CN105836703A - Method for preparing synthetic gas through photo-thermal chemical circulation decomposition of carbon dioxide - Google Patents
Method for preparing synthetic gas through photo-thermal chemical circulation decomposition of carbon dioxide Download PDFInfo
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- CN105836703A CN105836703A CN201610157304.8A CN201610157304A CN105836703A CN 105836703 A CN105836703 A CN 105836703A CN 201610157304 A CN201610157304 A CN 201610157304A CN 105836703 A CN105836703 A CN 105836703A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to the synthetic gas preparation technology, aims at providing a method for preparing synthetic gas through photo-thermal chemical circulation decomposition of carbon dioxide. The method includes the following steps: carrying out uniform ultrasonic vibration of a titanium dioxide nano powder and deionized water, pouring the obtained mixed suspension into a quartz glass ware, and drying; placing a prepared titanium dioxide thin film in a sealed cavity body, carrying out a reaction at normal temperature and pressure and by light source irradiation, then introducing CO2 with water vapor, heating the cavity body to 300 to 600 DEG C, carrying out a reaction, and finally, obtaining the synthetic gas including hydrogen, carbon monoxide and methane. Photochemistry and thermochemistry are combined together, so the temperature required for the first step of thermochemical circulation is greatly reduced, and the circulation conditions are improved; operations required to be carried out are simpler and more convenient, the highest heat source temperature is relatively low, and the heat sources of solar energy, nuclear energy and other forms are adopted. The method can produce methane having more use value, prepares CO and H2 and the like at the same time, and has the potential for synthesis of a variety of chemical raw materials.
Description
Technical field
The invention belongs to synthesis gas technology of preparing, be about thermochemical cycle decomposition carbon dioxide and water system regions, especially
Relate to a kind of light thermochemical cycle decomposition carbon dioxide and water prepares synthesis gas (including hydrogen, carbon monoxide, methane)
Method.
Background technology
Synthesis gas is with H2Being the key component a kind of unstripped gas for chemosynthesis with CO, it can be as intermediate
Prepare various high-quality liquid fuel and chemicals for petroleum chemical industry or by F-T synthesis, as hydrogen, methanol and
Dimethyl ether etc..The most most synthesis gas preparation technologies are still employing coal gasification or the mode of natural gas gasifying, along with change
The most exhausted and the most serious environmental problem of the stone energy, the development synthesis gas production technology with Renewable resource as raw material
To alleviating, world energy sources is short and environmental pollution has great importance.
Based on metal-oxide, redox Thermochemical Decomposition carbon dioxide and water circulation are generally made up of two steps: first
Step is that metal-oxide at high temperature decomposes generation oxygen and metal simple-substance or the metal-oxide of relatively low quantivalence；Second
Step is that the metal-oxide of metal simple-substance or relatively low quantivalence occurs carbon dioxide and water decomposition reaction at a lower temperature
Carry out producing synthesis gas.Whole process can be expressed as follows:
2/xMO2→2/x MO2-x+O2 (1)
2/xMO2-x+H2O+CO2→1/xMO2+CO+H2 (2)
First step decomposition reaction is the process of a high temperature endothermic, it usually needs the highest reaction temperature (> 1600 DEG C), therefore
Salar light-gathering high temperature heat source must be used to drive reaction to carry out.Second step carbon dioxide and water decomposition reaction are heat releases
Process, its reaction temperature is relatively low.It is readily seen by formula (1) and formula (2): the overall reaction of whole process is exactly
H2O+CO2→H2+CO+O2。
It can be seen that two-step thermochemical cycles key has a problem in that first step decomposition reaction temperature is too high.Therefore, as
What uses new method to improve reaction condition, makes decomposition temperature reduce particularly significant.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, it is provided that a kind of light thermochemical cycle decomposition
Carbon dioxide prepares the method for synthesis gas.The method light based on titanium dioxide metal-oxide thermochemical cycle decomposition dioxy
Change carbon and water prepares synthesis gas (including hydrogen, carbon monoxide, methane).
For solving above-mentioned technical problem, the solution of the present invention is:
A kind of method providing smooth thermochemical cycle decomposition carbon dioxide to prepare synthesis gas, comprises the steps:
(1) titanic oxide nano powder that particle diameter is less than 100nm is placed in test tube, and adds 2/3 test tube volume
Deionized water, making titanic oxide nano powder is 1:100 with the mass ratio of deionized water；Put in ultrasonic wave concussion instrument and shake
Swing uniformly, obtain mixing suspension；
(2) pour step (1) gained mixing suspension into quartz glass ware, be placed at 110 DEG C drying 3 hours,
Obtain homogeneous precipitation titanium deoxid film bottom silica ware；
(3) take off in step (2) prepare titanium deoxid film, be placed in airtight cavity, normal temperature and pressure (0～50 DEG C,
Use light source to irradiate reaction 0.5～2h under 0.1MPa), react as follows:
TiO2→TiO2-m+m/2O2, 0 < m < 2 (that is, m is to be less than any number between 2 more than 0)；
(4) in step (3), cavity is passed through the CO with steam2, cavity is heated to 300～600 DEG C, enters
The following reaction of row:
TiO2-x+xCO2→TiO2+xCO
TiO2-y+yH2O→TiO2+yH2
TiO2-z+z/2H2O+z/4CO2→TiO2+z/4CH4
Wherein, x+y+z=m；X, y, z are equal > 0 (that is, x, y, z three sum is m, and x, y, z is more than 0
Any number)；
Finally give the synthesis gas including hydrogen, carbon monoxide and methane.
In the present invention, the bottom surface within described quartz glass ware is plane, suspension elaborating at quartz glass ware
Thickness is 0.1～1mm.
In the present invention, the overall reaction of step (3) and step (4) is: 3H2O+2CO2→CO+H2+CH4+3O2。
Compared with prior art, the invention has the beneficial effects as follows:
1, photochemistry is joined together with heat chemistry, utilize nano titanium oxide metal-oxide normal temperature and pressure (0～50 DEG C,
Resolve into the feature of metal suboxide and oxygen under 0.1MPa) through illumination, greatly reduce thermochemical cycles
Temperature needed for one step, improves cycling condition；
2, the operation carried out needed for the method is simpler convenient, and all kinds of methods such as two-step thermochemical cycles is the highest
Heat source temperature the highest (> 1600 DEG C), typically use Salar light-gathering, and the high source temperature of this method is relatively low
(< 500 DEG C), the thermal source of other various ways such as solar energy, nuclear energy can be used；
3, the method is prepared synthesis gas and can be produced the methane of great value, and this is not have in thermochemical cycles
Product, and prepare CO and H simultaneously2Deng, there are the potentiality synthesizing multiple industrial chemicals.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail:
Embodiment 1
(1) weigh the particle diameter titania powder less than 100nm, be placed in test tube, and in test tube, add 2/3
The deionized water of test tube volume, wherein titanic oxide nano powder is 1:100 with the mass ratio of deionized water, and puts into super
In sound wave shock instrument, concussion is uniformly；
(2) pour gained mixing suspension in step (1) into quartz glass ware, be placed at 110 DEG C drying 3 little
Time, it is deposited in the titanium deoxid film bottom silica ware uniformly；
(3) the titanium dioxide burning that at normal temperatures and pressures (0～50 DEG C, 0.1MPa), will prepare in step (2)
Thing thin film is placed in airtight cavity, and uses light source to irradiate reaction 0.5h；
TiO2→TiO2-m+m/2O2, m < 2；
(4) it is passed through with water in the cavity equipped with the titanium dioxide metal-oxide film after illumination in step (3)
The CO of steam2, cavity is heated to 300 DEG C and reacts；
The chemical reaction that this step occurs is as follows:
TiO2-x+xCO2→TiO2+xCO
TiO2-y+yH2O→TiO2+yH2
TiO2-z+z/2H2O+z/4CO2→TiO2+z/4CH4
Wherein, x+y+z=m；x,y,z>0；
In the present invention, the overall reaction of step (3) and step (4) is: 3H2O+2CO2→CO+H2+CH4+3O2。
Embodiment 2
(1) weigh the particle diameter titania powder less than 100nm, be placed in test tube, and in test tube, add 2/3
The deionized water of test tube volume, wherein titanic oxide nano powder is 1:100 with the mass ratio of deionized water, and puts into super
In sound wave shock instrument, concussion is uniformly；
(2) pour gained mixing suspension in step (1) into quartz glass ware, be placed at 110 DEG C drying 3 little
Time, it is deposited in the titanium deoxid film bottom silica ware uniformly；
(3) the titanium dioxide burning that at normal temperatures and pressures (0～50 DEG C, 0.1MPa), will prepare in step (2)
Thing thin film is placed in airtight cavity, and uses light source to irradiate reaction 1h；
TiO2→TiO2-m+m/2O2, m < 2；
(4) it is passed through with water in the cavity equipped with the titanium dioxide metal-oxide film after illumination in step (3)
The CO of steam2, cavity is heated to 500 DEG C and reacts；
The chemical reaction that this step occurs is as follows:
TiO2-x+xCO2→TiO2+xCO
TiO2-y+yH2O→TiO2+yH2
TiO2-z+z/2H2O+z/4CO2→TiO2+z/4CH4
Wherein, x+y+z=m；x,y,z>0；
In the present invention, the overall reaction of step (3) and step (4) is: 3H2O+2CO2→CO+H2+CH4+3O2。
Embodiment 3
(1) weigh the particle diameter titania powder less than 100nm, be placed in test tube, and in test tube, add 2/3
The deionized water of test tube volume, wherein titanic oxide nano powder is 1:100 with the mass ratio of deionized water, and puts into super
In sound wave shock instrument, concussion is uniformly；
(2) pour gained mixing suspension in step (1) into quartz glass ware, be placed at 110 DEG C drying 3 little
Time, it is deposited in the titanium deoxid film bottom silica ware uniformly；
(3) the titanium dioxide burning that at normal temperatures and pressures (0～50 DEG C, 0.1MPa), will prepare in step (2)
Thing thin film is placed in airtight cavity, and uses light source to irradiate reaction 2h；
TiO2→TiO2-m+m/2O2, m < 2；
(4) it is passed through with water in the cavity equipped with the titanium dioxide metal-oxide film after illumination in step (3)
The CO of steam2, cavity is heated to 600 DEG C and reacts；
The chemical reaction that this step occurs is as follows:
TiO2-x+xCO2→TiO2+xCO
TiO2-y+yH2O→TiO2+yH2
TiO2-z+z/2H2O+z/4CO2→TiO2+z/4CH4
Wherein, x+y+z=m；x,y,z>0；
In the present invention, the overall reaction of step (3) and step (4) is: 3H2O+2CO2→CO+H2+CH4+3O2。
Finally, in addition it is also necessary to be only the specific embodiment of the present invention it is noted that listed above.Obviously, the present invention does not limits
In above example, it is also possible to there are many deformation.
The present invention can summarize with other the concrete form without prejudice to the spirit or central characteristics of the present invention.Therefore, no matter
From the point of view of which point, the embodiment above of the present invention all can only be considered the description of the invention and can not limit the present invention.
Claims indicate the scope of the present invention, and the scope of the present invention is not pointed out in above-mentioned explanation, therefore, with this
Any change in the suitable implication of claims of invention and scope, is all considered as being included in the model of claims
In enclosing.
Claims (2)
1. the method that a light thermochemical cycle decomposition carbon dioxide prepares synthesis gas, it is characterised in that include following step
Rapid:
(1) titanic oxide nano powder that particle diameter is less than 100nm is placed in test tube, and adds 2/3 test tube volume
Deionized water, making titanic oxide nano powder is 1:100 with the mass ratio of deionized water；Put in ultrasonic wave concussion instrument and shake
Swing uniformly, obtain mixing suspension；
(2) pour step (1) gained mixing suspension into quartz glass ware, be placed at 110 DEG C drying 3 hours,
Obtain homogeneous precipitation titanium deoxid film bottom silica ware；
(3) take off the titanium deoxid film prepared in step (2), be placed in airtight cavity, use at normal temperatures and pressures
Light source irradiates reaction 0.5～2h, reacts as follows:
TiO2→TiO2-m+m/2O2, 0 < m < 2；
(4) in step (3), cavity is passed through the CO with steam2, cavity is heated to 300～600 DEG C, enters
The following reaction of row:
TiO2-x+xCO2→TiO2+xCO
TiO2-y+yH2O→TiO2+yH2
TiO2-z+z/2H2O+z/4CO2→TiO2+z/4CH4
Wherein, x+y+z=m, and x, y, z are equal > 0；
Finally give the synthesis gas including hydrogen, carbon monoxide and methane.
Method the most according to claim 1, it is characterised in that the bottom surface within described quartz glass ware is in flat
Planar, suspension is 0.1～1mm at the thickness of elaborating of quartz glass ware.
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| CN201610157304.8A CN105836703B (en) | 2016-03-18 | 2016-03-18 | A kind of method that smooth thermochemical cycle decomposition carbon dioxide prepares synthesis gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793070A (en) * | 2018-07-11 | 2018-11-13 | 浙江大学 | Solar energy hierarchical sub-prime based on light-transmission type photo-thermal chemical cycle material utilizes system |
| CN108954871A (en) * | 2018-07-11 | 2018-12-07 | 浙江大学 | Solar energy hierarchical sub-prime based on light-transmission type photo-thermal chemical cycle material utilizes method |
| CN109114825A (en) * | 2018-07-11 | 2019-01-01 | 浙江大学 | Solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104477910A (en) * | 2014-11-26 | 2015-04-01 | 浙江大学 | Method for preparing carbon monoxide from carbon dioxide by photothermal chemical cyclic decomposition |
| CN105289565A (en) * | 2015-10-29 | 2016-02-03 | 福州大学 | TiO<2>@SiO<2> photocatalyst and application of same to photocatalytic reduction for CO<2> |
-
2016
- 2016-03-18 CN CN201610157304.8A patent/CN105836703B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104477910A (en) * | 2014-11-26 | 2015-04-01 | 浙江大学 | Method for preparing carbon monoxide from carbon dioxide by photothermal chemical cyclic decomposition |
| CN105289565A (en) * | 2015-10-29 | 2016-02-03 | 福州大学 | TiO<2>@SiO<2> photocatalyst and application of same to photocatalytic reduction for CO<2> |
Non-Patent Citations (1)
| Title |
|---|
| YANWEI ZHANG ET AL.: "A novel photo-thermochemical cycle for the dissociation of CO2 using solar energy", 《APPLIED ENERGY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793070A (en) * | 2018-07-11 | 2018-11-13 | 浙江大学 | Solar energy hierarchical sub-prime based on light-transmission type photo-thermal chemical cycle material utilizes system |
| CN108954871A (en) * | 2018-07-11 | 2018-12-07 | 浙江大学 | Solar energy hierarchical sub-prime based on light-transmission type photo-thermal chemical cycle material utilizes method |
| CN109114825A (en) * | 2018-07-11 | 2019-01-01 | 浙江大学 | Solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes method |
| CN109114825B (en) * | 2018-07-11 | 2020-10-30 | 浙江大学 | Solar energy grading and quality-grading utilization method based on heat collection type photo-thermal chemical circulation material |
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