CN108822883A - Cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method - Google Patents
Cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method Download PDFInfo
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- CN108822883A CN108822883A CN201810630071.8A CN201810630071A CN108822883A CN 108822883 A CN108822883 A CN 108822883A CN 201810630071 A CN201810630071 A CN 201810630071A CN 108822883 A CN108822883 A CN 108822883A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 15
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 12
- 239000010941 cobalt Substances 0.000 title claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012876 carrier material Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000005485 electric heating Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- -1 carbon alkane Chemical class 0.000 abstract 2
- 238000005457 optimization Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000005416 organic matter Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910002370 SrTiO3 Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/8946—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 alkali or alkaline earth metals
-
- B01J35/39—
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
Abstract
Strontium titanates is loaded altogether the invention discloses a kind of cobalt and plasma activated metal realizes photo-thermal Fischer-Tropsch synthesis method.Photo-thermal catalyst assembles ultraviolet light, visible light and infrared portions in simulated solar irradiation by absorbing, and is catalytic process for light, heat supply, induces photo-thermal Fischer-Tropsch synthesis, improve reaction temperature, and then accelerate reaction rate.The optimization of methane and more carbon alkane, the yield of alkene and selectivity in organic product can be achieved by the regulation to photo-thermal catalytic component.It needs just to can be carried out under the conditions of high pressure and electric heating compared to traditional F- T synthesis, this technology carry out F- T synthesis can under the conditions of low pressure and sunlight are irradiated by photochemical and thermal reaction, reduce energy consumption, save reaction cost.In addition, this technology has also obtained the yield and selectivity relative to the higher more carbon alkane of traditional F- T synthesis, alkene, later period separation costs are reduced, high value added product yield increases, and has certain commercial application prospect.
Description
Technical field
The present invention relates to the preparation and application of a kind of photo-thermal catalyst, in particular to cobalt and plasma activated metal loads altogether
Strontium titanates realizes photo-thermal Fischer-Tropsch synthesis method.
Background technique
Specific gravity of the petroleum in world's energy-consuming gradually rises, it has also become the big energy of the first in the world.China's oil is in energy
Ratio in source structure constantly increases, but oil production rate increases lower than consumption growth.In recent years, process of industrialization accelerate and
The use of fossil energy leads to CO in atmosphere2The content of isothermal chamber gas increases, and forms greenhouse effects, and then produce many lifes
State environmental problem.Therefore, it is badly in need of accelerating the exploitation and popularization of new energy technology.Artificial light synthetic technology can use light and catalysis
Carbon dioxide and water are converted organic-fuel by agent, this without suspected of solve energy and environmental problem provide one it is potential feasible
Approach.
Traditional thermocatalytic F- T synthesis is also to realize that carbon dioxide, carbon monoxide are converted into one of approach of organic matter.
However, higher cost limits the market competitiveness of F- T synthesis：On the one hand, traditional F- T synthesis needs a large amount of electric energy
Heat supply, the operating pressure of 20-30 atmospheric pressure are also required to expend mass energy to compress reaction gas；On the other hand, traditional to take
It is also that the separation in later period increases cost that support synthetic product, which has lower selectivity,.Therefore, research and development new catalyst is anti-to reduce
It should be able to consume and improve reaction product and selectively be of great significance.
Currently, the research of fischer-tropsch synthetic catalyst is concentrated mainly on the catalysis that Ru, Ni, Co and Fe etc. are efficient, highly selective
The exploitation of agent.Ru base catalyst is the highest catalyst of F- T synthesis activity, and the selectivity of heavy hydrocarbon is high, but its price
Valuableness, can not large-scale use；Ni base catalyst organic matter yield with higher, but it more carbon organic matters selectivity compared with
Difference, and catalyst can be lost when in use, can not also be put into production and be applied.Therefore, common in industry at present
Fischer-tropsch synthetic catalyst is mainly Fe base and Co base catalyst.Wherein Fe base catalyst is easier to generate in Fischer-Tropsch synthesis
Low-carbon product；Co base catalyst has the spies such as high activity, high linear saturation heavy hydrocarbon-selective and low water gas shift reaction
Point.
In this case, explore new catalyst to change reaction path, so improve more carbon products yield and
Selectivity, while the energy consumption for reducing reaction becomes the important breakthrough mouth for breaking conventional synthesis mode.By being changed into of luminous energy
It learns and can and be stored in the form of organic matter, be a kind of artificial important channel for utilizing solar energy.Photo-thermal catalysis refers to photo-thermal
Catalyst absorbs ultraviolet light, visible light and infrared part in sunlight, is reaction for light, heat supply, improves temperature of reaction system, add
Fast response rate.The patent that we have obtained authorization is " a kind of to utilize sunlight and the direct chemical recycling of carbon dioxide system of photo-thermal catalyst
The technology of standby the organic-fuel " (patent No.：ZL201410246792.0 in), it has been demonstrated that photo-thermal is catalyzed hydrogenation of carbon dioxide
Feasibility, present invention be distinguished in that demonstrating the feasibility that photo-thermal catalytic CO adds hydrogen (i.e. F- T synthesis).I
Patent " a kind of Fischer-Tropsch synthesis method that low methane selectively under low pressure is realized using photo-thermal-F- T synthesis " (Shen for having applied
Please number：201710707327.6) it realizes Fe base catalyst and is catalyzed F- T synthesis applied to photo-thermal, photo-thermal is then catalyzed by the present invention
The material system of F- T synthesis has further been extended to metal (Co and Au, Ag, Cu) and semiconductor (SrTiO3) composite material.
Summary of the invention
In order to solve the problems in the prior art, the present invention provides a kind of cobalt and plasma activated metal loads strontium titanates altogether
It realizes photo-thermal Fischer-Tropsch synthesis method, while assisting Fischer-Tropsch synthesis for light, heat supply using solar energy, solve to add in the prior art
Energy consumption is high with thermocatalytic process, high production cost, more carbon (C for pressure1+) lower and photocatalytic process the low efficiency of selectivity etc. asks
Topic.
The technical scheme is that：
Cobalt and plasma activated metal load strontium titanates altogether and realize that photo-thermal Fischer-Tropsch synthesis method, photo-thermal catalyst pass through absorption
Ultraviolet light, visible light and infrared part (see Fig. 1) in sunlight improve reaction temperature, are that catalytic process is induced for light, heat supply
Photo-thermal Fischer-Tropsch synthesis, and then accelerate reaction rate.
The photo-thermal catalyst is Co and plasma activated metal (Au, Ag, Cu are one of) the two mutual load exists
SrTiO3On carrier material.
The photo-thermal F- T synthesis refers to it is not necessary that by way of additionally heating, photo-thermal catalyst is assembling simulated solar
Under the irradiation condition of light, while ultraviolet light, visible light and infrared part is absorbed and utilized, improves reactant by itself photo-thermal effect
It is temperature and then the generation and progress for inducing and accelerating Fischer-Tropsch synthesis.
The preparation method of the photo-thermal catalyst will be contained Co or be waited using dipping-sintering process or light deposition-sintering process
The precursor solution of ion activity metal is mixed with carrier material, be evaporated using electric heating mixing platform heated solution and
H2Reduction is fired in-Ar mixed atmosphere, or makes active element light deposition on carrier for light using simulated solar irradiation is assembled.
Dipping-the sintering process prepares photo-thermal catalyst, includes the following steps：
(1) carrier material is dispersed in the Catalyst precursor solutions that the nitrate containing Co is configured to, Co element accounts for
Carrier material mass percent is 0.1%-10%, and certain volume water, which is added, makes liquor capacity increase to 20ml, passes through ultrasonic treatment
Carrier material is set to be uniformly dispersed within 10 minutes.Acquired solution is heated on heating stirring platform and is evaporated, and powder is transferred in mortar
Carefully grinding；
(2) gained powder in (1) is packed into tube furnace, in H2500-700 in-Ar percent by volume 10%-90% atmosphere
DEG C fire 4h；
(3) by the gained catalysis that powder is dispersed in the nitrate containing plasma activated metal, chloride is configured in (2)
In agent precursor solution, it is 0.0005%-0.5% that plasma activated metallic element, which accounts for material gross mass percentage, is added certain
Volume of water makes liquor capacity increase to 20ml, and acquired solution is heated on heating stirring platform and is evaporated；
(4) gained powder in (3) is packed into tube furnace, in H2300 DEG C of burnings in-Ar percent by volume 10%-90% atmosphere
1h processed.
Light deposition-the sintering process prepares photo-thermal catalyst, includes the following steps：
(1) carrier material is dispersed in the Catalyst precursor solutions that the nitrate containing Co is configured to, Co element accounts for
Carrier material mass percent is 0.1%-10%, and certain volume water, which is added, makes liquor capacity increase to 20ml, passes through ultrasonic treatment
Carrier material is set to be uniformly dispersed within 10 minutes.Acquired solution is heated on heating stirring platform and is evaporated, and powder is transferred in mortar
Carefully grinding；
(2) gained powder in (1) is packed into tube furnace, in H2500-700 in-Ar percent by volume 10%-90% atmosphere
DEG C fire 4h；
(3) by the gained catalysis that powder is dispersed in the nitrate containing plasma activated metal, chloride is configured in (2)
In agent precursor solution, it is 0.0005%-0.5% that plasma activated metallic element, which accounts for material gross mass percentage,；
(4) solution handled well is placed in mix and is stirred on platform, surface plate is covered on beaker, with convergence simulated solar illumination
Penetrating solution makes plasma activated metal light deposition on carrier, then multiple centrifuge washing obtained solid powder, and it is dry to place vacuum
It is dried for 24 hours in dry case.
The photo-thermal F- T synthesis can regulate and control organic matter by adjusting mass percent of the Co in photo-thermal catalyst
Total output and methane selectivity.
The photo-thermal F- T synthesis is replaced in photo-thermal catalyst and plasma activated metallic element or adjusts its content, can be with
Regulate and control the total output of organic matter and the selectivity of methane.
The photo-thermal F- T synthesis replaces the Mo-Co catalyst of different elements in photo-thermal catalyst, can regulate and control organic matter
The selectivity of total output and methane.
The beneficial effects of the invention are as follows：1. low energy consumption and efficient photo-thermal Fischer-Tropsch synthesis.Photo-thermal catalyst is direct
It is catalytic process for light, heat supply using ultraviolet light, visible light and the infrared part in sunlight, and is not necessarily to pressurized equipment, adds
Press strip part, under low pressure or condition of negative pressure, photo-thermal catalyst can be catalyzed H2Organic compound, simple process, energy are prepared with CO
It consumes lower.
2. the yield of carbon more than is high.Traditional F- T synthesis, products therefrom is from a carbon (C1) organic matter is to pentadecane (C15) organic matter
Product has generation, but CH4Content be higher than the sum of all other more carbon organic matters；The distribution of photo-thermal Fischer-Tropsch synthetic is very
Narrow, selectivity is very high, with low-carbon alkanes, alkene organic matter (C2-C3) based on, and CH4Content close to even lower than C2、C3It is organic
The sum of object.
In conclusion the present invention relates to be catalyzed using containing the photo-thermal of Co and plasma activated metal and semiconductor carrier
Agent is catalyzed CO and H in the case where assembling simulated solar irradiation irradiation condition2Reaction generates CH4With the technology of more carbon organic matters.The catalytic body
System improves reaction temperature, accelerates reaction rate by introducing plasma activated metal.By adjusting each component in photo-thermal catalyst
The ratio of methane in the product can be greatly lowered in ratio, and then improves the yield of more carbon.Traditional F- T synthesis generally requires
It is heating and could occur under condition of high voltage, energy consumption is high, and distribution of reaction products is wide, poor selectivity.Compared to traditional F- T synthesis,
This technology is improved in terms of energy consumption, more carbon yield two, and production cost reduces, and high value added product yield increases.Based on upper
Feature is stated, this invention has the potentiality that can be applied to industrialized production, has certain Commercial Prospect.
Detailed description of the invention
The uv-visible absorption spectra of Fig. 1 Co, plasma activated metal mutual load strontium titanates photo-thermal catalyst；
The XRD spectrum of Fig. 2 Co, plasma activated metal mutual load strontium titanates photo-thermal catalyst.
Specific embodiment
Invention is further explained by way of example and in conjunction with the accompanying drawings, but protection scope of the present invention is unlimited
In following embodiment.
Embodiment 1
Influence of the Au constituent content to photo-thermal catalyst catalytic performance：
Weigh more parts of 0.5g nanometers of SrTiO3Carrier is measured according to the Co metal quality percentage of 0.1%-10.0% and is prepared
Good Catalyst precursor solutions, by nanometer SrTiO3Carrier mixes in multiple beakers respectively with more parts of solution, and is added one
Determining volume of water makes liquor capacity increase to 20ml.Beaker, which is ultrasonically treated 10 minutes, makes carrier material be uniformly dispersed.Acquired solution exists
Heating is evaporated on heating stirring platform, and powder is transferred in mortar and is carefully ground.Above-mentioned sample is packed into tube furnace, in H2-
It is fired 4 hours for 500-700 DEG C in Ar percent by volume 10%-90% atmosphere, gained powder, which is transferred in mortar, carefully to be ground, and is obtained
To final sample.
It weighs 100mg Co-STO to be placed in reaction system, after being vacuumized to reaction system, is respectively by the mass ratio of the material
2：1 is passed through H2, CO, final air pressure be 55KPa, assemble simulated solar irradiation irradiation under react 2h.Repeatedly being optimized can send out
The content of existing Co is optimal for selectivity 2%.
The 2%Co-STO of four parts of above-mentioned preparations of 0.5g is weighed, it is molten that gained powder is dispersed in 1g/100ml gold chloride presoma
In liquid, it is 0.0005%-0.5% that Au element, which accounts for material gross mass percentage, and certain volume deionized water, which is added, increases to volume
20ml.Beaker, which is ultrasonically treated 10 minutes, makes powder be uniformly dispersed.By the solution of acquisition be transferred to electric heating mixing platform stir to
It is evaporated completely, then powder is transferred in mortar and is carefully ground.Sample is packed into tube furnace after grinding, in H2- Ar volume basis
It is fired 1 hour than 300 DEG C in 10%-90% atmosphere, sample after firing is ground, final sample is obtained, is respectively labeled as 2%
Co-0.0005%Au-STO, 2%Co-0.005%Au-STO, 2%Co-0.05%Au-STO, 2%Co-0.5%Au-STO,
2%Co-STO.It weighs 100mg final sample respectively to be placed in reaction system, after vacuumizing reaction system, then by substance
Amount is than being respectively 2：1 is passed through H2, CO, final air pressure be 55KPa, assemble simulated solar irradiation irradiation under react 2h.Photo-thermal is urged
Change activity, is specifically shown in Table 1.
The photo-thermal catalytic performance of 1 Co-Au-STO catalyst of table
Embodiment 2
Influence of the Ag element to photo-thermal catalyst catalytic performance：
The 2%Co-STO for weighing the preparation of 0.5g embodiment 1, the nitrate of Ag is dissolved in water, and to be configured to catalyst precursor molten
Liquid.Measure above-mentioned prepared Catalyst precursor solutions according to 0.5% Ag metal quality percentage, by 2%Co-STO with
Solution mixes in beaker, and certain volume deionized water, which is added, makes volume increase to 20ml.The mixture of acquisition is transferred to electricity to add
Thermal agitation platform is stirred to being evaporated completely, and then powder is transferred in mortar and is carefully ground.Sample is packed into tube furnace after grinding,
H2It is fired 1 hour for 300 DEG C in-Ar percent by volume 10%-90% atmosphere, sample after firing is ground, final sample is obtained, marked
It is denoted as 2%Co-0.5%Ag-STO.The total content of organic carbon of its photo-thermal catalysate is 115.4 μm of ol, and methane selectively is
43.7%.
Embodiment 3
Influence of the Cu element to photo-thermal catalyst catalytic performance：
The 5%Co-STO for weighing the preparation of 0.5g embodiment 2, the nitrate of Cu is dissolved in water, and to be configured to catalyst precursor molten
Liquid.Measure above-mentioned prepared Catalyst precursor solutions according to 0.5% Cu metal quality percentage, by 5%Co-STO with
Solution mixes in beaker, and certain volume deionized water, which is added, makes volume increase to 20ml.Beaker, which is ultrasonically treated 10 minutes, makes powder
Body is uniformly dispersed.The mixture of acquisition is transferred to electric heating mixing platform to stir to being evaporated completely, then powder is transferred to and is ground
It is carefully ground in alms bowl.Sample is packed into tube furnace after grinding, in H21 is fired for 300 DEG C in-Ar percent by volume 10%-90% atmosphere
Hour.Sample is ground after firing, and obtains final sample, is labeled as 5%Co-0.5%Cu-STO.Its photo-thermal catalysate it is total
Organic carbon content is 1233 μm of ol, methane selectively 73.9%.
Embodiment 4
Influence of the different loads sequence to photo-thermal catalyst catalytic performance：
Weigh 0.5g nanometers of SrTiO3Carrier measures prepared catalysis in example 3 according to 0.05% Au mass percent
Agent precursor solution, the two is mixed and added into certain volume water in beaker makes liquor capacity increase to 20ml.By beaker ultrasound
Processing makes carrier material be uniformly dispersed in 10 minutes.The mixture of acquisition is transferred to electric heating mixing platform to stir to being evaporated completely,
Then powder is transferred in mortar and is carefully ground.Sample is packed into tube furnace after grinding, in H2- Ar percent by volume 10%-
It is fired 1 hour for 300 DEG C in 90% atmosphere, sample after firing is ground.The 0.5g sample is weighed, according to 1% Co metal quality
Percentage measures prepared Catalyst precursor solutions in example 1, and the two is mixed and added into certain volume water in beaker to be made
Liquor capacity increases to 20ml, so that carrier material is uniformly dispersed by being ultrasonically treated 10 minutes, mixture is transferred to electric heating and is stirred
Mix platform stirring drying, grinding, in H2It is fired 4 hours for 500-700 DEG C in-Ar percent by volume 10%-90% atmosphere, grinding obtains
Final sample is labeled as 0.05%Au-1%Co-STO.
The method for copying embodiment 3 prepares 1%Co-0.05%Au-STO sample.It weighs 100mg sample and is packed into photo-thermal catalysis
It is respectively then 2 by the mass ratio of the material after being vacuumized to reaction system in reactor：1 is passed through H2, CO, final air pressure is
55KPa reacts 2h in the case where assembling simulated solar irradiation irradiation.Catalyst activity test result shows, 0.05%Au-1%Co-STO
And the total content of organic carbon of 1%Co-0.05%Au-STO is respectively 7.5 μm of ol and 113.3 μm of ol, methane selectively is respectively
34.3% and 58.7%.
Embodiment 5
Influence of the different loads mode to photo-thermal catalyst catalytic performance：
The 2%Co-STO for weighing the preparation of 0.5g embodiment 1 is measured in example 3 according to 0.05% Au mass percent and is prepared
Good Catalyst precursor solutions, mix in beaker with 2%Co-STO, and certain volume water, which is added, increases to liquor capacity
Beaker is made carrier material be uniformly dispersed by 20ml by ultrasonic treatment.The solution handled well is placed in mix and is stirred on platform, in beaker
Upper capping surface plate makes Au be deposited on carrier surface with simple substance form with simulated solar irradiation irradiation solution 30min is assembled.Remove table
Face ware, by suspension centrifugation separate sample with reaction solution, then be added distilled water clean, after be centrifuged again,
Repeatedly three times can will powder that centrifuge separation comes out be placed in a vacuum drying oven it is dry for 24 hours afterwards grinding uniformly can be obtained it is final
Product is labeled as P-2%Co-0.05%Au-STO.It weighs 100mg sample to be fitted into photo-thermal catalytic reactor, to reaction system
It is respectively then 2 by the mass ratio of the material after vacuumizing：1 is passed through H2, CO, final air pressure be 55KPa, assemble simulated solar
Light irradiation is lower to react 2h.The total content of organic carbon of its photo-thermal catalysate is 299.1 μm of ol, methane selectively 57.4%.
Claims (6)
1. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method, which is characterized in that photo-thermal catalysis
Agent realizes photo-thermal F- T synthesis, by CO and H under the irradiation condition for assembling simulated solar irradiation2Mixing is catalytically conveted to organise
Close object.
2. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method according to claim 1,
It is characterized in that, the photo-thermal catalyst is that Co and plasma activated metal Au, Ag, Cu one of which mutual load are carried in strontium titanates
On body material.
3. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method according to claim 1,
It is characterized in that, the photo-thermal F- T synthesis, refers to it is not necessary that by way of additionally heating, photo-thermal catalyst is assembling simulated solar
Under the irradiation condition of light, while ultraviolet light, visible light and infrared part is absorbed and utilized, improves reactant by itself photo-thermal effect
It is temperature and then the generation and progress for inducing and accelerating Fischer-Tropsch synthesis.
4. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method according to claim 2,
It is characterized in that, the photo-thermal catalyst can be divided into two classes：One kind is made by dipping-sintering process；Another kind of is heavy by light
Product-sintering process is made.
5. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method according to claim 4,
It is characterized in that, the photo-thermal catalyst uses dipping-sintering process, and synthesis includes the following steps：
(1) carrier material is dispersed in the Catalyst precursor solutions that the nitrate containing Co is configured to, Co element accounts for carrier
Quality of materials percentage is 0.1%-10%, and certain volume water, which is added, makes liquor capacity increase to 20ml, passes through 10 points of ultrasonic treatment
Clock makes carrier material be uniformly dispersed.Acquired solution is heated on heating stirring platform and is evaporated, and powder is transferred in mortar carefully
Grinding；
(2) gained powder in (1) is packed into tube furnace, in H2500-700 DEG C of firing in-Ar percent by volume 10%-90% atmosphere
4h；
(3) before (2) middle gained powder being dispersed in the nitrate containing plasma activated metal, the catalyst that chloride is configured to
It drives in liquid solution, it is 0.0005%-0.5% that plasma activated metallic element, which accounts for material gross mass percentage, and certain volume is added
Water makes liquor capacity increase to 20ml, and acquired solution is heated on heating stirring platform and is evaporated；
(4) gained powder in (3) is packed into tube furnace, in H2300 DEG C of firing 1h in-Ar percent by volume 10%-90% atmosphere.
6. cobalt and plasma activated metal load strontium titanates altogether and realize photo-thermal Fischer-Tropsch synthesis method according to claim 4,
It is characterized in that, the photo-thermal catalyst uses light deposition-sintering process, and synthesis includes the following steps：
(1) carrier material is dispersed in the Catalyst precursor solutions that the nitrate containing Co is configured to, Co element accounts for carrier
Quality of materials percentage is 0.1%-10%, and certain volume water, which is added, makes liquor capacity increase to 20ml, passes through 10 points of ultrasonic treatment
Clock makes carrier material be uniformly dispersed.Acquired solution is heated on heating stirring platform and is evaporated, and powder is transferred in mortar carefully
Grinding；
(2) gained powder in (1) is packed into tube furnace, in H2500-700 DEG C of firing in-Ar percent by volume 10%-90% atmosphere
4h；
(3) before (2) middle gained powder being dispersed in the nitrate containing plasma activated metal, the catalyst that chloride is configured to
It drives in liquid solution, it is 0.0005%-0.5% that plasma activated metallic element, which accounts for material gross mass percentage,；
(4) solution handled well is placed in mix and is stirred on platform, surface plate is covered on beaker, simulated solar irradiation irradiation is molten with assembling
Liquid makes plasma activated metal light deposition on carrier, then multiple centrifuge washing obtained solid powder, places vacuum oven
Middle drying is for 24 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113967476A (en) * | 2021-11-22 | 2022-01-25 | 北京化工大学 | Perovskite supported cobalt efficient catalyst, preparation method and method for preparing methanol by partial oxidation of methane |
| CN114029061A (en) * | 2021-11-22 | 2022-02-11 | 北京化工大学 | Double-metal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by co-conversion of methane and carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104403682A (en) * | 2014-12-09 | 2015-03-11 | 中国科学院山西煤炭化学研究所 | Photocatalysis Fischer-Tropsch synthesis method and used catalyst |
| CN107699271A (en) * | 2017-08-17 | 2018-02-16 | 天津大学 | A kind of Fischer-Tropsch synthesis method that low methane selectively under low pressure is realized using photo-thermal F- T synthesis |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104403682A (en) * | 2014-12-09 | 2015-03-11 | 中国科学院山西煤炭化学研究所 | Photocatalysis Fischer-Tropsch synthesis method and used catalyst |
| CN107699271A (en) * | 2017-08-17 | 2018-02-16 | 天津大学 | A kind of Fischer-Tropsch synthesis method that low methane selectively under low pressure is realized using photo-thermal F- T synthesis |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113967476A (en) * | 2021-11-22 | 2022-01-25 | 北京化工大学 | Perovskite supported cobalt efficient catalyst, preparation method and method for preparing methanol by partial oxidation of methane |
| CN114029061A (en) * | 2021-11-22 | 2022-02-11 | 北京化工大学 | Double-metal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by co-conversion of methane and carbon dioxide |
| CN114029061B (en) * | 2021-11-22 | 2023-10-20 | 北京化工大学 | Bimetal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion |
| CN113967476B (en) * | 2021-11-22 | 2024-03-26 | 北京化工大学 | Perovskite supported cobalt high-efficiency catalyst, preparation method and method for preparing methanol by partial oxidation of methane |
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