CN105664817B - A kind of optical fiber type photo catalysis reactor and by CO2It is converted to the method for methanol - Google Patents
A kind of optical fiber type photo catalysis reactor and by CO2It is converted to the method for methanol Download PDFInfo
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- CN105664817B CN105664817B CN201610144691.1A CN201610144691A CN105664817B CN 105664817 B CN105664817 B CN 105664817B CN 201610144691 A CN201610144691 A CN 201610144691A CN 105664817 B CN105664817 B CN 105664817B
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 79
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 59
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 45
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 43
- -1 rare earth modified titanium dioxide Chemical class 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 150000002895 organic esters Chemical class 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 5
- 239000003292 glue Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000003546 flue gas Substances 0.000 description 12
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- GZRQIDVFTAQASP-UHFFFAOYSA-N [Ce+3].[O-2].[Ti+4] Chemical compound [Ce+3].[O-2].[Ti+4] GZRQIDVFTAQASP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- URROIMSKGFJNKC-UHFFFAOYSA-N oxygen(2-) praseodymium(3+) titanium(4+) Chemical compound [O-2].[Ti+4].[Pr+3] URROIMSKGFJNKC-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The present invention relates to energy and environment field, a kind of optical fiber type photo catalysis reactor is disclosed and by CO2It is converted to the method for methanol.The reactor includes light source (1) and reaction container (2), material inlet (21) and material outlet (22) are provided on reaction container, being provided with load along its length in reaction container has the optical fiber (3) of rare earth modified titanium dioxide, the both ends of reaction container are both provided with sealing plate (5), and quartz glass plate (6) is at least provided on the sealing plate of one end, light source is arranged on the outside of at least one end of the reaction container equipped with quartz glass plate, for light beam to be injected by quartz glass plate in reaction container, wherein, the optical fiber (3) that loading has rare earth modified titanium dioxide includes optical fiber and the titanium dioxide layer doped with rare earth for being coated on fiber outer surface.Using the reactor by CO2Methanol is converted to, methanol yield is high, light utilization efficiency is high, specific surface area of catalyst is big and easily recycling.
Description
Technical field
The present invention relates to energy and environment fields, and in particular, to a kind of optical fiber type photo catalysis reactor and by CO2Conversion
Into the method for methanol.
Background technology
A large amount of greenhouse gases such as CO2、CH4Deng discharge caused by greenhouse effects become global concern hot spot.In recent years,
CO in air caused by human production activity2Concentration has accelerated influence of the greenhouse effects to global climate, how to have
Effect ground control CO2Discharge has become the task of top priority of various countries.Since coal is the most important primary energy in China, China CO2Row
It puts and mostlys come from fire coal, among these again based on coal-burning power plant, therefore, find a kind of effectively control power plant CO2The skill of discharge
Art is extremely urgent.
At present, coal-fired CO2Emission control technique is broadly divided into three categories：One kind is combustion post-control technology, including chemistry side
Method, physical method etc.；One kind is control technology, mainly Coal Gasification Technology before combustion；One kind is oxygen-enriched combustion technology.Various CO2
Control method there are the problem of have：High energy consumption, CO of high cost, recycling2Utilization rate is low.
Using the method for photo catalytic reduction by the high concentration CO in oxygen-enriched combusting flue gas2It is a kind of to be converted into the fuel such as methanol
It has much the emission reduction of potentiality simultaneously while utilizes CO2Effective way.It (is usually the TiO of Detitanium-ore-type using semi-conducting material2)
It, will be in vitalizing semiconductor when illumination of the energy higher than semiconductor energy gap is mapped to catalyst surface as catalyst
Electronics transits to conduction band from valence band, and being formed has very strongly active electron hole pair so that CO2Reduction reaction carried out.
Low energy consumption for this method, at low cost, pollution-free, is reducing CO2CO is also achieved while discharge2Recycling.
Wherein, photo catalysis reactor is to photo catalytic reduction CO2Efficiency and methanol yield have a major impact, but existing light
Reactor, such as suspension reactor, there are catalyst light utilization efficiency is low, specific surface area is small, is difficult to for conventional fixed bed reactors
The shortcomings of recycling, is unfavorable for the progress of light-catalyzed reaction.
Invention content
The purpose of the invention is to overcome drawbacks described above of the prior art, a kind of optical fiber type photo catalysis reactor is provided
With a kind of by CO2It is converted to the method for methanol.
To achieve these goals, in a first aspect, the present invention provides a kind of optical fiber type photo catalysis reactor, the optical fiber type
Photo catalysis reactor includes light source and reaction container, material inlet and material outlet is provided on the reaction container, in reaction container
Being provided with load along its length has the optical fiber of rare earth modified titanium dioxide, and the both ends of the reaction container are both provided with sealing
Plate, and quartz glass plate is at least provided on the sealing plate of one end, the light source is arranged on the reaction container equipped with quartz glass plate
At least one end outside, for by light beam by the quartz glass plate inject reaction container in, wherein, the load has rare earth
The optical fiber of modified titanium dioxide includes optical fiber and is coated on the titanium dioxide layer doped with rare earth of fiber outer surface.
Second aspect, the present invention provides a kind of by CO2The method of methanol is converted to, the method includes：CO will be contained2
Material supply into optical fiber type photo catalysis reactor of the present invention, carry out photo catalytic reduction reaction with by CO2It is converted to
Methanol.
The optical fiber type photo catalysis reactor of the present invention can improve methanol yield, be internally provided with supported rare earth for one kind
Modified nano-TiO2The compact type optical fiber type photo catalysis reactor of the optical fiber of layer, for CO will to be contained2Material (as rich
Oxygen flue gas) in CO2Methanol is converted to, methanol yield is high, and ((i.e. every gram is urged methanol yield of the invention in 200 μm of ol/h/g
200 μm of ol methanol are prepared in agent per hour) more than, up to 500 μm of ol/h/g, and methanol yield one in existing method
As be less than 100 μm of ol/h/g), light utilization efficiency is high, specific surface area of catalyst is big, easily recycling, low energy consumption, at low cost, pollution-free,
Reducing CO2CO is also achieved while discharge2Recycling.Specifically, in the present invention, (1) is born in fiber outer surface
Carry rare earth modified nano-TiO2Layer so that catalyst is in CO2Converting in the photo catalytic reduction reaction of methanol has higher catalysis
Activity.(2) catalyst is directly loaded in optical fiber surface, avoids and Jie is reacted present in traditional fixed photo catalysis reactor
The absorption and scattering of confrontation light, light utilization efficiency greatly improve；The surface area of catalyst also greatly improves, and enhances the place of reactor
Reason ability.(3) according to a preferred embodiment of the present invention, it is capable of providing stronger, more equal using double light sources in the present invention
Even lateral emitting intensity.(4) according to a preferred embodiment of the present invention, the inner wall of reactor is provided in the present invention
Aluminium foil reflective layer, improves light utilization efficiency；The outside of reactor is coated with heating tape, is received convenient for control temperature of reactor and product
Collection.(5) according to a preferred embodiment of the present invention, the present invention fixes optical fiber using fiber fixed frame, can make optical fiber
It is equably arranged in reactor, but also optical fiber dismounting is more flexible, conveniently；In addition, fiber fixed frame also is able to promote CO2
The rare earth modified titanium dioxide of air-flow and fiber outer surface comes into full contact with, and improves mass transfer effect and reaction rate.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the structure diagram of optical fiber type photo catalysis reactor in the embodiment of the present invention 1.
Fig. 2 is the vertical view of the fiber fixed frame in the embodiment of the present invention 1.
Reference sign
1 is light source；2 be reaction container；21 be material inlet；22 be material outlet；3 be that load has rare earth modified titanium dioxide
The optical fiber of titanium；4 be fiber fixed frame；41 be round frame body；42 be partition board；43 be fiber-optic fixing-hole；5 be sealing plate；6 be stone
English sheet glass.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing 1-2.It should be understood that this place
The specific embodiment of description is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, the present invention provides a kind of optical fiber type photo catalysis reactor, as shown in Figure 1, the optical fiber type photocatalysis
Reactor includes light source 1 and reaction container 2, material inlet 21 and material outlet 22 is provided on the reaction container 2, in reaction container 2
In be provided with load along its length and have the optical fiber 3 of rare earth modified titanium dioxide, the both ends of the reaction container 2 are both provided with close
Sealing plate 5, and quartz glass plate 6 is at least provided on the sealing plate 5 of one end, the light source 1 is arranged on equipped with quartz glass plate 6
The outside of at least one end of reaction container 2, for light beam to be injected by the quartz glass plate 6 in reaction container 2, wherein, it is described
The optical fiber 3 that load has rare earth modified titanium dioxide includes optical fiber and is coated on the titanium dioxide doped with rare earth of fiber outer surface
Titanium layer.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, sealing plate 5 and quartz glass plate 6 are circle
Shape, and the diameter of quartz glass plate 6 is less than the diameter of sealing plate 5.Wherein, for the specific big of sealing plate 5 and quartz glass plate 6
Small, those skilled in the art can be adjusted according to actual conditions, this is well known to those skilled in the art, no longer superfluous herein
It states.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, it is all provided on the sealing plate 5 at 2 both ends of reaction container
Quartz glass plate 6 is equipped with, and the number of light source 1 is 2, is separately positioned on the outside at the both ends of reaction container 2.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, sealing plate 5 is stainless steel plate.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, light source 1 is artificial light sources and/or natural light
Source.According to actual conditions, light source can be replaced between artificial light sources and lamp, and artificial light sources is not limited particularly
It is fixed, can different light sources be selected according to the type of catalyst, including xenon lamp, mercury lamp etc..
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, light source 1 is injected light beam by collector lens anti-
It answers in bucket 2.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, fiber fixed frame 4, institute are provided in reaction container 2
It states fiber fixed frame 4 and includes the two round frame bodies 41 of round frame body 41 and connection for being separately positioned on 2 both ends of reaction container
Partition board 42 is provided with fiber-optic fixing-hole 43 (as shown in Figure 2), for optical fiber 3 to be fixed on the round frame body 41.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, the diameter of round frame body 41 is not more than quartzy glass
The diameter of glass piece 6.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, it is reflective that the inner wall of reaction container 2 is provided with aluminium foil
Layer.
In the optical fiber type photo catalysis reactor of the present invention, under preferable case, the outside of reaction container 2 is provided with heating tape.
In the optical fiber type photo catalysis reactor of the present invention, it will be understood by those skilled in the art that load has rare earth to change
Property the optical fiber 3 of titanium dioxide include optical fiber and be coated on the titanium dioxide layer doped with rare earth of fiber outer surface, wherein, bear
It is loaded with the light that the optical fiber that the optical fiber 3 of rare earth modified titanium dioxide includes is the uncoated titanium dioxide layer doped with rare earth
It is fine.
Second aspect, the present invention provides a kind of by CO2The method of methanol is converted to, the method includes：CO will be contained2
Material supply into optical fiber type photo catalysis reactor of the present invention, carry out photo catalytic reduction reaction with by CO2It is converted to
Methanol.
In the case of process of the present invention it is preferred, the condition of photo catalytic reduction reaction includes：Temperature is 15-180 DEG C, light
It is 10-25mW/cm according to intensity2, contain CO2Material flow for 5-20ml/min, it is further preferred that containing CO2Object
In material, CO2Content be 85-90 volumes %, H2The content of O is 5-12 volumes %.Wherein, containing CO2Material in, in addition to
CO2And H2Outside O, remaining component is mainly oxygen and nitrogen.
In the method for the present invention, contain CO2Material can be contain water and high concentration CO2Various sources contain CO2
Material, the oxygen-enriched flue gas of Tathagata spontaneous combustion coal-fired plant.
In the case of process of the present invention it is preferred, this method further include be prepared by the following method load have it is rare earth modified
Titanium dioxide optical fiber, the method for optical fiber that preparation load has rare earth modified titanium dioxide includes：Remove optical fiber surface
Organic coating layer, the optical fiber for eliminating organic coating layer is totally immersed into the TiO 2 sol doped with rare earth, stand,
It then takes out optical fiber and carries out film process, drying process and calcination processing successively.
In the method for the present invention, for the method for organic coating layer that removes optical fiber surface, there is no particular limitation, can be with
For various methods commonly used in the art, such as the organic coating layer of optical fiber surface can be removed by way of calcination.
In the method for the present invention, in order to improve load effect of the rare earth modified titanium dioxide in fiber outer surface, preferably
In the case of, the time of standing is 20-40min.
In the method for the present invention, in order to improve load effect of the rare earth modified titanium dioxide in fiber outer surface, preferably
In the case of, the method for taking out optical fiber includes：Optical fiber is kept into plumbness in the TiO 2 sol doped with rare earth, with
The speed of 20-40mm/min is taken out from the TiO 2 sol doped with rare earth.
In the case of process of the present invention it is preferred, the condition of film process includes：Temperature is 15-35 DEG C, time 8-
10h。
In the case of process of the present invention it is preferred, the condition of drying process includes：Temperature is 60-120 DEG C, time 6-
8h。
In the case of process of the present invention it is preferred, the condition of calcination processing includes：Temperature is 400-500 DEG C, and the time is
1-3h。
Further, process of the present invention it is preferred in the case of, this method, which further includes, passes through method comprising the following steps
Prepare the TiO 2 sol doped with rare earth：
(1) by volume 1：3-5 mixes metatitanic acid organic ester with alcohol, obtains the alcoholic solution of metatitanic acid organic ester；
(2) by volume 1：2-3：5-8 mixes deionized water, acid and alcohol, obtains mixed liquor；
(3) rare-earth salts is added in into the mixed liquor that step (2) obtains and is mixed；
(4) under stiring, the product that step (3) obtains is added dropwise to the alcoholic solution of metatitanic acid organic ester that step (1) obtains
In, wherein, the volume ratio of product that alcoholic solution and the step (3) of the metatitanic acid organic ester that step (1) obtains obtain is 2.5-4:1,
And respectively in terms of titanium elements and rare earth element, metatitanic acid organic ester and step in the alcoholic solution of metatitanic acid organic ester that step (1) obtains
Suddenly the molar ratio of the rare-earth salts in the product that (3) obtain is 1：0.003-0.05.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (1), titanium
Sour organic ester is at least one of tetra-n-butyl titanate, tetraisopropyl titanate and tetraethyl titanate, further preferably metatitanic acid
Four N-butyls.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (1), institute
Alcohol is stated as at least one of absolute ethyl alcohol, the tert-butyl alcohol and isopropanol, further preferably absolute ethyl alcohol.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (2), institute
Acid is stated as glacial acetic acid (i.e. glacial acetic acid) and/or the hydrochloric acid solution of 36-38 weight %, further preferably glacial acetic acid.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (2), institute
Alcohol is stated as at least one of absolute ethyl alcohol, the tert-butyl alcohol and isopropanol, further preferably absolute ethyl alcohol.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (3), institute
Rare-earth salts rare earth elements are stated as at least one of cerium, praseodymium, lanthanum, samarium and holmium, further preferably cerium and/or praseodymium；It is described dilute
Earth salt is nitrate, acetate or the chloride of rare earth element.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, under preferable case, in step (4), institute
The speed for stating dropwise addition is 1.2-1.8ml/min.
In the method for the present invention, when preparing the TiO 2 sol doped with rare earth, step (4) is i.e. available doped with dilute
The TiO 2 sol of soil.In order to regulate and control the viscosity of colloidal sol, under preferable case, this method further includes：The production obtained to step (4)
Polyethylene glycol is added in object, is stirred.It is further preferred that on the basis of the product that 100ml steps (4) obtain, poly- second two
The addition of alcohol is 1-3g.
Embodiment
It below will the present invention will be described in detail, but is not intended to limit the present invention by attached drawing 1-2 and embodiment.With
In lower embodiment, unless otherwise instructed, each reagent is commercially available, and each method is various methods commonly used in the art.
Oxygen-enriched flue gas is the oxygen-enriched flue gas from coal-burning power plant, on the basis of oxygen-enriched flue gas, forms and is：CO2Content be
88 volume %, H2The content of O is 6 volume %, remaining component is mainly oxygen and nitrogen, and content is respectively 4 volume %, 2 bodies
Product % (remaining ingredient content is minimum, can be neglected).
Embodiment 1-1
The present embodiment is used for method of the preparation doped with the TiO 2 sol of rare earth for illustrating the present invention.
(1) by volume 1：4 mix tetra-n-butyl titanate with absolute ethyl alcohol, obtain the ethyl alcohol of tetra-n-butyl titanate
Solution；
(2) by volume 1：2.5：6 mix deionized water, glacial acetic acid and absolute ethyl alcohol, obtain mixed liquor；
(3) cerous nitrate is added in into the mixed liquor that step (2) obtains and is mixed；
(4) under stiring, product step (3) obtained is added dropwise to the titanium that step (1) obtains with the speed of 1.4ml/min
In the ethanol solution of sour four N-butyls, wherein, ethanol solution and the step (3) of the tetra-n-butyl titanate that step (1) obtains obtain
Product volume ratio be 3:1, and respectively in terms of titanium elements and rare-earth element cerium, the tetra-n-butyl titanate that step (1) obtains
The molar ratio of cerous nitrate in the product that tetra-n-butyl titanate in ethanol solution is obtained with step (3) is 1：0.02；
(5) polyethylene glycol is added in, and be stirred into the product that step (4) obtains, obtains two doped with cerium
Titanium oxide sol, wherein, on the basis of the product obtained by 100ml steps (4), the addition of polyethylene glycol is 2g.
Embodiment 1-2
The present embodiment is used for method of the preparation doped with the TiO 2 sol of rare earth for illustrating the present invention.
(1) by volume 1：3 mix tetraisopropyl titanate with the tert-butyl alcohol, obtain the tert-butyl alcohol of tetraisopropyl titanate
Solution；
(2) by volume 1：2：5 mix deionized water, the hydrochloric acid solution of 37 weight % and the tert-butyl alcohol, are mixed
Close liquid；
(3) praseodymium chloride is added in into the mixed liquor that step (2) obtains and is mixed；
(4) under stiring, product step (3) obtained is added dropwise to the titanium that step (1) obtains with the speed of 1.8ml/min
In the t-butanol solution of sour tetra-isopropyl, wherein, t-butanol solution and the step (3) of the tetraisopropyl titanate that step (1) obtains
The volume ratio of obtained product is 4:1, and respectively in terms of titanium elements and Rare Earth Elements of Praseodymium, four isopropyl of metatitanic acid that step (1) obtains
The molar ratio of praseodymium chloride in the product that tetraisopropyl titanate in the t-butanol solution of ester is obtained with step (3) is 1：0.05；
(5) polyethylene glycol is added in, and be stirred into the product that step (4) obtains, obtains two doped with praseodymium
Titanium oxide sol, wherein, on the basis of the product obtained by 100ml steps (4), the addition of polyethylene glycol is 1g.
Embodiment 1-3
The present embodiment is used for method of the preparation doped with the TiO 2 sol of rare earth for illustrating the present invention.
(1) by volume 1：5 mix tetraethyl titanate with isopropanol, and the isopropanol for obtaining tetraethyl titanate is molten
Liquid；
(2) by volume 1：3：8 mix deionized water, glacial acetic acid and isopropanol, obtain mixed liquor；
(3) lanthanum acetate is added in into the mixed liquor that step (2) obtains and is mixed；
(4) under stiring, product step (3) obtained is added dropwise to the titanium that step (1) obtains with the speed of 1.2ml/min
In the aqueous isopropanol of sour tetra-ethyl ester, wherein, aqueous isopropanol and the step (3) of the tetraethyl titanate that step (1) obtains obtain
Product volume ratio be 2.5:1, and respectively in terms of titanium elements and rare-earth elements of lanthanum, the tetraethyl titanate that step (1) obtains
The molar ratio of lanthanum acetate in the product that tetraethyl titanate in aqueous isopropanol is obtained with step (3) is 1：0.003；
(5) polyethylene glycol is added in, and be stirred into the product that step (4) obtains, obtains two doped with Rare Earth Lanthanum
Titanium oxide sol, wherein, on the basis of the product obtained by 100ml steps (4), the addition of polyethylene glycol is 3g.
Embodiment 2-1
The present embodiment is used for the method for illustrating to prepare the optical fiber that load has rare earth modified titanium dioxide.
The organic coating layer of optical fiber surface is removed, the optical fiber for eliminating organic coating layer is totally immersed into embodiment 1-1 and is obtained
To the TiO 2 sol doped with rare earth in, stand 30min, then by optical fiber in the TiO 2 sol doped with rare earth
Middle holding plumbness, is taken out with the speed of 30mm/min from the TiO 2 sol doped with rare earth, by the optical fiber of taking-up
Film process, drying process and calcination processing are carried out successively, wherein, the condition of film process includes：Temperature is 25 DEG C, and the time is
9h；The condition of drying process includes：Temperature is 100 DEG C, time 7h；The condition of calcination processing includes：Temperature is 450 DEG C, when
Between for 2h, obtaining load has the optical fiber of rare earth modified titanium dioxide.
Embodiment 2-2
The present embodiment is used for the method for illustrating to prepare the optical fiber that load has rare earth modified titanium dioxide.
The organic coating layer of optical fiber surface is removed, the optical fiber for eliminating organic coating layer is totally immersed into embodiment 1-2 and is obtained
To the TiO 2 sol doped with rare earth in, stand 20min, then by optical fiber in the TiO 2 sol doped with rare earth
Middle holding plumbness, is taken out with the speed of 20mm/min from the TiO 2 sol doped with rare earth, by the optical fiber of taking-up
Film process, drying process and calcination processing are carried out successively, wherein, the condition of film process includes：Temperature is 35 DEG C, and the time is
8h；The condition of drying process includes：Temperature is 65 DEG C, time 8h；The condition of calcination processing includes：Temperature is 400 DEG C, when
Between for 3h, obtaining load has the optical fiber of rare earth modified titanium dioxide.
Embodiment 2-3
The present embodiment is used for the method for illustrating to prepare the optical fiber that load has rare earth modified titanium dioxide.
The organic coating layer of optical fiber surface is removed, the optical fiber for eliminating organic coating layer is totally immersed into embodiment 1-3 and is obtained
To the TiO 2 sol doped with rare earth in, stand 40min, then by optical fiber in the TiO 2 sol doped with rare earth
Middle holding plumbness, is taken out with the speed of 40mm/min from the TiO 2 sol doped with rare earth, by the optical fiber of taking-up
Film process, drying process and calcination processing are carried out successively, wherein, the condition of film process includes：Temperature is 15 DEG C, and the time is
10h；The condition of drying process includes：Temperature is 120 DEG C, time 6h；The condition of calcination processing includes：Temperature is 500 DEG C,
Time is 1h, and obtaining load has the optical fiber of rare earth modified titanium dioxide.
Embodiment 3-1
With reference to Fig. 1-2, the present embodiment is used for the optical fiber type photo catalysis reactor for illustrating the present invention.
As illustrated in fig. 1 and 2, which includes light source 1 and reaction container 2, is set on the reaction container 2
There are material inlet 21 and material outlet 22, being provided with the load that embodiment 2-1 is prepared along its length in reaction container 2 has
The optical fiber 3 of rare earth modified titanium dioxide, the both ends of the reaction container 2 are both provided with sealing plate 5, and on the sealing plate 5 at both ends
Quartz glass plate 6 is both provided with, the number of the light source 1 is 2, is respectively arranged at the outside at the both ends of reaction container 2, for inciting somebody to action
Light beam is by collector lens and passes through in the injection reaction container 2 of quartz glass plate 6, wherein, load has rare earth modified titanium dioxide
Optical fiber 3 include optical fiber and be coated on the titanium dioxide layer doped with rare earth of fiber outer surface.
Wherein, the length of reaction container 2 is 15cm, and the diameter (internal diameter) at both ends is 6cm, sealing plate 5 and quartz glass plate 6
It is circle, and a diameter of 5cm of quartz glass plate 6, a diameter of 10cm of sealing plate 5, sealing plate 5 is stainless steel plate, light source 1
For mercury lamp.
Wherein, fiber fixed frame 4 is provided in reaction container 2, the fiber fixed frame 4 includes being separately positioned on reaction container 2
The partition board 42 of the round frame body 41 at both ends and the round frame body 41 of connection two, optical fiber is provided on the round frame body 41
Mounting hole 43, for optical fiber 3 to be fixed.A diameter of 5.5cm of round frame body 41.
Wherein, the inner wall of reaction container 2 is provided with aluminium foil reflective layer.
Wherein, the outside of reaction container 2 is provided with heating tape.
Embodiment 3-2
According to the optical fiber type photo catalysis reactor described in embodiment 3-1, the difference is that, load has rare earth modified titanium dioxide
The optical fiber 3 of titanium has the optical fiber of rare earth modified titanium dioxide for the embodiment 2-2 loads being prepared.
Embodiment 3-3
According to the optical fiber type photo catalysis reactor described in embodiment 3-1, the difference is that, load has rare earth modified titanium dioxide
The optical fiber 3 of titanium has the optical fiber of rare earth modified titanium dioxide for the embodiment 2-3 loads being prepared.
Embodiment 4-1
The present embodiment be used to illustrating the present invention by CO2It is converted to the method for methanol.
Oxygen-enriched flue gas is supplied by material inlet 21 into the optical fiber type photo catalysis reactor described in embodiment 3-1, into
The reaction of row photo catalytic reduction is with by CO2Methanol is converted to, wherein, the condition of photo catalytic reduction reaction includes：Temperature is 120 DEG C,
Intensity of illumination is 20mW/cm2, the flow of oxygen-enriched flue gas is 12ml/min.
After being catalyzed 10h, the object collected at the material outlet 22 of optical fiber type photo catalysis reactor is measured using gas chromatography
The composition and its content of material, are computed, and methanol yield is 488.7 μm of ol/h/g.
Embodiment 4-2
The present embodiment is used to illustrate CO2It is converted to the method for methanol.
Oxygen-enriched flue gas is supplied by material inlet 21 into the optical fiber type photo catalysis reactor described in embodiment 3-2, into
The reaction of row photo catalytic reduction is with by CO2Methanol is converted to, wherein, the condition of photo catalytic reduction reaction includes：Temperature is 30 DEG C, light
It is 25mW/cm according to intensity2, the flow of oxygen-enriched flue gas is 7ml/min.
After being catalyzed 10h, the object collected at the material outlet 22 of optical fiber type photo catalysis reactor is measured using gas chromatography
The composition and its content of material, are computed, and methanol yield is 420.8 μm of ol/h/g.
Embodiment 4-3
The present embodiment is used to illustrate CO2It is converted to the method for methanol.
Oxygen-enriched flue gas is supplied by material inlet 21 into the optical fiber type photo catalysis reactor described in embodiment 3-3, into
The reaction of row photo catalytic reduction is with by CO2Methanol is converted to, wherein, the condition of photo catalytic reduction reaction includes：Temperature is 175 DEG C,
Intensity of illumination is 12mW/cm2, the flow of oxygen-enriched flue gas is 18ml/min.
After being catalyzed 10h, the object collected at the material outlet 22 of optical fiber type photo catalysis reactor is measured using gas chromatography
The composition and its content of material, are computed, and methanol yield is 456.4 μm of ol/h/g.
The optical fiber type photo catalysis reactor of the present invention can improve methanol yield, be internally provided with supported rare earth for one kind
Modified nano-TiO2The compact type optical fiber type photo catalysis reactor of the optical fiber of layer, using it by CO2When converting methanol, first
Alcohol yield is high, light utilization efficiency is high, specific surface area of catalyst is big, easily recycle, low energy consumption, at low cost, pollution-free, is reducing CO2Row
CO is also achieved while putting2Recycling.
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, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme 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, 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.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of optical fiber type photo catalysis reactor, which is characterized in that the optical fiber type photo catalysis reactor includes light source (1) and reaction
Bucket (2) is provided with material inlet (21) and material outlet (22) on the reaction container (2), in reaction container (2) along its length
Being provided with load has the optical fiber (3) of rare earth modified titanium dioxide, and the both ends of the reaction container (2) are both provided with sealing plate (5),
And quartz glass plate (6) is at least provided on the sealing plate (5) of one end, the light source (1) is arranged on equipped with quartz glass plate (6)
Reaction container (2) at least one end outside, for light beam to be injected by the quartz glass plate (6) in reaction container (2),
In, it is described load have the optical fiber (3) of rare earth modified titanium dioxide including optical fiber and be coated on fiber outer surface doped with dilute
The titanium dioxide layer of soil；
Wherein, the optical fiber for having rare earth modified titanium dioxide that loads is prepared by method comprising the following steps：It goes
Except the organic coating layer of optical fiber surface, it is molten that the optical fiber for eliminating organic coating layer is totally immersed into titanium dioxide doped with rare earth
It in glue, stands, then take out optical fiber and carries out film process, drying process and calcination processing successively；
Wherein, the TiO 2 sol doped with rare earth is prepared by method comprising the following steps：
(1) by volume 1：3-5 mixes metatitanic acid organic ester with alcohol, obtains the alcoholic solution of metatitanic acid organic ester；
(2) by volume 1：2-3：5-8 mixes deionized water, acid and alcohol, obtains mixed liquor；
(3) rare-earth salts is added in into the mixed liquor that step (2) obtains and is mixed；The rare-earth salts rare earth elements are cerium
And/or praseodymium；
(4) under stiring, the product that step (3) obtains is added dropwise in the alcoholic solution of metatitanic acid organic ester that step (1) obtains,
In, the volume ratio of product that alcoholic solution and the step (3) of the metatitanic acid organic ester that step (1) obtains obtain is 2.5-4:1, and respectively
In terms of titanium elements and rare earth element, the metatitanic acid organic ester in the alcoholic solution of metatitanic acid organic ester that step (1) obtains is obtained with step (3)
To product in rare-earth salts molar ratio be 1：0.003-0.05, the speed of the dropwise addition is 1.2-1.8ml/min.
2. optical fiber type photo catalysis reactor according to claim 1, wherein, the sealing plate at the reaction container (2) both ends
(5) quartz glass plate (6) is both provided on, and the number of the light source (1) is 2, is separately positioned on the both ends of reaction container (2)
Outside.
3. optical fiber type photo catalysis reactor according to claim 1, wherein, it is provided with optical fiber in the reaction container (2) and consolidates
Determine frame (4), the fiber fixed frame (4) is including being separately positioned on the round frame body (41) at reaction container (2) both ends and connection two
The partition board (42) of the circle frame body (41) is provided with fiber-optic fixing-hole (43) on the round frame body (41), for by light
Fine (3) are fixed.
4. optical fiber type photo catalysis reactor according to claim 3, wherein, the diameter of the circle frame body (41) is not more than
The diameter of the quartz glass plate (6).
5. optical fiber type photo catalysis reactor according to claim 1, wherein, the inner wall of the reaction container (2) is provided with aluminium
Foil reflective layer.
6. optical fiber type photo catalysis reactor according to claim 1, wherein, the outside of the reaction container (2), which is provided with, to be added
The torrid zone.
It is 7. a kind of by CO2It is converted to the method for methanol, which is characterized in that the method includes：CO will be contained2Material supply to
In optical fiber type photo catalysis reactor in claim 1-6 described in any one, photo catalytic reduction reaction is carried out with by CO2Conversion
Into methanol.
8. according to the method described in claim 7, wherein, the condition of the photo catalytic reduction reaction includes：Temperature is 15-180
DEG C, intensity of illumination 10-25mW/cm2, it is described to contain CO2Material flow be 5-20ml/min.
9. according to the method described in claim 8, wherein, contain CO described2Material in, CO2Content be 85-90 bodies
Product %, H2The content of O is 5-12 volumes %.
10. according to the method described in any one in claim 7-9, wherein, preparing the load has rare earth modified dioxy
In the method for changing the optical fiber of titanium, the time of the standing is 20-40min.
11. according to the method described in any one in claim 7-9, wherein, preparing the load has rare earth modified dioxy
In the method for changing the optical fiber of titanium, the method for taking out optical fiber includes：By optical fiber in the TiO 2 sol doped with rare earth
Plumbness is kept, is taken out from the TiO 2 sol doped with rare earth with the speed of 20-40mm/min.
12. according to the method described in any one in claim 7-9, wherein, preparing the load has rare earth modified dioxy
In the method for changing the optical fiber of titanium, the condition of the film process includes：Temperature is 15-35 DEG C, time 8-10h.
13. according to the method described in any one in claim 7-9, wherein, preparing the load has rare earth modified dioxy
In the method for changing the optical fiber of titanium, the condition of the drying process includes：Temperature is 60-120 DEG C, time 6-8h.
14. according to the method described in any one in claim 7-9, wherein, preparing the load has rare earth modified dioxy
In the method for changing the optical fiber of titanium, the condition of the calcination processing includes：Temperature is 400-500 DEG C, time 1-3h.
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| CN108187729B (en) * | 2018-01-15 | 2021-03-12 | 中国科学院上海高等研究院 | Composite catalyst film and preparation method and application thereof |
| CN111853714B (en) * | 2020-07-07 | 2022-02-25 | 北京科技大学 | Photocatalytic optical fiber lamp and manufacturing method thereof |
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