoxide-olefin polymeric, can inhibit under high reaction temperature carbon atom number for 1~4 it is low Grade hydrocarbon, CO2Such gas componant generates, can efficiently generate hydrocarbon, and carbon monoxide-olefin polymeric can have under high-temperature Effect ground effect, to make it possible the high-octane gasoline fraction of manufacture.
Hereinafter, to the hydro carbons of the carbon monoxide-olefin polymeric involved by the present embodiment being prepared into involved by present embodiment Manufacturing method, used carbon monoxide-olefin polymeric involved by present embodiment hydro carbons manufacturing method, illustrate successively.
The FT synthetic catalysts active component used in present embodiment is carried on concave-convex stone and magnesium aluminate spinel with auxiliary agent On complex carrier.
It is used as ruthenium salt in active component, ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium, six ammonium of chlorination can be enumerated and close the water solubilitys such as ruthenium Ruthenium salt.In addition, as cobalt salt, it is preferable to use cobalt chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate, cobaltous formate.In addition, about for soaking The solution of ruthenium salt, cobalt salt that stain supports may be formed as the solution of the organic solvents such as alcohol, ether, ketone other than aqueous solution. At this point, selection dissolves in the salt of various organic solvents.
The content of ruthenium in FT synthetic catalysts is scaled 0.1~5 mass % relative to catalyst benchmark with amount of metal, excellent It is selected as 0.3~2.5 mass %, more preferably 0.5~2 mass %.The content of ruthenium is related with activated centre.The content of ruthenium is less than When 0.1 mass %, activated centre becomes insufficient, to there is the anxiety that cannot obtain sufficient catalytic activity.On the other hand, ruthenium contains Amount more than 5 mass % when, ruthenium cannot be fully supported on carrier, reduced dispersion, easily cause not with carrier components phase interaction Ruthenium species generate.Therefore, catalyst cost can only be increased by supporting the ruthenium of necessity or more, and it is not preferable.
The content of cobalt in FT synthetic catalysts is scaled 5~20 mass % relative to catalyst benchmark with amount of metal, excellent It is selected as 5~18 mass %, more preferably 5~20 mass %.When the content of cobalt is less than 3 mass %, the cobalt mistake as active metal It is few, there is the anxiety that not can confirm that significant active rising.On the other hand, when the content of cobalt is more than 20 mass %, later drying, Under calcination processing, FT reaction conditions, the cohesion of cobalt is easy to carry out, and has the anxiety for leading to activated centre reduction.In turn, the content mistake of cobalt When amount, it is possible to cause the specific surface area of catalyst, pore volume to lower, and the yield of the gas componant in product is easy to increase Add, it is not preferable.
Promoter metal content in FT synthetic catalysts relative to catalyst benchmark in terms of amount of metal conversion preferably 0.1~ 10 mass %, more preferably 0.1~5 mass %, further preferably 0.1~0.5 mass %.
It about the time of drying, calcining, must not make sweeping generalizations according to the difference for the treatment of capacity, but usually 1~20 hour. If processing time is less than 1 hour, the evaporation of moisture is possible to become inadequate, and the activation of FT active metal species subtracts Weak, it is not preferable.In addition, even if basic compared with 20 hours or less situations if processing time is more than 20 hours catalytic activity Do not change, so if consider workability, productivity, then preferably 20 hours or less.Wherein, the drying, calcination processing can To carry out in air, or can not also be carried out under reactive atmosphere as nitrogen, helium, it can also be under the reducing atmospheres such as hydrogen It carries out, without special provision.
The manufacturing method of FT synthetic catalysts, the method being spray-dried in addition to above-mentioned dipping supports method.To at this time Slurry concentration, without special provision, but if slurry concentration is too low, then the precipitation that will produce, catalyst component becomes uneven Even, it is not preferable., whereas if slurry concentration is excessively high, then the conveying of slurry can become difficult, therefore select the slurry of appropriateness dense Degree, and active component is caused to waste.In turn, at this time to adjust the concentration of slurry, improve mouldability, the spheroidizing of catalyst For the purpose of, silicon dioxide gel etc. can also be added and be used as binder.As the additive amount of binder at this time, do not make preferably Catalytic activity reduce degree, usually the range of 5~20 mass % select.
Due to containing spinel oxide carrier in carrier in complex carrier, there is special crystal form format, can be formed The carrier surface of active metal insertion or promoter metal, can not only efficiently use active metal, but also can improve active component Dispersion, and the addition of natural material bumps stone avoids the formation of the composite oxides of catalytically inactive, can play bond it is steady Fixed effect, therefore the dispersion performance of active component, and energy and active component can be improved while keeping vector stabilisation Fine dispersion is formed, cost is reduced, saves the common carriers such as molecular sieve；Further, the preparation for adjusting complex carrier, by concave-convex stone It is controlled 1 with the ratio of spinel compound：2-5 advantageously forms the carrier of bimodal distribution, is conducive to the various of carrier property Property, and effectively control vector specific surface area and pore structure, the complex carrier of formation had not only had larger specific surface area, but also can be with shape It at special crystal form, interacts with active component, is conducive to the flow distribution of target product, improves gasoline fraction yield, and energy The compression strength and wear-resisting property of catalyst are kept, this is significantly different with common zeolite or common single carrier.
And complex carrier is obtained also by fairly simple effective mixing method, or can be total to by the way that lye is added Precipitation obtains, and the Kong Rong of carrier, ratio can be effectively adjusted by the operating parameter in control preparation process, such as temperature, pH value Surface area and pore structure keep Active components distribution more uniform, improve the selectivity of effective product, reduce liquid hydrocarbon synthesis at This, improves the bonded energy between carrier primary particle, improves the abrasion resistance properties of catalyst, extend the service life of catalyst.
The manufacturing method of hydro carbons：The manufacturing method of the hydro carbons of present embodiment has：Use above-mentioned FT synthetic catalysts group It closes object to be reacted by the FT of synthesis gas Synthin, if hydro carbons is made to be contacted with carbon monoxide-olefin polymeric, passes through cracking reaction, isomery Change various reactions, the hydro carbons such as reaction to be converted.As a result, gasoline fraction increases, gasoline distribution is improved.
The FT synthetic catalysts especially used in present embodiment are even if under hot conditions as 230~350 DEG C CO conversion ratios and C5+ selectivity (selectivity of the synthesis for the hydro carbons that carbon atom number is 5 or more) also high excellent catalyst.
The form of reactor about each reaction can enumerate fixed bed, fluid bed, suspension bed, slurry bed (slurry Bed) etc., there is no particular limitation.
In having used the manufacturing method of hydro carbons of above-mentioned carbon monoxide-olefin polymeric, the catalyst group prepared as described above is used Object is closed, for reaction.The manufacturing method of the hydro carbons based on fixed bed is recorded below.The activity that catalyst is carried out by fixed bed is commented When valence, due to there is the anxiety for generating the pressure difference in reactor preferably to be squeezed as the shape of catalyst in powder catalyst The molded products such as product, pearl product.As the big of FT synthetic catalysts, zeolite and the carbon monoxide-olefin polymeric used in present embodiment It is small, depend on reactor scale, but as catalyst shape preferable particle size be 0.5mm~5mm, more preferably 1.0mm~ 3mm.When grain size is 0.5mm or more, the differential pressure in reactor can fully be inhibited to rise.On the other hand, existed by setting grain size 3mm is hereinafter, can make the coefficient of efficiency of catalyst improve, so as to efficiently being reacted.
Carbon monoxide-olefin polymeric involved by present embodiment can carry out reduction treatment (activation in advance before for reaction Processing).
By the reduction treatment, catalyst can be activated to reaction and show desired catalytic activity.It is not carrying out When the reduction treatment, FT active metal species are not reduced sufficiently, to show desired catalytic activity.Also original place It is preferably 140~350 DEG C to manage temperature, more preferably 150~300 DEG C.If be less than 140 DEG C, FT active metal species not by Fully reduction, to which sufficient reactivity cannot be obtained.
In the reduction treatment, preferably use using hydrogen as the reducibility gas of principal component.In used reproducibility gas Can include the ingredient, such as vapor, nitrogen, rare gas etc. other than hydrogen not interfere the amount of the degree of reduction range in body. The reduction treatment is not only influenced by above-mentioned treatment temperature, is also influenced by hydrogen partial pressure and processing time.Hydrogen partial pressure in reduction treatment Preferably 0.1~10MPa, more preferably 0.5~6MPa, it is most preferably 0.9~3MPa.The reduction treatment time because catalytic amount, Hydrogen ventilatory capacity etc. and it is different, it is often preferred that 0.1~72 hour, more preferably 1~48 hour, most preferably 3~48 hours.If Processing time is less than 0.1 hour, then has the anxiety that the activation of catalyst becomes inadequate.On the other hand, although even if being surpassed Prolonged reduction treatment in 72 hours is crossed, harmful effect will not be brought to catalyst, but does not find that catalytic performance improves, from And lead to the problem of processing cost increase etc. it is undesirable.
It, can be to involved by the present embodiment for having carried out reduction treatment as described above in the manufacturing method of hydro carbons Synthesis gas is passed through in carbon monoxide-olefin polymeric to carry out.
As long as used synthesis gas is mixed into it using hydrogen and carbon monoxide as principal component, not interfering the range of reaction His ingredient is not related yet.Such as an example, the catalyst involved by present embodiment can used Use is by synthesis gas obtained from gasification of biomass in the manufacturing method of the hydro carbons of composition.Kind as biomass at this time Class can enumerate the agricultural aquatic resources biomass such as grain, building materials, paper pulp, agricultural, forestry, animal husbandry waste the like waste The artificial forest such as biomass, sugarcane, palm, seaweed biomass (plantation biomass) etc..Wherein, it is preferable to use and grain There is no the waste biomass of competition not utilized.Gasification process about biomass is not particularly limited.Such as life The gasification process of substance has the various methods such as direct gasification, indirect gasification, atmospheric gasification, gas-pressurized, in addition, as gasification It is a variety of to be divided into fixed bed, fluid bed, entrained bed etc. for stove form.Using the carbon monoxide-olefin polymeric involved by present embodiment Hydro carbons manufacturing method in, can use by either of which method gasification made of biomass.
As reality the hydrogen and carbon monoxide intrinsic standoff ratio range, 0.6~2.7 be it is suitable, preferably 0.8~ 2.5, more preferably 1~2.3.If the intrinsic standoff ratio is less than 0.6, the tendency that the yield of the hydro carbons generated reduces can be found, separately Outside, if the intrinsic standoff ratio is more than 2.7, the increased tendency of gas componant in the hydro carbons generated can be found.
In turn, in the manufacturing method for the hydro carbons for having used the carbon monoxide-olefin polymeric involved by present embodiment, even if closing It is also what there is no problem at carbon dioxide coexists in gas.As the carbon dioxide coexisted in synthesis gas, even such as by oil The carbon dioxide that the reforming reaction of product, natural gas wait until can also be used unquestionably.In addition, can be in synthesis gas The carbon dioxide for being mixed into the other compositions for not interfering FT to react coexists.For example, it may be by the vapor weight of petroleum product etc. Carbon dioxide containing vapor, the nitrogen being partially oxidized etc. as the substance that whole reaction is released.
On FT synthetic catalysts, if the usually H of synthesis gas2/ CO molar ratios are identical, then reaction temperature is lower, chain life Long probability, C5+ selectivity (selectivity of the synthesis for the hydro carbons that carbon atom number is 5 or more) can become higher, and CO conversion ratios can become It obtains lower., whereas if reaction temperature is higher, then chain growth probability and C5+ can selectively become lower, but CO conversion ratios can become It obtains higher.In addition, if H2/ CO ratios increase, then CO conversion ratios can increase, and chain growth probability and C5+ are selectively reduced, if H2/ CO is than low, then in contrast.About the effect that these parameters are come for FT reaction zones, size can be according to the kind of the catalyst used Class etc. and it is different.This implementation is being carried out by being carried out at the same time 1 terrace work of FT reactions and conversion reaction in same reactor When the manufacturing method of the hydro carbons of mode, reaction temperature use 230~350 DEG C, preferably 240~310 DEG C, more preferably 250~ 300℃.By the way that reaction temperature is set in 350 DEG C hereinafter, can inhibit the undesirable gas componant on FT synthetic catalysts It generates, and the gas componant caused by the overcracking on zeolite can be inhibited to generate.
CO conversion ratios=[(the CO molal quantitys in unstrpped gas per unit time)-is (in exit gas per unit time CO molal quantitys)]/(the CO molal quantitys in unstrpped gas per unit time) × 100.
In embodiment below, CO analyses are by having used activated carbon (Active Carbon) (60/ in splitter 80 sieve meshes) thermal conductivity type gas-chromatography (TCD-GC) carry out.In unstrpped gas, 25 are added with used as internal standard Synthesis gas (the H of the Ar of volume %2With the mixed gas of CO).Qualitative and quantitative analysis is by by the peak position of CO and peak face Product is compared to progress with Ar.In addition, the composition analysis of product is to pass through hydrogen flame ion using capillary column (TC-1) What detector gas-chromatography (FID-GC) carried out.The identification of the chemical composition of catalyst is to emit spectrophotometric analysis by ICP What method was found out.
Specific implementation mode
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
Prepare complex carrier 10g：Deionized water is added in a kettle, stirring is added attapulgite, is uniformly mixed, Slurry A is made；Using magnesium nitrate, aluminum nitrate as presoma, using citric acid or ethylene glycol as complexing agent, wiring solution-forming is simultaneously mixed Uniformly, moisture evaporation is then carried out, solution is transformed into sticky gel, last 100-150 DEG C dry 1-12 by transparent colloidal sol Hour, 200-400 DEG C of roasting roasts for 1-4 hours, and magnesium aluminate spinel metal oxide MgAl2O4 is made after roasting；In slurry A The magnesium aluminate spinel oxide is added, control temperature continues to be uniformly mixed, be ultrasonically treated, and slurry B is made；By slurry B Roasting obtains the concave-convex stone and spinel oxide complex carrier of catalyst after spray drying forming；
It is sent out using incipient impregnation, is impregnated in 5g complex carriers and be dissolved with 0.5g zinc nitrates, 100-120 DEG C of drying, 500 After DEG C roasting 1-8 hour, further the aqueous solution of the ruthenic chloride of dipping 1.0 and place 1 hour, drying 3 at 100 DEG C in air Hour, and then calcined 3 hours at 500 DEG C, obtain the catalyst a1 as FT synthetic catalysts.By X-ray diffraction method into Row structural analysis as a result, it has been found that the complex carrier in catalyst a1 has bimodal distribution, and maintains the structure of magnesium aluminate spinel. In addition, emitting the chemical composition analysis that spectrophotometric method carries out catalyst a1 by ICP, as a result, it has been found that ruthenium is converted with metal 5 mass % are calculated as, zinc is calculated as 1 mass % with metal conversion.
In order to confirm the activity of catalyst a1, the catalyst a1 of 6g is carried out with the silicon carbide of 100 sieve meshes of 34.6g dilute It releases, is filled into the reaction tube that internal diameter is 10mm, with hydrogen partial pressure be 0.9MPaG, temperature is 170 DEG C, flow is 100 (STP) Ml/ minutes (STP：Standard temperatureand pressure) it is passed through hydrogen and is restored for 3 hours.After reduction, switching For H2The synthesis gas (Ar for including about 25 volume %) that/CO ratios are about 2, sets to temperature as 260 DEG C, stagnation pressure 0.9MPaG It is reacted.
Comparative example 1
Using single molecular sieve carrier, catalyst b is obtained similarly to Example 1, is carried containing active component ruthenium-zinc zeolite The catalyst b of body.Emit the chemical composition analysis that spectrophotometric method carries out catalyst b by ICP, as a result, it has been found that ruthenium is with gold Belong to conversion and be calculated as 5.0 mass %, zinc is calculated as 1 mass % with metal conversion.FT reactions by method similarly to Example 1 into Row.
The composition analysis result of the product obtained by reaction result and at this time is shown in table 1.
Embodiment 2
Active component precursors become 0.3g ruthenic chlorides and 0.4g cobalt nitrate solutions, other are identical as 1 condition of embodiment, use Catalyst a2 implements at 270 DEG C of reaction temperature, in addition to this, is reacted with method similarly to Example 1.It will reaction As a result the composition analysis result of the product and at this time obtained is shown in table 1.
Embodiment 3
Active component precursors become ruthenic chloride, cobalt nitrate and ferric chloride solution, active in catalyst a3 using catalyst a3 The Ru of metal:Co:Fe mass ratioes are 1：1-4：1-3 is implemented at 280 DEG C of reaction temperature, in addition to this, with same with embodiment 1 The method of sample is reacted.The composition analysis result of the product obtained by reaction result and at this time is shown in table 1.
Embodiment 4
The complex carrier of 4.5g is weighed, the aqueous solution of the nickel nitrate and zinc nitrate that make it be immersed in simultaneously is placed 1 hour, and bodies are waited Dipping is accumulated, then, is dried 4 hours in air, at 120 DEG C, then roasting is impregnated active component cobalt nitrate using infusion process In the complex carrier containing auxiliary agent, 100 DEG C of dryings 5 hours, and then calcined 4 hours at 600 DEG C, then to obtain as FT The catalyst a4 of synthetic catalyst.Structural analysis is carried out by X-ray diffraction method, as a result, it has been found that the complex carrier in catalyst a4 With bimodal distribution, and maintain the structure of magnesium aluminate spinel.It is catalyzed in addition, emitting spectrophotometric method by ICP The chemical composition analysis of agent a4, as a result, it has been found that cobalt is calculated as 10.0 mass %, zinc 1%, nickel 1% with metal conversion.Use catalyst A4 implements at being 350 DEG C in reduction temperature, in addition to this, is reacted with method similarly to Example 1.
Comparative example 2
Complex carrier is replaced using common alumina support, other conditions are same as Example 4, manufacture FT synthesis catalytics Agent.Emit the chemical composition analysis that spectrophotometric method carries out catalyst c by ICP, as a result, it has been found that cobalt is in terms of metal conversion For 10 mass %.
Comparative example 3
It is applicable in common Attapulgite carrier and replaces complex carrier, other conditions are same as Example 4, and manufacture FT synthesis is urged Agent.Emit the chemical composition analysis that spectrophotometric method carries out catalyst d by ICP, as a result, it has been found that cobalt is converted with metal 10 mass % are calculated as, the catalytic effect of zinc 1%, nickel 1%, above-mentioned catalyst is listed in table 1.
1 embodiment of table and comparative example fischer-tropsch synthetic catalyst evaluation result
According to the result of table 1 it is found that including to be carried on complex carrier containing FT active metal promoter metals having used FT synthetic catalysts in the case of, and used comprising the feelings containing the different carbon monoxide-olefin polymeric of FT active metals or carrier Condition is compared, and CO conversion ratios are very high, and the ratio of the gasoline fraction in product becomes very high, and carbon atom number is the hydrocarbon meeting of long-chain Selectively cracking or isomerization are converted into gasoline fraction, and petrol content is high, can reach 90% or more.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims Subject to fixed protection domain.

Claims (7)

1. a kind of preparation method of hydro carbons catalyst for fischer-tropsch synthesis composition, which is characterized in that the Fiscber-Tropscb synthesis catalysis Active component in agent is the one or more of Co, Fe, Ru, and active component content is converted relative to catalyst benchmark with amount of metal For 0.1~30 mass %, metal promoter is selected from the one or more of Ni, Zn, Mn, Zr, and relative to catalyst benchmark with metal Amount is scaled 0.1-5 mass %；Active component and auxiliary agent are carried on concave-convex stone and spinel oxide complex carrier, concave-convex stone and The mass ratio of spinel complex oxide is 1：2-5, carbon monoxide-olefin polymeric complex carrier are distributed with mesopore-macropore, specific to wrap Include following steps：
(1) deionized water is added in a kettle, stirring is added attapulgite, is uniformly mixed, and slurry A is made；
(2) using magnesium nitrate, aluminum nitrate as presoma, using citric acid or ethylene glycol as complexing agent, wiring solution-forming is simultaneously mixed equal It is even, moisture evaporation is then carried out, solution is transformed into sticky gel by transparent colloidal sol, and finally dry, roasting is made after roasting Magnesium aluminate spinel metal oxide MgAl2O4；
(3) the magnesium aluminate spinel oxide is added in slurry A, control temperature continues to be uniformly mixed, be ultrasonically treated, system Obtain slurry B；
(4) roasting after slurry B spray drying formings is obtained into the concave-convex stone and spinel oxide complex carrier of catalyst；
(5) auxiliary agent introduces：By one or more soluble salt solutions incipient impregnations of Ni, Zn, Mn, Zr to step (4) On complex carrier, then dry, roasting；
(6) active component introduces：By one or more soluble salt solutions incipient impregnations that active component is Co, Fe, Ru It onto step (5) obtained complex carrier containing auxiliary agent, then dries, roasting obtains carbon monoxide-olefin polymeric.
2. preparation method as described in claim 1, which is characterized in that step (5) described drying condition is 100-120 DEG C, when Between 10-20 hours, the condition of roasting is 250-500 DEG C and roasts 1-8 hours；Drying condition is in the step (6)：100-130 DEG C, time 12-20 hour, the condition of roasting is 400-800 DEG C and roasts 1-8 hours；It is nitric acid that cobalt salt solution is used in step (6) Cobalt.
3. preparation method as claimed in claim 1 or 2, which is characterized in that step (2) drying condition is 100-150 DEG C of drying 1-12 hours, roasting condition was 200-400 DEG C and roasts 1-4 hours；Step (3) described temperature is 100-200 DEG C；Step (4) institute It is 350-800 DEG C to state roasting condition, is roasted 1-4 hours.
4. preparation method as claimed in claim 1 or 2, which is characterized in that the metal promoter is the combination of Ni and Zn.
5. preparation method as claimed in claim 1 or 2, which is characterized in that the first aperture of carrier is 10-32nm, accounts for catalyst The 25-40% of pore structure；Second aperture is 60-80nm, accounts for the 40-55% of catalyst pore structure.
6. the carbon monoxide-olefin polymeric that preparation method as described in any one in claim 1-5 obtains is in hydro carbons Fischer-Tropsch synthesis Application, which is characterized in that carbon monoxide-olefin polymeric is filled in fixed bed reactors, control catalytic reaction temperature be 260- 350 DEG C, pressure 0.5-5MPa.
7. application as claimed in claim 6, which is characterized in that restored before reaction, reducing condition is：Pure hydrogen atmosphere, 140~350 DEG C, hydrogen partial pressure is 0.1 ~ 10MPa, volume space velocity 500-2000h-1, the recovery time is 0.1 ~ 72 hour.
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