CN105884605B - A kind of method of Resources of Carbon Dioxide - Google Patents
A kind of method of Resources of Carbon Dioxide Download PDFInfo
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- CN105884605B CN105884605B CN201510816636.8A CN201510816636A CN105884605B CN 105884605 B CN105884605 B CN 105884605B CN 201510816636 A CN201510816636 A CN 201510816636A CN 105884605 B CN105884605 B CN 105884605B
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- carbon dioxide
- nano nickel
- source
- formic acid
- nickel
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 50
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019253 formic acid Nutrition 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 36
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 6
- 239000003317 industrial substance Substances 0.000 abstract description 4
- 210000002966 serum Anatomy 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 17
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- -1 carbon ion Chemical class 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/393—
-
- B01J35/613—
-
- B01J35/615—
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides a kind of method of Resources of Carbon Dioxide, under the conditions of existing for the nano nickel, carbon dioxide source is reacted with reducing agent, obtains formic acid or acetic acid.Compared with prior art, the present invention completes the recycling of carbon dioxide using nano nickel as catalyst, and reaction condition is mild；Catalytic selectivity is high, and product only has formic acid or acetic acid, and the two is all industrial chemicals, is with a wide range of applications；Catalytic efficiency is higher, and catalytic activity is influenced smaller by pH value, and equipment is simple, and cost is relatively low.
Description
Technical field
The invention belongs to resource reutilization field more particularly to a kind of methods of Resources of Carbon Dioxide.
Background technique
Currently, energy shortage and environmental pollution are the two large problems of facing mankind.Carbon dioxide excessively disappears because of fossil fuel
It consumes and largely discharges and cause environmental pollution, but it is also a kind of potential carbon resource, how effectively to realize its resource utilization
It is one of the important topic of various countries' common concern.
The recycling of carbon dioxide mainly passes through chemical method and is reduced directly to alkane, formaldehyde, methanol, ethyl alcohol, first
The useful chemical products such as acid, acetic acid, urea.But the reduction of carbon dioxide needs high-energy and provides electron donor, it is such as high
The reducing agent H of energy2, carbon ion or extra power (luminous energy) etc..
Photocatalytic reduction of carbon oxide is a kind of environmentally protective effective technology, mainly with TiO2, sulfide, ferrite be
Main photochemical catalyst by adulterating other substances such as metal, complex, organic matter etc., or is carried on zeolite, nanotube, SiO2
Deng, the selectivity of the activating agent product of photocatalytic reduction of carbon oxide is provided, but its photochemical catalyst used there are low efficiency, change
Learn the problems such as performance is unstable, visible light does not influence；Electro-catalysis restores carbon dioxide due to its simple, efficient mode, by
More and more concerns and research, but it needs to be additionally provided reaction potential, there are increase energy consumption of reaction, current utilization rate compared with
It is low, have the disadvantages of by-product generates.
Currently, the catalytic hydrogenation of carbon dioxide is considered as most viable method, wherein for economically with mistake
Cross metal complex be catalyst, activate carbon dioxide molecule, by catalytic hydrogenation reaction be have the most using carbon dioxide it is uncommon
The method of prestige.But the method for existing hydrogenation catalyst reduction all carries out under hot conditions (usually 500 DEG C~600 DEG C),
It needs to be additionally provided a large amount of energy consumptions, or even also needs valuable metal or metal oxide as catalyst.Therefore, seek and
It is particularly important to expand the method that simple at normal temperature, effective hydrogenation catalyst reduction carbon dioxide is industrial reduction.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of normal temperature and pressure carbon dioxide recycling
Method.
The present invention provides a kind of methods of Resources of Carbon Dioxide, comprising:
Under the conditions of existing for the nano nickel, carbon dioxide source is reacted with reducing agent, obtains formic acid.
Preferably, the partial size of the nano nickel is 15~25nm.
Preferably, the nano nickel is prepared in accordance with the following methods: under alkaline condition, nickel source and sodium borohydride being existed
It is reacted in liquid phase, obtains nano nickel.
Preferably, the carbon dioxide source is one of carbon dioxide, bicarbonate solution and carbonate solution or more
Kind.
Preferably, the molar concentration of the bicarbonate solution and carbonate solution is each independently 1~1000mmol/
L。
Preferably, the mass ratio of the nano nickel and carbon dioxide source is more than or equal to 3.
Preferably, the mass ratio of the nano nickel and carbon dioxide source is (3~100): 1.
Preferably, the reducing agent is hydrogen and/or hydrazine hydrate.
Preferably, the molar ratio of the reducing agent and carbon dioxide source is more than or equal to 1.5.
Preferably, the reaction carries out in aqueous solution.
The present invention provides a kind of method of Resources of Carbon Dioxide, under the conditions of existing for the nano nickel, by carbon dioxide
Source is reacted with reducing agent, obtains formic acid.Compared with prior art, the present invention completes carbon dioxide by catalyst of nano nickel
Recycling, reaction condition is mild；Catalytic selectivity is high, and product only has formic acid, and it is industrial chemicals, is had a wide range of applications
Value；Catalytic efficiency is higher, and catalytic activity is influenced smaller by pH value, and equipment is simple, and cost is relatively low.
Detailed description of the invention
Fig. 1 is nano nickel preparation facilities schematic diagram in the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope photo of the nano nickel prepared in the embodiment of the present invention 1；
Fig. 3 is the X ray diffracting spectrum of the nano nickel prepared in the embodiment of the present invention 1；
Fig. 4 is the high-efficient liquid phase chromatogram of liquid component in the embodiment of the present invention 2；
Fig. 5 is the cumulant of formic acid and the standard relationship curve graph in reaction time in the embodiment of the present invention 2；
Fig. 6 is the standard relationship curve graph that carbon reduction rate changes over time in the embodiment of the present invention 3；
Fig. 7 is the standard relationship curve graph that carbon reduction rate changes over time in the embodiment of the present invention 4；
Fig. 8 is the standard relationship curve graph that carbon reduction rate changes over time in the embodiment of the present invention 5；
Fig. 9 is the standard relationship curve graph of product formic acid concentration changes with time in the embodiment of the present invention 6；
Figure 10 is the standard relationship curve graph that carbon reduction rate changes over time in the embodiment of the present invention 6；
Figure 11 is the standard relationship curve graph that carbon reduction rate changes over time in the embodiment of the present invention 7 and embodiment 8；
Figure 12 is formic acid concn column diagram obtained in the embodiment of the present invention 9.
Specific embodiment
Below in conjunction with the attached drawing of the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
The present invention provides a kind of Resources of Carbon Dioxide, comprising: under the conditions of existing for the nano nickel, by carbon dioxide source
It is reacted with reducing agent, obtains formic acid.
Wherein, the present invention is not particularly limited the source of nano nickel, carbon dioxide source and reducing agent, to be commercially available or
Self-control.
The partial size of the nano nickel is preferably 15~25nm, more preferably 17~22nm；The specific surface area of the nano nickel
Preferably 80~150m2/ g, more preferably 90~120m2/ g is further preferably 90~110m2/g.The nano nickel preferably passes through liquid
Prepared by phase reduction method, more preferably prepared in accordance with the following methods: under alkaline condition, by nickel source and sodium borohydride in liquid
It is reacted in phase, obtains nano nickel.
Wherein, the nickel source is nickel source well known to those skilled in the art, has no special limitation, the present invention is preferred
For nickel salt, more preferably nickel chloride；The alkaline environment is preferably provided with sodium hydroxide solution, more preferably by sodium borohydride and hydrogen
It is added after sodium hydroxide solution mixing；The liquid phase is preferably the aqueous solution of alcohol, more preferably ethanol water；The alcohol
The volume ratio of alcohol and water is preferably (1~10): 1, more preferably (2~8) in aqueous solution: 1, be further preferably (2~6): 1, it is optimal
It is selected as 4:1；The reaction preferably carries out under conditions of inert gas shielding；The inert gas is that those skilled in the art are ripe
The inert gas known, has no special limitation, and the present invention is preferably nitrogen.
The carbon dioxide source is carbon dioxide source well known to those skilled in the art, has no special limitation, this
It is preferably one of carbon dioxide, bicarbonate solution and carbonate solution or a variety of, more preferably carbon dioxide in invention
And/or bicarbonate solution；The molar concentration of the bicarbonate solution and carbonate solution each independently be preferably 1~
1000mmol/L, more preferably 1~500mmol/L are further preferably 1~300mmol/L, are further preferably 1~200mol/L, then excellent
It is selected as 1~100mmol/L, most preferably 10~100mmol/L；The bicarbonate solution is well known to those skilled in the art
Bicarbonate solution has no special limitation, is preferably sodium bicarbonate solution and/or potassium bicarbonate solution in the present invention；
The carbonate solution is carbonate solution well known to those skilled in the art, has no special limitation, excellent in the present invention
It is selected as sodium carbonate liquor and/or solution of potassium carbonate.Using bicarbonate solution or carbonate solution as carbon dioxide source, product
Measure easily controllable, and reaction product is easy to detect.
The reducing agent is preferably hydrogen and/or hydrazine hydrate；The molar ratio of the reducing agent and carbon dioxide source is preferably big
In be equal to 1.5, more preferably (1.5~20): 1, be further preferably (1.5~10): 1, be further preferably (1.5~8): 1, further preferably for
(1.5~6): 1, most preferably (2~4): 1.
According to the present invention, the reaction preferably carries out in aqueous solution；Reaction system react initial pH value be preferably 5~
8, more preferably 5~7, most preferably 5.5~6.5；The pH value of reaction system can be adjusted with acid or alkali, more preferably with salt
Acid or sodium hydroxide are adjusted；The pressure of the reaction is preferably 1.2~1.5 atmospheric pressure；The reaction is preferably being vibrated
Under conditions of carry out；The speed of the oscillation is preferably 150~400rpm, preferably 150~300rpm, further preferably for 180~
260rpm, most preferably 200~240rpm；The temperature of the reaction is preferably 25 DEG C~35 DEG C；The reaction time is preferably
20~300h, more preferably 20~200h are further preferably 20~100h, most preferably 20~80h.
The present invention completes the recycling of carbon dioxide using nano nickel as catalyst, and reaction condition is mild；Catalysis selection
Property it is high, product only has formic acid, and it is industrial chemicals, is with a wide range of applications；Catalytic efficiency is higher, and catalytic activity is by pH
Value influence is smaller, and equipment is simple, and cost is relatively low.
In order to further illustrate the present invention, with reference to embodiments to a kind of Resources of Carbon Dioxide provided by the invention
Method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
By 38g NiCl2·H2O is dissolved in the mixed solution of 500ml ethyl alcohol and water (volume ratio of ethyl alcohol and water is 4:1)
In, it is transferred in there-necked flask after mixing well；By 14.16g NaBH4It adds in 400ml anaerobic water with 1NaOH as reducing agent；It mentions
Preceding 15min is exposed into there-necked flask into N2To remove NiCl2Oxygen in solution, is then vigorously stirred on one side, is leaked on one side by constant pressure
Reducing agent is slowly added dropwise in bucket thereto, after to be restored dose drips off, continues to be vigorously stirred 30min, to guarantee that reaction sufficiently, is then used
Anaerobic water and ethanol washing 5~6 times, be put into vacuum oven 65 DEG C it is dried overnight, obtain nano nickel, place it in anaerobism hand
It is saved backup in casing.
Fig. 1 is nano nickel preparation facilities schematic diagram.
Nano nickel obtained in embodiment 1 is analyzed using transmission electron microscope, obtains its transmission electron microscope photo (TEM),
As shown in Figure 2.As shown in Figure 2, the size of nano nickel is about 15~25nm.
Nano nickel obtained in embodiment 1 is analyzed using X-ray diffraction, obtains its X ray diffracting spectrum, is such as schemed
Shown in 3.From the figure 3, it may be seen that nano nickel obtained in embodiment 1 is mainly by Ni0Composition, the oxide of small part Ni are covered on it
Surface, i.e. NiO and Ni (OH)2。
Embodiment 2
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, use volume
Than pH value is adjusted to 6 for 5% dilute HCl, N is exposed in advance210min is added 1g embodiment 1 and prepares to remove oxygen in serum bottle
Nano nickel after expose H25min makes H2Full serum bottle head space, covers rubber stopper, is sealed with aluminium lid, then additionally expose into a small amount of H2
Make the final H of head space2For 1.2~1.5 atmospheric pressure, there are three Duplicate Samples for experiment.The serum bottle installed is put into shaking table, temperature control
35 DEG C, speed 220rpm is shaken, it is every to be exposed for 24 hours into a H2Make 1 atmospheric pressure of head space air pressure, timing detects headspace gas (GC)
And liquid component (HPLC), as shown in figure 4, Fig. 4 is the high-efficient liquid phase chromatogram of liquid component, final product is true as shown in Figure 4
It is set to formic acid.
Fig. 5 is the cumulant of formic acid and the standard relationship curve graph in reaction time in embodiment 2, as shown in Figure 5, with anti-
Increase between seasonable, the yield of formic acid are continuously increased, and may finally generate the formic acid of crystallization 300mg/L, total carbon reduction rate
(CFormic acid/CThe total carbon of additionIt × 100) is about 65% or so.The method achieve pass through the catalysis of nickel catalytic hydrogenation at normal temperatures and pressures to complete
The recycling of carbon dioxide, reaction condition are mild；Catalytic selectivity is high, and product only has formic acid, and formic acid is industrial chemicals, is had
Wide application value.
Embodiment 3
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, use volume
Than pH value is adjusted to 6 for 5% dilute HCl, N is exposed in advance210min is added 1g embodiment 1 and prepares to remove oxygen in serum bottle
Nano nickel after expose H25min makes H2Full serum bottle head space, covers rubber stopper, is sealed with aluminium lid, then additionally expose into a small amount of H2
Make the final H of head space2For 1.2~1.5 atmospheric pressure.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed
220rpm, experiment are divided into two groups of A groups and B group, and every 24 h of A group is exposed into a H2Make 1 atmospheric pressure of head space air pressure, B group only has
Initially expose the H into 1.2~1.5 atmospheric pressure2It no longer exposes in reaction process into H afterwards2, timing detect two groups of headspace gas (GC) and
Liquid component (HPLC) obtains the standard relationship curve graph that two groups of carbon reduction rates change over time, as shown in Figure 6.
It will be appreciated from fig. 6 that appropriate expose into H2Carbon reduction rate can be improved, be increased to 65% by 58%, increase formic acid accumulation
Amount.
Embodiment 4
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, it is divided into 5
Group, respectively with volume ratio be 5% dilute HCl or 10mmol/L NaOH by pH value be adjusted to 3.79,5.25,6.97,8.71 with
9.84, N is exposed in advance210min exposes H after the standby nano nickel of 1g embodiment 1 is added to remove oxygen in serum bottle25min makes H2It fills
It is full of serum bottle head space, covers rubber stopper, sealed with aluminium lid, then additionally expose into a small amount of H2Make the final H of head space2It is big for 1.2~1.5
Air pressure, there are three Duplicate Samples for experiment.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, speed 220rpm is shaken, by 35ml
10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, the dilute HCl for being 5% with volume ratio
PH value is adjusted to 6, exposes N in advance210min exposes H after the nano nickel of 1g preparation is added to remove oxygen in serum bottle25min makes H2
Full serum bottle head space, covers rubber stopper, is sealed with aluminium lid, then additionally expose into a small amount of H2Make the final H of head space2It is 1.2~1.5
Atmospheric pressure.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed 220rpm, timing detects headspace gas (GC)
And liquid component (HPLC), the standard relationship curve graph that carbon reduction rate changes over time is obtained, as shown in Figure 7.It is restored by carbon
Rate indicates the catalytic activity of nano nickel under different pH value, and as shown in Figure 7, catalyst used in the present invention is influenced by pH value
Less, carbon reduction rate is between 48%~58%；PH value is lower, and the catalytic effect of used catalyst is better, catalytic activity
As the reduction of pH value successively increases, i.e. pH3.79> pH5.25> pH6.97> pH8.71> pH9.84；Thus, this method hydrogenation catalyst
The activity of reduction carbon dioxide is influenced very small by pH value, and acid-proof alkaline is superior.
Embodiment 5
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, use volume
Than pH value is adjusted to 6 for 5% dilute HCl, N is exposed in advance210min is divided into five groups to remove oxygen in serum bottle, by experiment, respectively
H is exposed after nano nickel prepared by 0.1g, 0.5g, 1g, 2g and 3g embodiment 1 is added25min makes H2Full serum bottle head space, covers rubber
Rubber plug is sealed with aluminium lid, then is additionally exposed into a small amount of H2Make the final H of head space2For 1.2~1.5 atmospheric pressure, there are three parallel for experiment
Sample.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed 220rpm, it is every to be exposed for 24 hours into a H2Make head space air pressure
For 1 atmospheric pressure, timing detects headspace gas (GC) and liquid component (HPLC), obtains the standard that carbon reduction rate changes over time
Graph of relation, as shown in Figure 8.Different catalysts quality influences to use in Fig. 8 to hydrogenation catalyst reduction carbon dioxide
Carbon reduction rate indicates.
As shown in Figure 8,2g is optimum catalyst dosage, and in this range of catalysts of 0.1~2g, carbon reduction rate successively increases
Add, in NaHCO3In the case that solution is 10mmol/L, sodium bicarbonate reduction rate highest accessible 100%, but 3g catalyst
Carbon reduction rate and 2g catalyst substantially difference it is little, economically consider, 2g is optimum catalyst dosage.
Embodiment 6
Respectively by 35ml 1mmol/L, 10mmol/L, 25mmol/L, 50mmol/L and 100mmol/L NaHCO3Solution
(as CO2Source) it is fitted into the serum bottle that total volume is 65ml, it is respectively 5% with volume ratio so that experiment is divided into five groups
PH value is adjusted to 6 by dilute HCl, exposes N in advance210min is divided into five groups to remove oxygen in serum bottle, by experiment, is separately added into
H is exposed after nano nickel prepared by 0.1g, 0.5g, 1g, 2g and 3g embodiment 125min makes H2Full serum bottle head space, covers rubber
Plug, is sealed, then additionally expose into a small amount of H with aluminium lid2Make the final H of head space2For 1.2~1.5 atmospheric pressure, there are three Duplicate Samples for experiment.
The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed 220rpm, timing detect headspace gas (GC) and liquid at
Divide (HPLC), obtains the standard relationship curve graph of product formic acid concentration changes with time, as shown in Figure 9；Obtain carbon reduction rate with
The standard relationship curve graph of time change, as shown in Figure 10.
As shown in Figure 9, as the increase of initial bicarbonate na concn, formic acid concn successively increase, 1000mg/ is reached as high as
L。
As shown in Figure 10, when concentration of carbon is lower, carbon reduction rate can be close to 100%, but with sodium bicarbonate concentration
Increase, carbon reduction rate reduces.
It can thus be seen that increasing sodium bicarbonate concentration can be improved effective catalytic capability of unit catalyst.
Embodiment 7
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, use volume
Than pH value is adjusted to 6 for 5% dilute HCl, N is exposed in advance210min to remove oxygen in serum bottle, experiment be divided into two groups of C1 groups and
C2 group is added 0.05mol and 0.1mol hydrazine hydrate after being separately added into the nano nickel of the preparation of 1g embodiment 1, covers rubber stopper, use aluminium
Lid sealing.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed 220rpm, timing detects headspace gas (GC)
And liquid component (HPLC), the canonical plotting that carbon reduction rate changes over time is obtained, as shown in figure 11.
Embodiment 8
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) it is fitted into the serum bottle that total volume is 65ml, it uses
PH value is adjusted to 9.28 by the NaOH solution of 10mmol/L, exposes N in advance2For 10min to remove oxygen in serum bottle, experiment is divided into two
Group D1 group and D2 group are added 0.05mol and 0.1mol hydrazine hydrate after being separately added into the nano nickel of the preparation of 1g embodiment 1, cover rubber
Rubber plug is sealed with aluminium lid.The serum bottle installed is put into shaking table, 35 DEG C of temperature control, shakes speed 220rpm, timing detects head space
Gas (GC) and liquid component (HPLC), obtain the canonical plotting that carbon reduction rate changes over time, as shown in figure 11.
As seen from Figure 11, hydrazine hydrate can substitute high-purity H2For CO2Reduction provide hydrogen source even can obtain it is higher
Reduction rate.In acid condition, faster still alkalinity can obtain higher reduction rate to catalysis rate of reduction；Enough hydrazines,
Reduction rate can be increased to 80% or so by suitable pH value；Illustrate that hydrazine hydrate is good hydrogen source.
Embodiment 9
It is 80%H by volume fraction2With 20%CO2Mixed gas expose in 75ml serum bottle, 10min is aerated, after gland
It being exposed inside into mixed gas again, makes 1.5 atmospheric pressure of final pressure, bottle is provided with 35ml deionized water, and experiment is divided into three groups,
And pH value is adjusted to 5.5,8.75 and 10.5 by the NaOH with volume ratio for 5% dilute HCl or 10mmol/L respectively, is separately added into 1g
Nano nickel obtained in embodiment 1, covers rubber stopper, is sealed with aluminium lid.The serum bottle installed is put into shaking table, temperature control 35
DEG C, speed 220rpm is shaken, formic acid concn is detected after reacting 115h, obtains formic acid concn column diagram, as shown in figure 12.
As shown in Figure 12, CO2Can nano nickel catalysis under with H2Generate formic acid；When pH value is acid condition, formic acid conversion
Rate highest, carbon is with CO2Existing form is easier to be catalyzed by nano nickel and restore.
Claims (6)
1. a kind of method of Resources of Carbon Dioxide characterized by comprising
Under the conditions of existing for the nano nickel, carbon dioxide source is reacted with reducing agent, obtains formic acid；
The temperature of the reaction is 25 DEG C~35 DEG C；
The reducing agent is hydrogen and/or hydrazine hydrate；
The pressure of the reaction is 1.2~1.5 atmospheric pressure；
The partial size of nano nickel is 15~25nm；
The carbon dioxide source is one of carbon dioxide, bicarbonate solution and carbonate solution or a variety of；
The mass ratio of the nano nickel and carbon dioxide source is more than or equal to 3.
2. the method according to claim 1, wherein the nano nickel is prepared in accordance with the following methods: in alkali
Under the conditions of property, nickel source is reacted in the liquid phase with sodium borohydride, obtains nano nickel.
3. the method according to claim 1, wherein the bicarbonate solution and carbonate solution is mole dense
Degree is each independently 1~1000mmol/L.
4. the method according to claim 1, wherein the mass ratio of the nano nickel and carbon dioxide source be (3~
100): 1.
5. the method according to claim 1, wherein the molar ratio of the reducing agent and carbon dioxide source be greater than etc.
In 1.5.
6. the method according to claim 1, wherein the reaction carries out in aqueous solution.
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| CN1404950A (en) * | 2002-11-15 | 2003-03-26 | 北京科技大学 | Method for preapaing nano nickel and its alloy powder in water solution by chemical reduction method |
| CN1644282A (en) * | 2005-01-13 | 2005-07-27 | 南京大学 | Production for nanometer nickel powder |
| CN103755548A (en) * | 2013-12-30 | 2014-04-30 | 上海交通大学 | Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate |
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| CN1404950A (en) * | 2002-11-15 | 2003-03-26 | 北京科技大学 | Method for preapaing nano nickel and its alloy powder in water solution by chemical reduction method |
| CN1644282A (en) * | 2005-01-13 | 2005-07-27 | 南京大学 | Production for nanometer nickel powder |
| CN103755548A (en) * | 2013-12-30 | 2014-04-30 | 上海交通大学 | Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate |
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| Title |
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| A novel method of NaHCO3 reduction into formic acid with N2H4.H2O over Ni catalyst;feiyanchen等;《RSC Advances communication》;20150112;第5卷;第11257-11260页 |
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