CN106006828B - It is a kind of to promote photoreduction CO using sodium sulfite2And N2Method - Google Patents
It is a kind of to promote photoreduction CO using sodium sulfite2And N2Method Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 24
- 238000007540 photo-reduction reaction Methods 0.000 title description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title description 2
- 229910052708 sodium Inorganic materials 0.000 title description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 10
- 238000005950 photosensitized reaction Methods 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005945 translocation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Na is utilized the present invention relates to a kind of2SO3Photochemical systems are promoted to restore CO2And N2Method.This method are as follows: sodium sulfite is added in water, and is passed through CO2Or N2, control system pH value is 5.0~9.0, realizes CO by carrying out ultraviolet irradiation to system under the conditions of can make sodium sulfite that the ultraviolet irradiation of photosensitized reaction occur2And N2Reduction.It activates and hinders this method solve the inert molecule in traditional photochemical systems, overcome CO2" the bottleneck reaction " of reduction and fixed nitrogen process, and react whole process and carried out in water phase, without adding organic sacrifice agent.It is used for CO2Reduction and fixed nitrogen reaction have many advantages, such as efficient, highly selective, environmental-friendly and without secondary pollution.
Description
Technical field
The invention belongs to photochemistry fields, and in particular to a kind of CO2And N2Photochemical reduction method is suitable for the energy, environment
Using the exploitation of gas resource in equal fields.
Background technique
The burning of fossil fuel is still current most important energy supply means, but not turning off with the resource-type energy
It adopts, the energy and shortage of resources national conditions in China are increasingly severe.Meanwhile along with a large amount of CO in the use process of fossil-fueled2's
It discharges, CO in atmosphere2The raising of concentration causes the heat preservation effect of earth surface further obvious, results in going out for global warming phenomenon
It is existing.Therefore, while developing new alternate resources, greenhouse gases brought by solution resource consumption are exceeded, trade waste is dirty
The environmental problems such as dye are imperative.
It is well known that CO2And N2It is two kinds of gases that content is more in air, and carbon contained by both gases, nitrogen are first
Necessary basic element in element or industrial and agricultural production.Carbon compound is not only to constitute the basic of organism, or at present
Most important Energy supply material；And composition of the nitrogen in addition to participating in organism protein, hormone, adjust the new old generation of organism
It thanks, the also production with the chemicals such as chemical fertilizer, pesticide is closely related.Therefore, under mild conditions, CO is realized2And N2Molecule has
Effect utilizes most important for building a resource-conserving society.In recent years, researchers have developed a series of CO2And N2Reduction
Method, wherein homogeneous photoreduction gains great popularity since its is easy to operate and high conversion efficiency.But CO at this stage2With
N2Reduction reaction is still faced with many obstructions: (1) CO2And N2The physicochemical properties of molecule are relatively stable, needed for molecule activation
Structural rearrangement can be high, such as CO2The single electron activation barrier of reduction is up to -1.9V.Therefore, higher activation barrier becomes CO2
And N2" the reaction bottleneck " of reduction reaction.(2)CO2Or N2The generation of reduzate generally requires the participation of hydrogen atom or proton,
And traditional photochemical systems generally use organic sacrificial agent as hydrogen atom and proton donor, as triethylamine, triethanolamine and
Tricyclic amine etc..Organic sacrificial agent and the use of organic solvent not only increase the cost of reduction reaction, the discharge of reaction waste
Burden is increased to environmental improvement.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiency of conventional, prior art, provide a kind of using water as proton confession
Body promotes photoreduction CO using sodium sulfite2And N2New method.The method of the present invention is generated using sodium sulfite photodissociation
High energy aqueous electron and hydrogen atom, realize CO2And N2The direct activation of molecule overcomes the " bottleneck in traditional photochemical systems
Reaction ".Meanwhile this method has also abandoned traditional organic sacrificial agent, is successfully realized CO in economic, clean water environment2
To HCOOH and N2To NH4 +Efficient Conversion, have many advantages, such as that efficient, environmental-friendly, selectivity is high, without secondary pollution.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
It is a kind of to promote photochemical systems to restore CO using sodium sulfite2And N2Method, it is characterised in that: be added in water
Sodium sulfite, and it is passed through CO2Or N2, control system pH value is 5.0~9.0, can make sodium sulfite that the ultraviolet of photosensitized reaction occur
Ultraviolet irradiation is carried out to system under irradiation condition and realizes CO2And N2Reduction.
According to the above scheme, the concentration of the sodium sulfite is 25~100 mM/ls.
According to the above scheme, the system pH is preferably controlled to 6.5-7.5.The system pH passes through dilute sulfuric acid or sodium hydroxide
It adjusts.
According to the above scheme, the wavelength of the ultraviolet irradiation light source need to be less than 270nm.
According to the above scheme, being stirred before the ultraviolet irradiation to system is uniformly mixed it.
According to the above scheme, the CO2Reduzate is HCOOH；N2Reduzate is NH4 +。
According to the above scheme, the CO2Or N2Gas first passes through the drexel bottle for including secondary distilled water, then passes to Na2SO3
It is restored in solution system.Thus it can avoid carrying out with reaction, Na2SO3Solution evaporation rate is too fast.
This method utilizes Na2SO3As sensitiser absorption ultraviolet light, and generate high energy aqueous electron.Meanwhile Na2SO3It is logical
It crosses the proton that hydrolysis is captured in water and generates NaHSO3, NaHSO3Hydrogen atom can be quickly generated under the attack of aqueous electron.?
The reduction of inert molecule is realized under the synergistic effect of hydrogen atom and high energy aqueous electron.Such as in CO2In reduction experiment, aqueous electron
It can directly and CO2Molecule combines, by CO2Molecule effective activation is to CO2 ·-.Then, the hydrogen atom and CO in system2 ·-Spontaneous combination
HCOOH is generated, the HCOOH cumulative production of four hours of the system is about 26mg/L.In N2It is hydrogen atom first in reduction experiment
With N2In conjunction with completion N2Activation, then via a series of hydrogen atom addition reaction generate N2H4Molecule.Finally, N2H4Molecule is logical
It crosses subsequent electronics-proton translocation approach and is eventually converted into NH4 +, the NH of eight hours of the system4 +Cumulative production is 6.65mg/
L.In N2In reduction experiment, NaHSO3The generation of system hydrogen atom is not only contributed to, weaker proton compatibility also makes
NaHSO3As than H2O more excellent proton donor.Thus aqueous electron and NaHSO3It can be respectively as electron donor and matter
Sub- donor, is effectively facilitated N2Electronics-proton translocation approach generation in reduction experiment, to accelerate N2H4Molecule is to NH4 +Turn
Change.
The present invention has the advantages that
1、Na2SO3It is the common raw material of industry, preparation method is simply mature, and it is from a wealth of sources, and its light reaction conversion is eventually
Product is Na2SO4, not will cause secondary pollution.
2, reaction condition is mild, normal temperature and pressure can fast reaction, be not necessarily to complex appts, easy to operate, no risk, nothing
Professional need to be engaged to operate.
3, the proton donor reacted is water, environmentally friendly without the addition of organic sacrificial agent and organic solvent.
4, the present invention uses Na2SO3Make photosensitizer, not only can induce the generation that High energy water closes electronics, it is further to hydrolyze
Product NaHSO3Can also promotion system active hydrogen atom generation and subsequent proton transfer, to increase substantially CO2With
N2Reduction efficiency.System selectivity of product with higher, reduction effect are substantially better than common KI photoreduction
System.
Detailed description of the invention
Fig. 1 is the CO of the method for the present invention and KI photoreduction system2Reducing property comparison diagram；
Fig. 2 is the method for the present invention various concentration Na2SO3To the influence diagram of HCOOH yield；
Fig. 3 is influence diagram of the method for the present invention different pH condition to HCOOH yield；
Fig. 4 is the N of the method for the present invention and KI photoreduction system2Reducing property comparison diagram；
Fig. 5 is the method for the present invention different pH condition to NH4 +The influence diagram of yield；
Fig. 6 is the method for the present invention various concentration Na2SO3To NH4 +The influence diagram of yield；
Specific embodiment
Carry out the summary of the invention that the present invention will be described in detail below by specific implementation case, described specific embodiment is only used
To explain the present invention, it is not intended to limit the present invention.
Embodiment 1CO2It is restored to HCOOH
For CO2The reduction and utilization of molecule, with the high-purity CO of business2For reaction gas, HCOOH is target product.It selects
Na2SO3The CO of this method is measured under the irradiation of 254nm ultraviolet lamp for photosensitizer2Reducing property.Steps are as follows:
Take the Na of 50mmol/L2SO3Solution 50mL is continually fed into high-purity CO thereto2Gas, when ventilation, are 40 minutes a length of,
Gas flow rate is 30 ml/mins, and the pH value of system is made to tend to be neutral).It is uniformly mixed solution with magnetic stirrer, is turned
Speed is 400rpm.254nm ultraviolet irradiation (light source power 16W) investigates Na2SO3Photo catalytic reduction CO2Performance.Simultaneously to pass
System KI photoreduction system is control experiment, the result is shown in Figure 1.Shown in Fig. 1, when reacting 4h, the yield of HCOOH reaches
26mg/L is far longer than KI photochemical systems；The quantum yield of entire photochemical systems is 0.022mol/einstein, is KI
10 times of photochemical systems.
The different Na of embodiment 22SO3CO is restored under concentration2For HCOOH
It is respectively the Na of 25mmol/L, 50mmol/L, 75mmol/L, 100mmol/L with concentration2SO3Aqueous solution is that reaction is situated between
Matter is passed through CO thereto2To saturation, at this point, initial reaction solution ph is 7.0 or so.Then in the ultraviolet light irradiation of 254nm
Under, evaluate different Na2SO3Photochemistry CO of the concentration to the system2The influence of reducing property, is as a result shown in Fig. 3.As shown in Fig. 2,
Na2SO3When concentration is 75mmol/L, the CO of the system2Reducing property is best.Na2SO3When concentration is 50 mmol/L, Na2SO3's
The output ratio of investment and HCOOH are maximum.
Embodiment 3 restores CO under different ph values2For HCOOH
It is the Na of 50mmol/L with concentration2SO3Aqueous solution is reaction medium, is passed through CO thereto2To saturation, then respectively plus
The initial pH value for entering dilute sulfuric acid or sodium hydrate regulator solution is 5.0,7.0 and 9.0.Then it is commented under the ultraviolet light irradiation of 254nm
The photochemistry CO of the valence system2As a result reducing property is shown in Fig. 3.As shown in figure 3, the CO under neutrallty condition2Reducing property is best.
Embodiment 4N2It is restored to NH4 +
For N2The reduction and utilization of molecule, with business high-purity N2For gas source, NH4 +For target product.It selects
Na2SO3The fixed nitrogen performance of this method is measured under the irradiation of 254nm ultraviolet lamp for photosensitizer.
Take the Na of 100mmol/L2SO3Solution 250mL, is continually fed into high-purity N thereto2Gas.Then it is adjusted with dilute sulfuric acid
System pH makes the pH value of system tend to be neutral.254nm ultraviolet irradiation (light source power 16W) investigates Na2SO3Photocatalysis is also
Former N2Performance.It is uniformly mixed solution with magnetic stirrer, revolving speed 400rpm.Simultaneously with traditional KI photoreduction
System is control experiment group, as a result sees Fig. 4.Shown in Fig. 4, when reacting 8h, NH4 +Yield reached 6.65mg/L, photochemistry
The quantum yield of system be 0.245mol/einstein, be far longer than KI photoreduction system fixed nitrogen performance (λ=
254nm)。
Embodiment 5 restores N under different ph values2For NH4 +
Using concentration for 100mmol/L sodium sulfite aqueous solution as reaction medium, then each lead into N again2To saturation, so
It is respectively 5.0,7.0 and 9.0 that dilute sulfuric acid is added thereto afterwards and adjusts the initial pH of solution.It is evaluated under the ultraviolet light irradiation of 254nm
The photochemistry fixed nitrogen performance of the system, is as a result shown in Fig. 5.As shown in figure 5, the fixed nitrogen performance under neutrallty condition is best.
Embodiment 6N2It is restored to NH4 +
Using concentration for 50mmol/L sodium sulfite aqueous solution as reaction medium, be continually fed into high-purity N thereto2Gas.
Then dilute sulfuric acid regulation system pH value is used, the pH value of system is made to tend to be neutral.254nm ultraviolet irradiation (light source power is 16 W),
Investigate Na2SO3Photo catalytic reduction N2Performance, the results showed that reaction 8h when, NH4 +Yield reached 1.07 mg/L.As a result see
Fig. 6.
Claims (5)
1. a kind of promote photochemical systems to restore CO using sodium sulfite2And N2Method, it is characterised in that: be added in water sub-
Sodium sulphate, and it is passed through CO2Or N2, control system pH value is 5.0~9.0, in the ultraviolet photograph that can make sodium sulfite that photosensitized reaction occur
CO is realized by carrying out ultraviolet irradiation to system under the conditions of penetrating2And N2Reduction；The system pH control is 6.5-7.5；The purple
The wavelength of external exposure light source need to be less than 270 nm.
2. according to claim 1 promote photochemical systems to restore CO using sodium sulfite2And N2Method, feature exists
In: the concentration of the sodium sulfite is 25~100 mM/ls.
3. according to claim 1 promote photochemical systems to restore CO using sodium sulfite2And N2Method, feature exists
In: being stirred before the ultraviolet irradiation to system is uniformly mixed it.
4. according to claim 1 promote photochemical systems to restore CO using sodium sulfite2And N2Method, feature exists
In: the CO2Reduzate is HCOOH；N2Reduzate is NH4 +。
5. according to claim 1 promote photochemical systems to restore CO using sodium sulfite2And N2Method, feature exists
In: the CO2Or N2Gas first passes through the drexel bottle for including secondary distilled water, then passes to Na2SO3It is gone back in solution system
It is former.
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| CN201610351261.7A CN106006828B (en) | 2016-05-25 | 2016-05-25 | It is a kind of to promote photoreduction CO using sodium sulfite2And N2Method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101732987A (en) * | 2008-11-21 | 2010-06-16 | 中国石油大学(北京) | Method for photocatalytic reduction of carbon oxide |
| CN103787448A (en) * | 2014-02-20 | 2014-05-14 | 南京大学 | Denitrification method combining denitrification agent and ultraviolet light |
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| CN101732987A (en) * | 2008-11-21 | 2010-06-16 | 中国石油大学(北京) | Method for photocatalytic reduction of carbon oxide |
| CN103787448A (en) * | 2014-02-20 | 2014-05-14 | 南京大学 | Denitrification method combining denitrification agent and ultraviolet light |
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