CN108654591A - A kind of loaded catalyst and the preparation method and application thereof and Fischer-Tropsch synthesis method - Google Patents
A kind of loaded catalyst and the preparation method and application thereof and Fischer-Tropsch synthesis method Download PDFInfo
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- CN108654591A CN108654591A CN201710194682.8A CN201710194682A CN108654591A CN 108654591 A CN108654591 A CN 108654591A CN 201710194682 A CN201710194682 A CN 201710194682A CN 108654591 A CN108654591 A CN 108654591A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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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- 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
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Abstract
The invention discloses a kind of loaded catalyst, preparation method and application and Fischer-Tropsch synthesis methods, the catalyst includes carrier, load carbon component on this carrier and active metal component, wherein, the active metal component includes at least one selected from the non-noble metal first metal component M of group VIII1With at least one the second metal component M selected from Section VI B and/or VIIB races2, catalyst satisfaction (M2/M1)XPS/(M2/M1)XRF=2.0 20.0, wherein (M2/M1)XPSIt is the weight ratio of the second metal component of catalyst and the first metal component that are characterized with x-ray photoelectron spectroscopy based on the element, (M2/M1)XRFIt is the weight ratio of the second metal component and the first metal component based on the element in the catalyst characterized with X-ray fluorescence spectra.Compared with the catalyst of prior art preparation, loaded catalyst of the invention is keeping the higher active and higher C of fischer-tropsch reaction5+Under the premise of selectivity, the isomer selective of product significantly improves.
Description
Technical field
The present invention relates to a kind of loaded catalyst and the preparation method and application thereof and Fischer-Tropsch synthesis methods.
Background technology
In the case of current international energy situation drastically upheaval, energy availability and demand dog-eat-dog, further high-efficiency cleaning profit
There is important strategic importance with coal and natural gas resource.Nytron physical performance based on the manufacture of the technologies such as F- T synthesis is excellent
It is different, can be directly used in mixed way using or with the fuel of low quality crude oil production, with meet increasingly harsher environmental protection and
The requirement of oil property index.Currently, the Sasol companies in South Africa and the Shell companies of Britain/Holland grasp expense advanced in the world
Support industrialization synthesis oil tech, the reactor used have calandria type fixed bed and two kinds of slurry bed system.Sasol companies are in Qatar
Oryx factories be maximum slurry bed system synthesis oilmill in the world, using cobalt-base catalyst.Shell companies and country of Qatar
The Pearl projects of the joint construction in oil company are the maximum natural gas synthetic oil factories of current world's production capacity, and production technology is with cobalt
Based on base catalyst and calandria type fixed bed reactor, operating status is good.
Fischer-Tropsch synthesis cobalt-based catalyst is commonly used in other than active component Co metals, is usually drawn in catalyst preparation
Enter other metals and comes regulating catalyst activity, selectivity and service life as auxiliary agent.Document report studies have shown that these metal promoteds
Agent, especially precious metal additive have a significant impact the activity of Fischer-Tropsch synthesis and the selectivity of liquid hydrocarbon
(ChemCatChem,2010,2,1030-1058)。
CN102909033B discloses a kind of Co based Fischer-Tropsch synthesis catalyst, using platinum modified aluminas as carrier, is with cobalt
Active component.Catalyst preparation process includes preparing platinum colloidal sol and Aluminum sol respectively, and platinum colloidal sol is sufficiently stirred to be formed with Aluminum sol
Then gel is dried and roasts to obtain platinum modified aluminium oxide supports, infusion process load active component cobalt is finally used.
CN102441402B discloses a kind of fischer-tropsch synthetic catalyst and its application, which contains carrier and be supported on
On the carrier selected from iron and/or cobalt active metal component and one or more of promoter metal components in noble metal；
The preparation method of the catalyst includes：(1) iron containing compounds and/or cobalt compound solution with carrier impregnate anti-
It answers；(2) product that dry and calcination steps (1) obtain；It (3) will be containing at least one solution and step selected from precious metal chemical complex
(2) product obtained carries out impregnation；(4) product that dry and calcination steps (3) obtain；The wherein described step (3) it is molten
Liquid contains alkali, and the molar ratio of the alkali and noble metal is 20~200.The content of promoter metal is 0.01-0.3 weight %, preferably
For 0.02-0.15 weight %.Although this method can improve to a certain extent tenor it is relatively low in the case of catalyst activity,
But the activity of catalyst still needs to be further increased.
Invention content
The purpose of the present invention is to provide a kind of in the premise for keeping the higher active and higher C5+ selectivity of fischer-tropsch reaction
Under, fischer-tropsch synthetic catalyst that the isomer selective of product significantly improves and the preparation method and application thereof and F- T synthesis side
Method.
Fischer-tropsch synthetic catalyst provided by the invention is a kind of loaded catalyst, including carrier, load are on this carrier
Carbon component and active metal component, wherein the active metal component includes at least one being selected from group VIII base metal
The first metal component M1With at least one the second metal component M selected from Section VI B and/or VIIB races metal2, the catalyst is full
Foot (M2/M1)XPS/(M2/M1)XRF=2.0-20.0, wherein (M2/M1)XPSIt is the catalyst characterized with x-ray photoelectron spectroscopy
The weight ratio of two metal components and the first metal component based on the element, (M2/M1)XRFIt is the catalysis characterized with X-ray fluorescence spectra
The weight ratio of second metal component and the first metal component based on the element in agent.
The present invention also provides a kind of preparation methods of loaded catalyst, include the following steps：
(1) it is selected from the non-noble metal first metal component M of group VIII with containing at least one1Compound solution leaching
Then carrier after dipping is dried, roasts or does not roast, reduction activation by stain carrier successively；
(2) under reduction or inert atmosphere, the product that step (1) is obtained is impregnated with the solution containing high boiling point organic compound
It is heat-treated later, obtains precursor containing Pd/carbon catalyst；
(3) in a reducing atmosphere with the solution of the compound containing the second metal component selected from Section VI B and/or VIIB races
The precursor containing Pd/carbon catalyst that impregnation steps (2) obtain obtains the loaded catalyst through dry and optional roasting.
The present invention also provides the loaded catalysts made from the above method and above-mentioned loaded catalyst to take in catalysis
Hold in the palm the application in synthetic reaction.
Invention further provides a kind of Fischer-Tropsch synthesis method, this method includes being included in Fischer-Tropsch synthesis condition
It is lower by carbon monoxide and hydrogen and catalyst haptoreaction, wherein the catalyst is above-mentioned loaded catalyst.
Compared with the catalyst of prior art preparation, catalyst of the invention is keeping higher fischer-tropsch reaction active and higher
Under the premise of C5+ selectivity, the isomer selective of product significantly improves.Other features and advantages of the present invention will be subsequent
Specific embodiment part is described in detail.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X of the W 4f of comparative catalyst D1 made from catalyst R1 made from the embodiment of the present invention 1 and comparative example 1
X-ray photoelectron spectroscopy X figure；
Fig. 2 is the X of the Co 2p of comparative catalyst D1 made from catalyst R1 made from the embodiment of the present invention 1 and comparative example 1
X-ray photoelectron spectroscopy X figure.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of loaded catalyst, including carrier, load carbon component on this carrier and activity gold
Belong to component, which is characterized in that the active metal component includes at least one selected from non-noble metal first metal of group VIII
Component M1With at least one the second metal component M selected from Section VI B and/or VIIB races2, the catalyst satisfaction (M2/M1)XPS/
(M2/M1)XRF=2.0-20.0, it is preferable that the catalyst meets (M2/M1)XPS/(M2/M1)XRF=2.5-10, further preferably
Ground, the catalyst meet (M2/M1)XPS/(M2/M1)XRF=3-5, wherein (M2/M1)XPSIt is to be characterized with x-ray photoelectron spectroscopy
The second metal component of catalyst and the first metal component weight ratio based on the element, (M2/M1)XRFIt is with X-ray fluorescence spectra
The weight ratio of second metal component and the first metal component based on the element in the catalyst of characterization.
In the present invention, (M2/M1)XPSIt refer to the second metal component and first in the catalyst that x-ray photoelectron spectroscopy characterizes
Metal component is obtained with the weight ratio of elemental metal with the conversion of respective metal elemental characteristic peak peak area.Wherein X-ray photoelectricity
The measuring instrument of sub- power spectrum is the ESCALab250 type instruments of Thermo Scientific companies, and measuring condition is：Excitation light source
For the monochromator Al K α X-rays of 150kW, in conjunction with the peaks C 1s (284.8eV) capable of being used to correct.
In the present invention, (M2/M1)XRFRefer to the second metal component and the first gold medal in the catalyst that X-ray fluorescence spectra characterizes
Belong to component with the weight ratio of elemental metal.Wherein the measuring instrument of X-ray fluorescence spectra is Rigaku electric machine industry strain formula
3271 type instrument of commercial firm, measuring condition are：Pressed powder pellet is molded, rhodium target, laser voltage 50kV, laser current 50mA.
Preferably, based on the element and on the basis of the total weight of catalyst, the content of first metal component is 5-70
The content of weight %, the second metal component are 0.01-10 weight %, and the content of the carbon component is 1-30 weight %, remaining is
Carrier；It is further preferred that based on the element on the basis of the total weight of catalyst, the content of first metal component is 8-50
The content of weight %, the second metal component are 0.02-8 weight %, and the content of the carbon component is 2-20 weight %, remaining is load
Body.
Also contain under the conditions of, according to the invention it is preferred to, in the catalyst it is at least one selected from Pt, Pd, Ru, Rh, Ir,
The metal promoter of La, Zr, Ce, Y, Cu, metal promoter content based on the element is 0.01-10 weight %, preferably 0.02-8 weights
Measure %, further preferably 0.05-5 weight %.
According to catalyst provided by the invention, it is preferable that the carbon composition weight m in every gram of catalyst based on the elementCWith load
The specific surface area S of body meets mC/ S=0.10-4.0mg/ (m2/g)；It is further preferred that the carbon in every gram of catalyst based on the element
Composition weight mCMeet m with the specific surface area S of carrierC/ S=0.20-2.5mg/ (m2/g)；It is further preferred that every gram of catalysis
Carbon composition weight m in agent based on the elementCMeet m with the specific surface area S of carrierC/ S=0.50-2.0mg/ (m2/g)。
The present invention loaded catalyst and the prior art the difference is that the second metal oriented load in the first metal
The structure feature and component containing charcoal on grain surface, a kind of specific implementation mode according to the present invention, the first metal of the catalyst
Group is divided at least one of Fe, Co, Ni, preferably Co, and the second metal component is at least one of Mo, W, Re, Mn.
The present invention does not specially require the carrier of the catalyst, and carrier can various can be used for being catalyzed F- T synthesis
The catalyst carrier of reaction, the present invention are preferably aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, oxidation
It is one or more in beryllium, clay, molecular sieve, it is preferably one or more in aluminium oxide, silica, titanium oxide.The load
Body can also be one or more in the above-mentioned carrier after being modified using one or more in phosphorus, silicon, fluorine, boron.On
It states modified carrier to be commercially available, can also be modified to obtain using existing method.
According to another aspect of the present invention, the present invention also provides a kind of preparation method of loaded catalyst, the preparations
Method includes the following steps：
(1) it is selected from the non-noble metal first metal component M of group VIII with containing at least one1Compound solution leaching
Then carrier after dipping is dried, roasts or does not roast, reduction activation by stain carrier successively；
(2) under reduction or inert atmosphere, the product that step (1) is obtained is impregnated with the solution containing high boiling point organic compound
It is heat-treated later, obtains precursor containing Pd/carbon catalyst；
(3) in a reducing atmosphere with the solution of the compound containing the second metal component selected from Section VI B and/or VIIB races
The precursor containing Pd/carbon catalyst that impregnation steps (2) obtain obtains the loaded catalyst through dry and optional roasting.
According to the present invention, first metal component is one or more in Fe, Co, Ni element, it is preferable that institute
It is Co to state the first metal component；The compound of first metal component is containing one or more nitre in Fe, Co, Ni element
At least one of hydrochlorate, acetate, sulfate, subcarbonate, chloride；The change containing the first metal active constituent
In the solution for closing object, preferably with the content of the first metal component of elemental metal for 50-1000 grams per liters, further preferably
100-700 grams per liters.
The present invention in step (1), (2) and (3) dipping method and condition be not particularly limited, can be identical or not
Together, the various methods that wherein dipping method can be known to the skilled person, for example, equi-volume impregnating, supersaturation leaching
Stain method, it is preferable that the step (1) and step (2) use incipient impregnation, and maceration extract volume used is based on carrier water absorption rate
It calculates, maceration extract volume used in step (3) is 0.5-10 times, preferably 1-3 times of step (1) maceration extract volume.Immersion condition can
Think that normal condition, the immersion condition of step (1) are preferably：10-90 DEG C of temperature, time 1-10 hour；Further preferably：Temperature
15-40 DEG C of degree, time 2-6 hour.The immersion condition of step (2) and (3) is independent preferably：10-90 DEG C of temperature, time 0.1-
10 hours；Further preferably：15-40 DEG C of temperature, time 0.5-2 hour.
According to the present invention, the carrier after the dipping that step 1) obtains first is dried to go forward side by side and an one-step baking or not roast,
Then the reduction activation is carried out again.The drying and roasting are this field normal condition.Such as drying condition can be：Temperature
40-200 DEG C of degree, time 0.1-24 hour, roasting condition can be：200-600 DEG C of temperature, time 0.1-24 hour.
Step (1) reduction activation can carry out in the mixed atmosphere of hydrogen and inert gas, such as hydrogen and nitrogen and/
Or carried out in the gaseous mixture of argon gas, it is carried out preferably in pure hydrogen.The condition of the reduction activation is not particularly limited, temperature
Preferably 200-500 DEG C, further preferably 300-500 DEG C, more preferably 350-450 DEG C, time are preferably 1-12 hours, into
One step is preferably 1-5 hours, more preferably 2-4 hours.The pressure of the reduction can be that normal pressure may be pressurization, specifically
, the partial pressure of hydrogen can be 0.1-4MPa, preferably 0.1-2MPa.Pressure in the present invention refers to absolute pressure.
According to the present invention, the purpose being heat-treated described in step (2) is so that being immersed in the high boiling point organic compound on carrier
Carbon component is formed through dehydration carbonization to be supported on carrier, the atmosphere of the heat treatment does not specially require, preferably in oxygen free condition
Lower progress.For heat treatment condition, preferably：Temperature is 200-900 DEG C, and the time is 0.1-24 hours, it is further preferred that warm
Degree is 300-700 DEG C, and the time is 1-12 hours.
High boiling point organic compound described in step (2) is the organic matter that common boiling point is higher than 150 DEG C, it is preferable that the height
Boiling organics are at least one of carbohydrate, polyhydroxy organic matter；Wherein, the carbohydrate is sucrose, Portugal
At least one of grape sugar, fructose, maltose, starch, the polyhydroxy organic matter be ethylene glycol, glycerine, 1,2-PD,
At least one of 1,3-PD, polyethylene glycol, the polyethylene glycol can be commercial reagents, preferably number-average molecular weight
For the polyethylene glycol of 190-1050.
According to the present invention, the compound of second metal component is containing one or more in Mo, W, Re, Mn element
At least one of soluble compound；In step (3) in the solution of the compound containing the second metal component based on the element
The compounds content of second metal component is preferably 0.1-100 grams per liters, preferably 0.2-50 grams per liters.
Preferred steps (1) and step (2) solvent for use are water, step (3) solvent for use be water, methanol, ethyl alcohol, propyl alcohol,
At least one of ethylene glycol, hexane, hexamethylene.
According to the present invention, the first metal component and step (2) heat treatment in step (1) after reduction are formed by carbon
Component may advantageously facilitate the oriented load of the second metal component in step (3).Therefore, the above method is preferably included step (1)
Product after reduction activation in hydrogen and/or inert atmosphere, as be cooled to room temperature in nitrogen and/or argon gas or step (2) needed for
The dipping of step (2) is carried out after temperature again.This method further preferably includes by the product after step (2) heat treatment in hydrogen or inertia
Be cooled to room temperature under atmosphere or step (3) required temperature after carry out dipping described in step (3) again.
According to the present invention, mode and condition that the product after being impregnated to step (3) is dried be known in those skilled in the art,
The metal active constituent in catalyst is aoxidized in order to prevent, and the drying is preferably under vacuum or inert gas or reduction
Property gas shield under carry out, it is preferable to use the mode of the gas drying of step 3) dipping atmosphere does the obtained product of dipping
It is dry.As needed, the carrier after drying can further be roasted, the condition of the roasting can be conventional roasting item
Part, for example, under vacuum or inert gas or reducibility gas protection is lower carries out, temperature is 200-600 DEG C, the time is
0.1-24 hours.After completing step (3), it is preferably further passed through O2/N2Volume ratio is that the gaseous mixture 0.5-4 of 0.05-1.0% is small
When, to be passivated metal active constituent therein, obtain the catalyst that can directly preserve in air.
In accordance with the present invention it is preferred that compound, the compound containing the second metal component, height boiling containing the first metal component
The dosage of point organic matter and the condition of step (2) described heat treatment make on the basis of the total weight of catalyst and based on the element,
The content of first metal component is 5-70 weight %, and the content of the second metal component is 0.01-10 weight %, and carbon component contains
Amount is 1-30 weight %, remaining is carrier；It is further preferred that the content of first metal component is 8-50 weight %, the
The content of two metal components is 0.02-8 weight %, and the content of the carbon component is 2-20 weight %, remaining is carrier.
Further include the steps that introducing metal promoter, the metal promoter are into carrier under the conditions of, according to the invention it is preferred to
Selected from least one of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu.The step of introducing metal promoter can be in step (2)
Any one period one or many progress before or after step (2).When the step including introducing metal promoter, preferably
It is introduced using infusion process, includes the solution impregnating carrier with the compound containing metal promoter, then carried out corresponding dry and optional
Roasting.If introduced several times, corresponding dry and optional roasting is all carried out after dipping every time.Described impregnates, does
The operations such as dry and roasting are to be carried out under normal condition well known to those skilled in the art, and details are not described herein again.When including introducing
When the step of metal promoter, the dosage of the compound solution containing metal promoter makes the metal promoter in final catalyst based on the element
Content is 0.01-10 weight %, preferably 0.02-8 weight %, further preferably 0.05-5 weight %.
In accordance with the present invention it is preferred that the selection of the carrier makes finally every gram with step (2) dipping and heat treatment
The content m of the carbon component in catalyst based on the elementCMeet m with the specific surface S of carrierC/ S=0.1-4.0mg/ (m2/ g),
Further preferably mC/ S=0.20-2.5mg/ (m2/ g), it is still more preferably mC/ S=0.50-2.0mg/ (m2/g)。
As described above, the carrier can be the various carriers that can be used as fischer-tropsch synthetic catalyst carrier, as aluminium oxide,
It is one or more in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, preferably oxygen
Change one or more in aluminium, silica, titanium oxide.The carrier can also be using one kind in phosphorus, silicon, fluorine, boron or more
It plants one or more in the above-mentioned carrier after being modified.Above-mentioned modified carrier is commercially available, and can also be used
Existing method is modified to obtain.
The present invention also provides the loaded catalysts made from the above method and the catalyst in Fischer-Tropsch synthesis
In application.
Compared with prior art, the present invention provides catalyst and is keeping the higher active and higher C of fischer-tropsch reaction5+Selectivity
Under the premise of, the isomer selective of product significantly improves.It traces it to its cause, it may be possible to which the second metal oriented load of formation is in cobalt gold
Metal particles surface simultaneously makes the catalyst with the special construction of surface layer carbon component isolation while having appropriate F- T synthesis
It can be with isomery performance.
The present invention also provides a kind of Fischer-Tropsch synthesis method, this method includes, by an oxygen under the conditions of Fischer-Tropsch synthesis
Change carbon and hydrogen and catalyst haptoreaction, wherein the catalyst is above-mentioned loaded catalyst.
Catalytic condition is referred to prior art progress, for example, the molar ratio of hydrogen and carbon monoxide is 0.5-
2.6, preferably 1.5-2.4, further preferably 1.8-2.2, reaction pressure 1-10MPa, preferably 1-4MPa, reaction temperature
It is 150-300 DEG C, preferably 180-250 DEG C.
It should be noted that the method for the present invention is not only suitable for the Fischer-Tropsch synthesis of synthesis gas and catalyst, it is also suitable
In the Fischer-Tropsch synthesis for directly contacting hydrogen and carbon monoxide with catalyst.
The catalytic device any can be enough that the unstripped gas is made to urge with described under the cited reaction conditions
It is carried out in the catalytic reactor of agent, such as fixed bed reactors, paste state bed reactor, fluidized-bed reactor and bubbling bed
It is one or more in reactor.
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.It is described in following embodiments
Percentage composition is unless otherwise instructed mass percentage.The CO converted defined in it accounts for the ratio of air inlet CO and is converted for CO
Rate XCO, be converted to methane CO account for converted CO mole percent be methane selectively SCH4, generate C5+ hydro carbons CO account for
The mole percent for converting CO is C5+ selectivity SC5+, generate the matter that the Alkane isomer in wax (solid at room temperature) accounts for all waxes
Amount percentage is isomer selective Siso。
The measuring instrument of x-ray photoelectron spectroscopy is the ESCALab250 type instruments of Thermo Scientific companies, is surveyed
Amount condition is：Excitation light source be 150kW monochromator Al K α X-rays, in conjunction with can using the peaks C 1s (284.8eV) correction；X is penetrated
The measuring instrument of line fluorescence spectrum is 3271 type instrument of Rigaku electric machine industry Co., Ltd., and measuring condition is：Powder sample
Compression molding, rhodium target, laser voltage 50kV, laser current 50mA.
Embodiment 1
(1) catalyst preparation and characterization
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2(Japanese fuji silicon company puts down carrier
Equal 40-80 micron of granularity), standing is stirred evenly after 4 hours at 20 DEG C, through 120 DEG C of drying, is roasted 4 hours at 400 DEG C, 400 DEG C of hydrogen
Reduction 4 hours, Hydrogen Vapor Pressure are 0.1 megapascal.It is down to room temperature after reduction, and 36.1 milliliter 14.5 is added under logical hydrogen atmosphere
The aqueous solution of grams per liter sucrose after standing 2 hours, after 120 DEG C of drying, is carbonized in 500 DEG C of thermal dehydrations.It is down to room temperature, and
The ammonium metatungstate aqueous solution of 55.1 milliliters of 9.07 grams per liters of tungstenic is added under logical hydrogen atmosphere, stands 2 hours, then dried up with hydrogen.
Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R1,
It is formed, XPS and XRF characterization results are shown in Table 1, and wherein x-ray photoelectron spectroscopy figure is as shown in Figure 1 and Figure 2.According to W 4f and Co
The corresponding peak area conversion of electron binding energy of 2p obtains surface layer atomic ratio (M2/M1)XPS.Table 1 also gives through thermogravimetric analysis, often
Carbon composition weight m in gram catalyst based on the elementCWith the ratio m of carrier specific surface SC/S。
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
The Fischer-Tropsch synthesis performance of catalyst R1 is evaluated in fixed bed reactors.Unstripped gas group becomes H2/CO/N2=
56%/28%/16% (percentage by volume), reaction pressure 2.0MPa, 210 DEG C of reaction temperature.Reaction takes gas after carrying out 24 hours
Body sample carries out chromatography, and is calculated according to above-mentioned definition, the results are shown in Table 2.
Comparative example 1
(1) catalyst preparation and characterization
Prepare the comparative catalyst D1 without charcoal component, remaining metal component same as catalyst R1.
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2(Japanese fuji silicon company puts down carrier
Equal 40-80 micron of granularity), standing is stirred evenly after 4 hours at 20 DEG C, through 120 DEG C of drying, is roasted 4 hours at 400 DEG C, 400 DEG C of hydrogen
Reduction 4 hours, Hydrogen Vapor Pressure are 0.1 megapascal.It is down to room temperature after reduction, and 55.1 milliliters of tungstenics are added under logical hydrogen atmosphere
The ammonium metatungstate aqueous solution of 9.07 grams per liters stands 2 hours, then is dried up with hydrogen.Then through O2/N2Volume ratio be 0.5% it is mixed
It closes gas to be passivated 0.5 hour, it is spare to be stored in drier.Obtained catalyst is denoted as D1, and characterization result is shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
Catalyst D1 is evaluated with evaluation condition in the same manner as shown in Example 1, the results are shown in Table 2.
Comparative example 2
(1) catalyst preparation and characterization
Prepare the comparative catalyst D2 of not tungstenic component, remaining component same as catalyst R1.
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2(Japanese fuji silicon company puts down carrier
Equal 40-80 micron of granularity), standing is stirred evenly after 4 hours at 20 DEG C, through 120 DEG C of drying, is roasted 4 hours at 400 DEG C, 400 DEG C of hydrogen
Reduction 4 hours, Hydrogen Vapor Pressure are 0.1 megapascal.It is down to room temperature after reduction, and 36.1 milliliter 14.5 is added under logical hydrogen atmosphere
The aqueous solution of grams per liter sucrose after standing 2 hours, after 120 DEG C of drying, is carbonized in 500 DEG C of thermal dehydrations.It is down to room temperature, then
Through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R1, characterization
It the results are shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
Catalyst D2 is evaluated with evaluation condition in the same manner as shown in Example 1, the results are shown in Table 1.
Comparative example 3
(1) catalyst preparation and characterization
The comparative catalyst D3 of component same as catalyst R1 is prepared using co-impregnation.
By metal salt concentration needed for equi-volume impregnating, be configured to 36.1 milliliters containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum,
The dipping solution of 14.5 grams per liter of sucrose, the cobalt nitrate of 13.9 grams per liter of tungsten, tetraammineplatinum chloride, sucrose, ammonium metatungstate.It will dipping
Liquid is decanted into 42.5 grams of SiO2Carrier (Japanese fuji silicon company, 40-80 microns of average particle size), standing is stirred evenly at 20 DEG C 4 hours
Afterwards, it is dried through 120 DEG C, roast 4 hours at 400 DEG C, 400 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 megapascal.It is dropped after reduction
To room temperature, then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst
It is denoted as D3, characterization result is shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
Catalyst D3 is evaluated with evaluation condition in the same manner as shown in Example 1, the results are shown in Table 2.
Embodiment 2
(1) catalyst preparation and characterization
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2(Japanese fuji silicon company puts down carrier
Equal 40-80 micron of granularity), standing is stirred evenly after 4 hours at 20 DEG C, through 120 DEG C of drying, is roasted 4 hours at 400 DEG C, 400 DEG C of hydrogen
Reduction 4 hours, Hydrogen Vapor Pressure are 0.1 megapascal.It is down to room temperature after reduction, and 36.1 milliliter 15.3 is added under logical hydrogen atmosphere
The aqueous solution of grams per liter glucose after standing 2 hours, after 120 DEG C of drying, is carbonized in 500 DEG C of thermal dehydrations.It is down to room temperature, and
The ammonium molybdate aqueous solution of 55.1 milliliters of 4.54 grams per liters containing molybdenum is added under logical hydrogen atmosphere, stands 2 hours, then dried up with hydrogen.
Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R2,
Characterization result is shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
The Fischer-Tropsch synthesis performance of catalyst R2 is evaluated in fixed bed reactors.Unstripped gas group becomes H2/CO/N2=
56%/28%/16% (percentage by volume), reaction pressure 2.0MPa, 220 DEG C of reaction temperature.Reaction takes gas after carrying out 24 hours
Body sample carries out chromatography, and is calculated according to above-mentioned definition, the results are shown in Table 2.
Embodiment 3
(1) catalyst preparation and characterization
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of ruthenium
The dipping solution of cobalt nitrate, nitrosyl ruthenium.Maceration extract is decanted into 42.5 grams of γ-Al2O3Carrier (Sasol aluminium oxide, average grain
40-80 micron of degree), standing is stirred evenly at 20 DEG C after 4 hours, through 120 DEG C of drying, is roasted 4 hours at 500 DEG C, 500 DEG C of hydrogen reducings
4 hours, Hydrogen Vapor Pressure was 1.0 megapascal.It is down to room temperature after reduction, and 36.1 milliliter of 11.7 grams per liter is added under logical hydrogen atmosphere
The aqueous solution of glycerine after standing 2 hours, after 100 DEG C of drying, is carbonized in 400 DEG C of thermal dehydrations.It is down to room temperature, and logical
The ammonium metatungstate aqueous solution of 55.1 milliliters of 9.07 grams per liters of tungstenic is added under hydrogen atmosphere, stands 2 hours, then dried up with hydrogen.So
By O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 1 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R3, characterization
It the results are shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
The Fischer-Tropsch synthesis performance of catalyst R3 is evaluated in fixed bed reactors.Unstripped gas group becomes H2/CO/N2=
56%/28%/16% (percentage by volume), reaction pressure 2.5MPa, 210 DEG C of reaction temperature.Reaction takes gas after carrying out 24 hours
Body sample carries out chromatography, and is calculated according to above-mentioned definition, the results are shown in Table 2.
Embodiment 4
(1) catalyst preparation and characterization
By metal salt concentration needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 0.69 grams per liter of iridium
The dipping solution of cobalt nitrate, iridium chloride.Maceration extract is decanted into 42.5 grams of γ-Al2O3Carrier (Sasol aluminium oxide, average particle size
40-80 microns), standing is stirred evenly at 20 DEG C after 4 hours, is dried, is roasted 4 hours at 350 DEG C, 350 DEG C of hydrogen reducings 4 through 120 DEG C
Hour, Hydrogen Vapor Pressure is 0.1 megapascal.It is down to room temperature after reduction, and 36.1 milliliter of 7.27 grams per liter sugarcane is added under logical hydrogen atmosphere
The aqueous solution of sugar after standing 2 hours, after 100 DEG C of drying, is carbonized in 500 DEG C of thermal dehydrations.It is down to room temperature, and in logical hydrogen
The ammonium molybdate aqueous solution of 55.1 milliliters of 1.81 grams per liters containing molybdenum is added under atmosphere, stands 2 hours, then dried up with hydrogen.Then it passes through
O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 2 hours, and it is spare to be stored in drier.Obtained catalyst is denoted as R4, characterization result
It is shown in Table 1.
(2) the catalysis Fischer-Tropsch synthesis performance of catalyst
The Fischer-Tropsch synthesis performance of catalyst R4 is evaluated in fixed bed reactors.Unstripped gas group becomes H2/CO/N2=
56%/28%/16% (percentage by volume), reaction pressure 2.5MPa, 210 DEG C of reaction temperature.Reaction takes gas after carrying out 24 hours
Body sample carries out chromatography, and is calculated according to above-mentioned definition, the results are shown in Table 2.
Table 1
Table 2
These embodiment results illustrate that the present invention provides catalyst compared with prior art, are keeping higher fischer-tropsch reaction
Active and higher C5+Under the premise of selectivity, the isomer selective of product significantly improves.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
Claims (25)
1. a kind of loaded catalyst, including carrier, load carbon component on this carrier and active metal component, feature exist
In the active metal component includes at least one selected from the non-noble metal first metal component M of group VIII1And at least one
The second metal component M selected from Section VI B and/or VIIB races metal2, the catalyst satisfaction (M2/M1)XPS/(M2/M1)XRF=
2.0-20.0, wherein (M2/M1)XPSIt is the second metal component of catalyst characterized with x-ray photoelectron spectroscopy and the first metal group
Divide weight ratio based on the element, (M2/M1)XRFIt is the second metal component and first in the catalyst characterized with X-ray fluorescence spectra
The weight ratio of metal component based on the element.
2. catalyst according to claim 1, wherein the catalyst meets (M2/M1)XPS/(M2/M1)XRF=2.5-10,
Preferably, the catalyst meets (M2/M1)XPS/(M2/M1)XRF=3-5.
3. catalyst according to claim 1 or 2, wherein described based on the element and on the basis of the total weight of catalyst
The content of first metal component is 5-70 weight %, and the content of the second metal component is 0.01-10 weight %, the carbon component
Content is 1-30 weight %, remaining is carrier；
Preferably, based on the element on the basis of the total weight of catalyst, the content of first metal component is 8-50 weight %,
The content of second metal component is 0.02-8 weight %, and the content of the carbon component is 2-20 weight %, remaining is carrier.
4. catalyst according to claim 1, wherein in the catalyst containing it is at least one selected from Pt, Pd, Ru, Rh,
The metal promoter of Ir, La, Zr, Ce, Y, Cu, based on the element and on the basis of the total weight of catalyst, the metal promoter content
For 0.01-10 weight %, preferably 0.02-8 weight %, further preferably 0.05-5 weight %.
5. catalyst according to claim 1 or 2, wherein the carbon composition weight m in every gram of catalyst based on the elementCWith load
The specific surface area S of body meets mC/ S=0.10-4.0mg/ (m2/g)；Preferably, the carbon component weight in every gram of catalyst based on the element
Measure mCMeet m with the specific surface area S of carrierC/ S=0.20-2.5mg/ (m2/g)；It is further preferred that with member in every gram of catalyst
The carbon composition weight m of element meterCMeet m with the specific surface area S of carrierC/ S=0.50-2.0mg/ (m2/g)。
6. according to the catalyst described in any one of claim 1-5, wherein the carrier is aluminium oxide, silica, oxidation
It is one or more in titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve.
7. according to the catalyst described in any one of claim 1-6, wherein the x-ray photoelectron spectroscopy is using excitation
Light source is that the monochromator Al K α X-rays of 150kW measure, and the measuring condition of the X-ray fluorescence spectra includes rhodium target, laser electricity
Pressure is 50kV and laser current is 50mA.
8. a kind of preparation method of loaded catalyst, includes the following steps：
(1) it is selected from the non-noble metal first metal component M of group VIII with containing at least one1Compound solution dipping carry
Then carrier after dipping is dried, roasts or does not roast, reduction activation by body successively；
(2) under reduction or inert atmosphere, after solution dipping of the product containing high boiling point organic compound that step (1) is obtained
It is heat-treated, obtains precursor containing Pd/carbon catalyst；
(3) in a reducing atmosphere with the solution dipping of the compound containing the second metal component selected from Section VI B and/or VIIB races
The precursor containing Pd/carbon catalyst that step (2) obtains obtains the loaded catalyst through dry and optional roasting.
9. preparation method according to claim 8, wherein the compound of first metal component is containing at least one the
At least one of the nitrate of VIII group non-noble metal j element, acetate, sulfate, subcarbonate, chloride, described
The compound of two metal components is at least one of the soluble compound containing at least one of Mo, W, Re, Mn element.
10. preparation method according to claim 8, wherein the high boiling point organic compound is carbohydrate, polyhydroxy has
At least one of machine object；Wherein, the carbohydrate is at least one in sucrose, glucose, fructose, maltose, starch
Kind, the polyhydroxy organic matter is at least one in ethylene glycol, glycerine, 1,2-PD, 1,3-PD, polyethylene glycol
Kind.
11. according to the preparation method described in any one of claim 8-10, wherein step (1), step (2) and step (3)
Described in the condition that impregnates can be identical or different, be independently selected from：Temperature is 10-90 DEG C, preferably 15-40 DEG C；When
Between be 0.1-10 hours, preferably 2-6 hours.
12. according to the preparation method described in any one of claim 8-11, wherein dry condition described in step (1)
Including：Temperature is 40-200 DEG C, and the time is 0.1-24 hours；The condition roasted described in step (1) includes：Temperature is 200-
600 DEG C, the time is 0.1-24 hours.
13. according to the preparation method described in any one of claim 8-12, wherein step (1) described reduction activation is in hydrogen
It is carried out under gas atmosphere, the condition of the reduction activation includes：Temperature is 200-500 DEG C, and the time is 1-12 hours.
14. according to the preparation method described in any one of claim 8-13, wherein step (2) the heat treatment condition packet
It includes：Temperature is 200-900 DEG C, and the time is 0.1-24 hours.
15. according to the preparation method described in any one of claim 8-14, wherein this method further includes going back step (1)
Original activation after product be cooled to room temperature under hydrogen or inert atmosphere or step (2) required temperature after carry out step (2) institute again
The dipping stated.
16. according to the preparation method described in any one of claim 8-15, wherein this method further includes by step (2) heat
Treated is walked again after precursor containing Pd/carbon catalyst is cooled to room temperature under hydrogen or inert atmosphere or step (3) required temperature
Suddenly the dipping described in (3).
17. according to the preparation method described in any one of claim 8-16, wherein this method further includes being obtained to step (3)
To solid be passed through O2/N2The gaseous mixture that volume ratio is 0.05-1.0% 0.5-4 hours.
18. preparation method according to claim 8, wherein contain the compound of the first metal component, contain the second metal component
Compound, the dosage of high boiling point organic compound and the condition of step (2) described heat treatment make using the total weight of catalyst as base
Accurate and based on the element, the content of first metal component is 5-70 weight %, and the content of the second metal component is that 0.01-10 is weighed
% is measured, carbon constituent content is 1-30 weight %, remaining is carrier.
19. preparation method according to claim 8, wherein also include molten with the compound containing metal promoter component
The step of liquid impregnates, the step one or many progress before or after step (2).
20. preparation method according to claim 19, wherein the metal promoter element include selected from Pt, Pd, Ru, Rh,
At least one of Ir, La, Zr, Ce, Y, Cu, the solution usage of the compound containing metal promoter component finally to be catalyzed
The metal promoter content in agent based on the element is 0.01-10 weight %, preferably 0.02-8 weight %, further preferably
0.05-5 weight %.
21. preparation method according to claim 8, wherein at the selection of the carrier and step (2) dipping and heat
Reason makes the content m of the carbon component in final every gram of catalyst based on the elementCMeet m with the specific surface S of carrierC/ S=
0.1-4.0mg/(m2/g)。
22. preparation method according to claim 8, wherein the carrier is aluminium oxide, silica, titanium oxide, oxidation
It is one or more in magnesium, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve.
23. loaded catalyst made from the preparation method described in any one of claim 8-22.
24. application of the loaded catalyst described in any one of claim 1-7 and 23 in Fischer-Tropsch synthesis.
25. a kind of Fischer-Tropsch synthesis method, this method include, by carbon monoxide and hydrogen and catalysis under the conditions of Fischer-Tropsch synthesis
Agent haptoreaction, wherein the catalyst is the loaded catalyst described in any one of claim 1-7 and 23, described
The molar ratio that Fischer-Tropsch synthesis condition includes hydrogen and carbon monoxide is 0.5-2.6, reaction pressure 1-10MPa, reaction temperature
Degree is 150-300 DEG C.
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| WO2024041636A1 (en) * | 2022-08-26 | 2024-02-29 | 中国石油化工股份有限公司 | Metal-modified molecular sieve, and preparation and use thereof |
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