CN108499550A - A kind of preparation method of catalyst for fischer-tropsch synthesis composition - Google Patents
A kind of preparation method of catalyst for fischer-tropsch synthesis composition Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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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
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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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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- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
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 comprising being carried on complex carrier TiO containing copper sulphate and FT active metals2‑SiO2‑ZrO2Carbon monoxide-olefin polymeric preparation method and the hydro carbons characterized by using above-mentioned FT synthetic catalysts manufacturing method.
Description
Technical field
It the present invention relates to the use of Fischer-Tropsch（FT）Reaction is 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, be related to comprising be carried on containing copper sulphate and FT active metals complex carrier carbon monoxide-olefin polymeric,
And the manufacturing method of the hydro carbons characterized by using above-mentioned FT synthetic catalysts.
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 is in 1,923 first letter i.e. F-T names finding first and with their names, abbreviation F-T synthesis or Fischer-Tropsch
Synthesis.By indirect liquefaction technology, not only can from coal the common petroleums product such as extracting gasoline, diesel oil, kerosene, but also
A variety of high value-added products such as the high quality oil product such as Aviation Fuel, lubricating oil and alkene, paraffin can be extracted.From
Since finding to produce hydrocarbon compound on the iron catalyst of alkalization from Fischer and Tropsch, Fiscber-Tropscb synthesis technology is just
Along with the fluctuation and political factor of world's crude oil price, prosperity and decline is indefinite.Fiscber-Tropscb synthesis takes the lead in starting to industrialize in Germany
First indirect liquefaction process units has been built up using, Rule chemical company in 1934, 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 suits to set up
At.FT reactions are the catalyst as active metal such as ruthenium of the iron using iron family element, cobalt, nickel, platinum family element.On the other hand,
Known methanol synthesis reaction is carried out by Cu-series catalyst, C2 oxygenatedchemicals（Ethyl alcohol, acetaldehyde etc.）Synthesis is catalyzed by rhodium system
Agent carries out.
Currently, Exxon-Mobil（Exxon-Mobil）, British Petroleum（BP-Amoco）, ConUS oil company
（ConocoPhillips）With synthetic oil company（Syntroleum）Deng also developing the Fiscber-Tropscb synthesis technique of oneself, transfer 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 generates alkene：
In addition nCO+ (2n) H2=CnH2n+nH2O also has some side reactions, such as：Generate methane：CO+3H2=CH4+H2O generates methanol：CO
+ 2H2=CH3OH generates ethyl alcohol：2CO+4H2=C2H5OH+H2O carbon deposits react：2CO=C+CO2 is other than above 6 are reacted, also
There is the side reaction of the oxygenatedchemicals such as the alcohol for generating higher carbon number and aldehyde, ketone, acid, ester.
Fischer-Tropsch catalyst synthetic catalyst is mainly made of the periodic tables group VIII metal such as Co, Fe, Ni, Ru, is
Activity, stability and the selectivity for improving catalyst, will also be added some auxiliary elements, such as metal oxide in addition to principal component
Or salt.Most of catalyst is required for carrier, such as aluminium oxide, silica, kaolin or diatomite.Synthetic catalyst system
It is just active only after CO+H2 or H2 reduction activations after standby.Currently, using more ripe indirect liquefaction catalyst in the world
Mainly there are iron system and cobalt system two major classes, the mainly Fe-series catalyst that SASOL is used.In SASOL fixed beds and slurry reactor
Precipitated iron catalyst is used in device, uses fused iron catalyst in a fluidized bed reactor.
The only Sasol of Fiscber-Tropscb synthesis cobalt and iron catalyst industrial applications in the world（Iron, cobalt）、Shell（Cobalt）
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 the company such as Rentech of synthetic oil（Iron）、Syntroleum
（Cobalt）；Also some professions are the company such as Johnson Matthey of catalyst（Iron, cobalt）、Albemarle（Iron, cobalt）Deng.
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.
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 being reacted by using containing copper sulphate and to FT
The FT synthetic catalysts of active metal species and the complex carrier with special construction, can manufacture and existing report
The method that gasoline fraction is manufactured by synthesis gas is high compared to activity, gas componant generates less and rich in aromatic series, cycloalkane, alkene
Hydrocarbon, branched alkane high-knock rating gasoline fraction, so as to complete the present invention.
A kind of catalyst for fischer-tropsch synthesis composition, which is characterized in that include：Make to show active gold to Fischer-Tropsch reaction
Belong to the catalyst that precursor dipping copper sulphate back loading is obtained in complex carrier, wherein the work in the Fischer-Tropsch catalyst
Property content relative to catalyst benchmark with amount of metal conversion be about 0.1~30 mass %, the complex carrier be TiO2-
SiO2-ZrO2, wherein Ti:Si:The molar ratio of Zr is 4-5：4-5：2-3, preferably 4：4：2.
The carbon monoxide-olefin polymeric, which is characterized in that active metal Co, Fe, Ru's is one or more.
The carbon monoxide-olefin polymeric, which is characterized in that the mass ratio of Ru and Co is 1：1-4.
The carbon monoxide-olefin polymeric, it is characterised in that auxiliary agent K is further included, relative to catalyst benchmark with amount of metal
Conversion is about 0.1-10%.
The complex carrier TiO2-SiO2-ZrO2Preparation process be：
(i) deionized water is added in reaction kettle a, TiO is added in stirring2, the pH value of acid control mixed liquor is added, is stirred
Uniformly, slurry A is made；Deionized water is added in reaction kettle b, stirring is added TiO2, is uniformly mixed, and slurry B is made；It will
Slurry A, B are uniformly mixed, and are stood, and slurry C is made；
(ii) Ludox is added in slurry C, is uniformly mixed, slurry D is made；
(iii) it is added in slurry D and contains zirconium solution, control temperature continues to be uniformly mixed, and slurry E is made；
(iv) granular powder will be obtained after slurry E spray drying formings, and granular powder roasted to obtain the compound load of catalyst
Body.
The preparation method of carbon monoxide-olefin polymeric, which is characterized in that include the following steps：
（1）Prepare complex carrier TiO2-SiO2-ZrO2；
（2）Copper sulphate is scattered in binder, after being air-dried, roasting；
（3）Roasting product is impregnated in the precursor solution of active metal, the complex carrier TiO is impregnated in after standing2-SiO2-
ZrO2, air drying, 120-200 DEG C roasts 2-5 hours, obtains catalyst for fischer-tropsch synthesis composition.
Wherein step（2）In the binder be silicon dioxide gel；The condition of the roasting is 100-200 DEG C of roasting
1-4 hours.The active metal precursor.In solution is cobalt nitrate, ruthenic chloride, iron chloride at least one.The active metal precursor.In is molten
Liquid is preferably cobalt nitrate and ruthenic chloride.
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 to Fischer-Tropsch reaction show active a kind with
On metal and copper sulphate, be carried on complex carrier TiO2-SiO2-ZrO2Fischer-Tropsch catalyst by being with hydrogen and carbon monoxide
The FT of the gas synthesis hydro carbons of principal component reacts.
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
85% or more.Moreover, the selectivity of catalyst is good, active higher, continuous operations 8-10 each moons, do not occur significantly inactivating mark
As can be adapted for operating with full load for 10 ton day of scale or more.
Carbon monoxide-olefin polymeric involved by present embodiment is the composition for including following substance：Contain sulfuric acid acid copper and FT
1 kind or more of the FT and complex carrier of active metal species are TiO2-SiO2-ZrO2The catalyst of synthesis.
Further include auxiliary agent K in carbon monoxide-olefin polymeric, relative to catalyst benchmark with amount of metal conversion about 0.1-10%.Potassium
Major part is with K2O forms exist, and play the role of electron auxiliary agent, carbon monoxide is contributed to dissociate, increase the selection of long chain hydrocarbons
Property, reduce methane selectively.
The addition of copper sulphate can reduce catalyst and be aoxidized, generally when conversion ratio is higher, the water partial pressure in reactor
Higher, when temperature is higher, this can cause catalyst to be aoxidized；Simultaneously as a small amount of sulfate ion exists to catalyst
Activity has certain benefit, it is noted that the presence of sulfate radical has facilitation rather than sulphion, sulphion is instead
It can be easy to cause catalyst poisoning, in this case, can affirm there is no benefit for catalyst higher than 5ppm.Therefore, centainly
The calcination temperature of catalyst is controlled, it is excessively high copper sulphate to be caused to decompose, catalytic action can not be played.With conventionally known method
It compares, it, can be effectively by the manufacturing method of the hydro carbons of the carbon monoxide-olefin polymeric or present embodiment of present embodiment
Manufacture high-octane gasoline fraction, not yet solved about copper sulphate detailed schematic it is bright, now in depth study in, but speculate
It is as follows：In the reaction using the carbon monoxide-olefin polymeric involved by present embodiment, closed by synthesis gas by FT synthetic catalysts
At hydro carbons contacted with carbon monoxide-olefin polymeric, can inhibit under high reaction temperature carbon atom number be 1 ~ 4 lower hydrocarbon,
CO2Such gas componant generates, can efficiently generate hydrocarbon, and carbon monoxide-olefin polymeric can effectively be made under high-temperature
With 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 active metal objects contained in FT synthetic catalysts as the carbon monoxide-olefin polymeric for constituting present embodiment
Kind, nickel, cobalt, iron, ruthenium can be enumerated.Wherein, as higher active metal species, preferably ruthenium, cobalt, the mass ratio of Ru and Co are
1：1-4.In addition, these metal species can be used alone, can also be applied in combination 2 kinds or more.In addition, into one in catalyst
Step includes auxiliary agent K, relative to catalyst benchmark with amount of metal conversion about 0.1-10%.
The copper sulphate contained in FT synthetic catalysts as the carbon monoxide-olefin polymeric for constituting present embodiment, can make
With commercially available reagent, furthermore it is also possible to use the copper sulphate manufactured by conventionally known method.By boucherizing in ruthenium
Salt, cobalt salt aqueous solution after, be dried, calcine.It is supported metal of more than two kinds as FT active metal species in copper sulphate
When, be dried after the aqueous solution being made to be immersed in copper sulphate to prepare the aqueous solution comprising both ruthenium salt and cobalt salt,
The mode of calcining, can also be dried after so that ruthenium saline solution and cobalt saline solution is individually immersed in copper sulphate,
The episodic pattern of calcining, does not provide particularly, and the addition that applicant chances on copper sulphate can utilize copper ion simultaneously
Auxiliary agent property and sulfate radical promotion, and from generate by-product advantage, in order to realize the effect of copper sulphate, control
The content of copper sulphate is 3-15wt%, preferably 5-8wt% in catalyst, and controls catalyst preparation temperature, and keeping it from can decompose
With collapse.
As ruthenium salt, ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium, six ammonium of chlorination can be enumerated and close the Water-soluble Rus salt such as ruthenium.In addition,
As cobalt salt, it is preferable to use cobalt chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate, cobaltous formate.In addition, about for impregnating the ruthenium supported
The solution of salt, cobalt salt may be formed as the solution of the organic solvents such as alcohol, ether, ketone other than aqueous solution.At this point, selection can
It is dissolved in the salt of various organic solvents.
The content of ruthenium in FT synthetic catalysts is scaled 0.1 ~ 3 mass % relative to catalyst benchmark with amount of metal, preferably
For 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 0.1 mass %
When, activated centre becomes insufficient, to there is the anxiety that cannot obtain sufficient catalytic activity.On the other hand, the content of ruthenium is more than 3 matter
When measuring %, ruthenium cannot be fully supported on the carriers such as copper sulphate, reduced dispersion, easily caused and do not interacted with carrier components
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, preferably
For 5 ~ 18 mass %, more preferably 5 ~ 20 mass %.When the content of cobalt is less than 3 mass %, the cobalt as active metal is very few, has not
It can confirm that the anxiety of significant active rising.On the other hand, when the content of cobalt is more than 20 mass %, later drying, at calcining
Under reason, FT reaction conditions, the cohesion of cobalt is easy to carry out, and has the anxiety for leading to activated centre reduction.In turn, when the content excess of cobalt,
It is likely to result in specific surface area, the pore volume attenuating of catalyst, and the yield of the gas componant in product is easy to increase, therefore
Not preferably.
In turn, in constituting the FT synthetic catalysts of carbon monoxide-olefin polymeric of present embodiment, in copper sulphate and FT activity
On the basis of metal species, alkali metal species can also be contained.As alkali metal species, lithium, sodium, potassium, rubidium etc. can be enumerated,
In preferably sodium, potassium.These alkali metal species can be used alone, can also two or more compound use.
For making FT synthetic catalysts also further contain alkali gold other than containing copper sulphate and FT active metal species
The method of species, is not particularly limited.For example, alkali metal species dipping can be made to support in the same manner as FT active metal species
On copper sulphate.Specifically, after for example making the aqueous solution of sodium salt, sylvite be immersed in copper sulphate, it is dried, calcines.This
Outside, it to FT active metal species and alkali metal species are supported the sequence in copper sulphate, is not particularly limited.
The content of the alkali metal such as sodium, potassium in FT synthetic catalysts is preferred in terms of amount of metal conversion relative to catalyst benchmark
For 0.05 ~ 2 mass %, more preferably 0.05 ~ 1 mass %, further preferably 0.1 ~ 0.5 mass %.By setting sodium, potassium contains
Amount inhibits the effect of the yield of gas componant to become notable more than 0.05 mass %.In addition, by being set in 2 mass % hereinafter,
FT activity can not be reduced and inhibit the yield of gas componant.
After so that FT active metal species as ruthenium, cobalt is immersed in copper sulphate, it is dried, calcines.Drying at this time
Be in principle when FT active metal species dipping being supported in copper sulphate in order to evaporate the water equal solvent that has used and into
Capable, temperature is preferably 80 ~ 200 DEG C, more preferably 120 ~ 150 DEG C.By the way that drying temperature is set in 80 DEG C or more, can promote
The evaporations such as water inlet.On the other hand, by the way that drying temperature is set in 150 DEG C hereinafter, can inhibit to be led by drastically evaporating water etc.
The active metal components unevenness of cause homogenizes.
In addition, calcination temperature is preferably 150 ~ 350 DEG C, more preferably 150 ~ 300 DEG C, further preferably 100 ~ 200 DEG C.
When calcination temperature is far more than 350 DEG C, the copper sulphate in catalyst component is decomposed into Cu oxide, and it is not preferable.Present embodiment
The copper sulphate of involved FT synthetic catalyst ingredients must exist in the form of sulfate, if it is only oxides additive,
The effect of present embodiment cannot then be obtained.On the other hand, if calcination temperature is too low, FT active metal species be cannot achieve
Activation, it is not preferable.
It about the time of drying, calcining, must not make sweeping generalizations according to the difference for the treatment of capacity, but usually 1 ~ 10 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 10 hours or less situations if processing time is more than 10 hours catalytic activity
Do not change, so if consider workability, productivity, then preferably 10 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.
In addition to above-mentioned dipping supports method, as the system containing copper sulphate and the FT synthetic catalysts of FT active metal species
Method is made, the aqueous slurry for preparing and including copper sulphate and FT active metal species, the method being spray-dried can be enumerated.It is right
Slurry concentration at this time, without special provision, but if slurry concentration is too low, then the precipitation that will produce, catalyst component becomes
Uneven, 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
Expect concentration, and active component is caused to waste.In turn, at this time to adjust the concentration of slurry, the mouldability for improving catalyst, ball
Shape turns to purpose, can also add silicon dioxide gel etc. and be used as binder.As the additive amount of binder at this time, preferably
The degree of catalytic activity reduction is not made, usually in the selection of the range of 5 ~ 20 mass %.
When obtaining FT synthetic catalysts by spray drying process, have will simultaneously contain copper sulphate, FT active metal species and
The method and then be further carried on complex carrier that Binder Composition slurry is sprayed, wherein about the air-supply in spray drying process
Temperature is preferably implemented in above-mentioned drying and calcination temperature.
Complex carrier TiO2-SiO2-ZrO2, due to having modified zirconia component in carrier, carrier can kept to stablize
Property while, improve the dispersion performance of active component, and good interaction can be carried out with copper sulphate, be conducive to target product
Flow distribution, improve gasoline fraction yield, and the compression strength and wear-resisting property of catalyst can be kept, this with common zeolite or
Person is common, and single carrier is significantly different.
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, the zirconium component of addition can improve the bonded energy between carrier primary particle, improve 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 the CO under hot conditions as 230 ~ 350 DEG C
Conversion ratio and C5+ selectivity（The 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）Deng 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.As an example of 1 terrace work, the manufacturing method of the hydro carbons based on fixed bed is recorded below.
When carrying out the activity rating of catalyst by fixed bed, due to there is the pressure difference generated in reactor in powder catalyst
Anxiety, therefore as the shape of catalyst, the preferably molded products such as extrusion, pearl product.As what is used in present embodiment
The size of FT synthetic catalysts, zeolite and carbon monoxide-olefin polymeric depends on the scale of reactor, but preferred as catalyst shape
Grain size is 0.5mm ~ 5mm, more preferably 1.0mm ~ 3mm.When grain size is 0.5mm or more, it can fully inhibit the difference in reactor
Pressure rises.On the other hand, by setting grain size in 3mm hereinafter, the coefficient of efficiency of catalyst can be made to improve, so as to efficient
It is reacted on ground.
Carbon monoxide-olefin polymeric involved by present embodiment can carry out reduction treatment in advance before for reaction（Activation
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 being less than 140 DEG C, FT active metal species are not filled
Divide 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 is logical because of catalytic amount, hydrogen
Tolerance 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 when processing
Between be less than 0.1 hour, then have the anxiety that the activation of catalyst becomes inadequate.On the other hand, although it is small even if being performed for more than 72
When prolonged reduction treatment, harmful effect will not be brought to catalyst, but do not find catalytic performance improve, to generate
The undesirable problems such as processing cost increase.
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 biomass such as biomass, sugarcane, palm, seaweed（plantation biomass）Deng.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, in addition, such as
The fruit intrinsic standoff ratio is more than 2.7, then can find the increased tendency of gas componant in the hydro carbons generated.
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（The selectivity of the synthesis for the hydro carbons that carbon atom number is 5 or more）It can become higher, 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 uses 230 ~ 350 DEG C, preferably 240 ~ 310 DEG C, more preferably 250 ~ 300
℃.If reaction temperature is 230 DEG C or more, both FT synthetic catalysts and zeolite can be acted on effectively, can pass through hydro carbons
Generation and its cracking reaction, isomerization reaction etc. manufacture high-octane gasoline fraction.In addition, by by reaction temperature
350 DEG C are set in hereinafter, the undesirable gas componant on FT synthetic catalysts can be inhibited to generate, and can inhibit by boiling
Gas componant caused by overcracking on stone generates.
CO conversion ratios=（CO molal quantitys in unstrpped gas per unit time）-（In exit gas per unit time
CO molal quantitys）］/（CO molal quantitys in unstrpped gas per unit time）×100.
In embodiment below, CO analyses are by having used activated carbon in splitter（Active Carbon）（60/
80 sieve meshes）Thermal conductivity type gas-chromatography（TCD-GC）It carries out.In unstrpped gas, 25 are added with used as internal standard
The synthesis gas of the Ar of volume %（H2With 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 use capillary column（TC-1）Pass through hydrogen flame ion
Detector gas-chromatography（FID-GC）It carries 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 reaction kettle a, TiO is added in stirring2, add acid control mixed liquor
PH value is uniformly mixed, and slurry A is made；Deionized water is added in reaction kettle b, TiO2 is added in stirring, is stirred
It is even, slurry B is made；Slurry A, B are uniformly mixed, stood, slurry C is made；Ludox is added in slurry C, is stirred
It is even, slurry D is made；ZrCl4 is added in slurry D, control temperature continues to be uniformly mixed, and slurry E is made；Slurry E is sprayed
Granular powder is obtained after mist drying and moulding, and granular powder roasted to obtain the complex carrier of catalyst；
The copper sulphate for weighing 9.00g is distributed to the two of the catalyst chemical conversion industry manufacture of 10.71g used as Binder Composition
Silica sol（SiO2Content is 20.6%）In, after then 3 hours dry at 130 DEG C in air, in air at 200 DEG C
It is calcined.Dipping is dissolved with the aqueous solution of 0.7 ruthenic chloride and places 1 hour in the calcining product of 5g.It then will mixing
Solution impregnates and complex carrier TiO2-SiO2-ZrO2, it is 3 hours dry at 100 DEG C in air, and then calcining 3 is small at 160 DEG C
When, obtain the catalyst a1 as FT synthetic catalysts.Structural analysis is carried out by X-ray diffraction method, as a result, it has been found that catalyst
Copper in a1 maintains the state of copper sulphate.In addition, emitting the chemical group that spectrophotometric method carries out catalyst a1 by ICP
At analysis, as a result, it has been found that ruthenium is calculated as 3 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 100（STP）
Ml/ minutes（STP：standard temperatureand pressure）Hydrogen is passed through to be restored within 3 hours.After reduction, switching
For H2The synthesis gas that/CO ratios are about 2（Include the Ar of about 25 volume %）, set to temperature as 260 DEG C, stagnation pressure be 0.9MPaG into
Row reaction.
Comparative example 1
The addition step of copper sulphate and binder is saved, in addition to this, obtains catalyst b similarly to Example 1, containing active
The catalyst b of component ruthenium-complex carrier.Emit the chemical composition analysis that spectrophotometric method carries out catalyst b by ICP,
As a result, it has been found that ruthenium is calculated as 3.0 mass % with metal conversion.FT reactions are carried out by method similarly to Example 1.
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 catalysis
Agent a2 implements at 270 DEG C of reaction temperature, in addition to this, is reacted with method similarly to Example 1.By reaction result
And the composition analysis result of the product obtained at this time is shown in table 1.
Embodiment 3
Active component precursors become ruthenic chloride, cobalt nitrate and ferric chloride solution, using catalyst a3, active metal in catalyst a3
Ru:Co:Fe mass ratioes are 1：1-4：1-3 implemented at 280 DEG C of reaction temperature, in addition to this, with similarly to Example 1
Method 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 copper sulphate for weighing 4.5g is mixed with a small amount of binder, dry, so that it is immersed in the water of 3.0g after roasting and is dissolved with
Cobalt nitrate Co (the NO of 3.46g3)2·6H2The aqueous solution of O is simultaneously placed 1 hour.Then, it dries 3 hours in air, at 80 DEG C,
Then use infusion process by active component and boucherizing in complex carrier TiO2-SiO2-ZrO2, and then calcined at 210 DEG C
4 hours, then to obtain the catalyst a4 as FT synthetic catalysts.Structural analysis is carried out by X-ray diffraction method, as a result
It was found that the copper in catalyst a4 maintains the state of copper sulphate.In addition, emitting spectrophotometric method by ICP carries out catalyst
The chemical composition analysis of a4, as a result, it has been found that cobalt is calculated as 10.0 mass % with metal conversion.Using catalyst a4, it is in reduction temperature
Implement at 350 DEG C, 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 synthetic catalysts.It is logical
The chemical composition analysis that ICP transmitting spectrophotometric methods carry out catalyst c is crossed, as a result, it has been found that cobalt is calculated as 10 matter with metal conversion
Measure %.
Comparative example 3
It is applicable in common zeolite ZSM-5 and replaces complex carrier, other conditions are same as Example 4, manufacture FT synthetic catalysts.It is logical
The chemical composition analysis that ICP transmitting spectrophotometric methods carry out catalyst d is crossed, as a result, it has been found that cobalt is calculated as 10 matter with metal conversion
Measure %.The catalytic effect of above-mentioned catalyst is listed in table 1.
1 embodiment of table and comparative example fischer-tropsch synthetic catalyst evaluation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Reaction temperature DEG C | 260 | 270 | 280 | 260 | 260 | 260 | 260 |
| CO conversion ratios % | 86.9 | 81.4 | 82.5 | 83.2 | 70.1 | 65.8 | 52.7 |
| CO2Conversion ratio % | 1.4 | 1.6 | 1.8 | 1.8 | 0.4 | 0.5 | 0.5 |
| CH4Conversion ratio % | 20.1 | 20.7 | 22.4 | 25.8 | 9.2 | 9.4 | 8.5 |
| C2-C4Selective % | 10.2 | 9.8 | 8.8 | 9.8 | 7.8 | 8.9 | 8.0 |
| C5+ selectivity % | 89.7 | 9.02 | 91.4 | 90.5 | 70. 8 | 72.4 | 73.5 |
| Petrol content C4-C10(wt%) | 88.9 | 91.3 | 92.9 | 93.2 | 40.2 | 40.8 | 42.8 |
| Kerosene distillate C11-C21(wt%) | 10.2 | 9.7 | 11.6 | 12.0 | 40.2 | 41.5 | 46.8 |
According to the result of table 1 it is found that having used comprising the FT for being carried on complex carrier containing FT active metals and copper sulphate
In the case of synthetic catalyst, from phase the case where use comprising containing FT active metals or carrier different carbon monoxide-olefin polymeric
Than CO conversion ratios are very high, and the ratio of the gasoline fraction in product becomes very high, and carbon atom number, which is the hydrocarbon of long-chain, to be selected
Property cracking or isomerization, be converted into gasoline fraction, petrol content is high, can reach 90%..
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 (2)
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
About 0.1~30 mass %, metal promoter are selected from the one or more of Ni, Zn, Mn, Zr, and relative to catalyst benchmark with gold
Category amount is scaled 0.1-5 mass %；Active component is carried on concave-convex stone and spinel oxide complex carrier, concave-convex stone with auxiliary agent
Mass ratio with spinel complex oxide is 1：2-5, carbon monoxide-olefin polymeric complex carrier are distributed with mesopore-macropore, specifically
Include the 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；
Step (2) drying condition is 100-150 DEG C 1-12 hours dry, and roasting condition is 200-400 DEG C and roasts 1-4 hours；Step
Suddenly (3) described temperature is 100-200 DEG C；Step (4) described roasting condition is 350-800 DEG C, is roasted 1-4 hours；The metal
Auxiliary agent is the combination of Ni and Zn.
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.
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Application publication date: 20180907 |