CN105884605A - Carbon dioxide recycling method - Google Patents
Carbon dioxide recycling method Download PDFInfo
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- CN105884605A CN105884605A CN201510816636.8A CN201510816636A CN105884605A CN 105884605 A CN105884605 A CN 105884605A CN 201510816636 A CN201510816636 A CN 201510816636A CN 105884605 A CN105884605 A CN 105884605A
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- Prior art keywords
- carbon dioxide
- nano nickel
- carbon
- nickel
- source
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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 29
- 238000004064 recycling Methods 0.000 title abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 235000019253 formic acid Nutrition 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 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 description 23
- 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 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen 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
- 239000002245 particle Substances 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical group [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 210000002966 serum Anatomy 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- 230000036962 time dependent Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 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
- 239000007788 liquid 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 9
- 230000001186 cumulative effect Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 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 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 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
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- -1 carbon ion Chemical class 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
- 150000001875 compounds Chemical class 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
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 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
- 238000002156 mixing Methods 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
- 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a carbon dioxide recycling method. In the presence of nano nickel, a carbon dioxide source reacts with a reducing agent to obtain methanoic acid or acetic acid. Compared with the prior art, the method has the advantages that nano nickel is used as a catalyst to recycle carbon dioxide, and reaction condition is mild; catalytic selectivity is high, only methanoic acid or acetic acid is produced, and both methanoic acid and acetic acid are chemical materials and have high application value; catalysis efficiency is high, the influence of pH value on catalysis activity is small, equipment is simple, and cost is low.
Description
Technical field
The invention belongs to resource reutilization field, a kind of method particularly relating to Resources of Carbon Dioxide.
Background technology
At present, energy shortage and environmental pollution are the two large problems of facing mankind.Carbon dioxide discharges in a large number because Fossil fuel consumes excessively and causes environmental pollution, but it is also a kind of potential carbon resource, the most effectively realizes one of the important topic that its recycling is various countries' common concern.
The resource of carbon dioxide is mainly reduced directly to the useful chemical products such as alkane, formaldehyde, methanol, ethanol, formic acid, acetic acid, carbamide by chemical method.But the reduction of carbon dioxide needs high-energy and provides electron donor, such as the reducing agent H of high energy2, carbon ion or extra power (luminous energy) etc..
Photocatalytic reduction of carbon oxide is the effective technology of a kind of environmental protection, mainly with TiO2, sulfide, ferrite be main photocatalyst, by other materials such as metal, coordination compound, Organic substance etc. of adulterating, or be carried on zeolite, nanotube, SiO2Deng, it is provided that the selectivity of the activating agent product of photocatalytic reduction of carbon oxide, but there is the problems such as efficiency is low, chemical property is unstable, visible ray not impact in its photocatalyst used；Electro-catalysis reduction carbon dioxide, due to its mode simple, efficient, receives more and more attention and studies, but it needs to be additionally provided reaction potential, there is increase energy consumption of reaction, and current utilization rate is relatively low, has the shortcomings such as by-product generation.
At present, economically for, the catalytic hydrogenation of carbon dioxide is considered as most viable method, wherein, with transient metal complex as catalyst, activate carbon dioxide molecule, be to utilize carbon dioxide method the most likely by catalytic hydrogenation reaction.But the method for existing hydrogenation catalyst reduction is all carried out under hot conditions (usually 500 DEG C～600 DEG C), needs to be additionally provided a large amount of energy consumption, even also needs to valuable metal or metal-oxide as catalyst.Therefore, seeking and expand hydrogenation catalyst the simplest, effective reduction carbon dioxide is that the method for industrial reduction is particularly important.
Summary of the invention
In view of this, a kind of method that the technical problem to be solved in the present invention is to provide normal temperature and pressure carbon dioxide resource.
A kind of method that the invention provides Resources of Carbon Dioxide, including:
Under conditions of nano nickel exists, carbon dioxide source is reacted with reducing agent, obtains formic acid.
Preferably, the particle diameter of described nano nickel is 15～25nm.
Preferably, described nano nickel is prepared in accordance with the following methods: in the basic conditions, nickel source is reacted in the liquid phase with sodium borohydride, obtains nano nickel.
Preferably, described carbon dioxide source is carbon dioxide, bicarbonate solution and one or more in carbonate solution.
Preferably, described bicarbonate solution is each independently 1～1000mmol/L with the molar concentration of carbonate solution.
Preferably, described nano nickel and the mass ratio of carbon dioxide source are more than or equal to 3.
Preferably, described nano nickel is (3～100) with the mass ratio of carbon dioxide source: 1.
Preferably, described reducing agent is hydrogen and/or hydrazine hydrate.
Preferably, described reducing agent and the mol ratio of carbon dioxide source are more than or equal to 1.5.
Preferably, described reaction is carried out in aqueous.
A kind of method that the invention provides Resources of Carbon Dioxide, under conditions of nano nickel exists, reacts carbon dioxide source with reducing agent, obtains formic acid.Compared with prior art, the present invention completes the resource of carbon dioxide with nano nickel for catalyst, and reaction condition is gentle；Catalytic selectivity is high, and product only has formic acid, and it is industrial chemicals, is with a wide range of applications；Catalytic efficiency is higher, and catalysis activity is affected less by pH value, and equipment is simple, and cost is relatively low.
Accompanying drawing explanation
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 of preparation in the embodiment of the present invention 1；
Fig. 3 is the X ray diffracting spectrum of the nano nickel of preparation 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 chart in response time in the embodiment of the present invention 2；
Fig. 6 is carbon percent reduction time dependent standard relationship curve chart in the embodiment of the present invention 3；
Fig. 7 is carbon percent reduction time dependent standard relationship curve chart in the embodiment of the present invention 4；
Fig. 8 is carbon percent reduction time dependent standard relationship curve chart in the embodiment of the present invention 5；
Fig. 9 is the standard relationship curve chart of product formic acid concentration changes with time in the embodiment of the present invention 6；
Figure 10 is carbon percent reduction time dependent standard relationship curve chart in the embodiment of the present invention 6；
Figure 11 is the embodiment of the present invention 7 and carbon percent reduction time dependent standard relationship curve chart in embodiment 8；
Figure 12 is the formic acid concn bar diagram obtained in the embodiment of the present invention 9.
Detailed description of the invention
Below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides a kind of Resources of Carbon Dioxide, including: under conditions of nano nickel exists, carbon dioxide source is reacted with reducing agent, obtains formic acid.
Wherein, nano nickel, carbon dioxide source are not particularly limited by the present invention with the source of reducing agent, for commercially available or self-control.
The particle diameter of described nano nickel is preferably 15～25nm, more preferably 17～22nm；The specific surface area of described nano nickel is preferably 80～150m2/ g, more preferably 90～120m2/ g, is further preferably 90～110m2/g.Described nano nickel is preferably prepared by liquid phase reduction, is prepared the most in accordance with the following methods: in the basic conditions, nickel source is reacted in the liquid phase with sodium borohydride, obtains nano nickel.
Wherein, the nickel source that described nickel source is well known to those skilled in the art, there is no special restriction, the present invention is preferably nickel salt, more preferably Nickel dichloride.；Described alkaline environment preferably provides with sodium hydroxide solution, is added after more preferably being mixed with sodium hydroxide solution by sodium borohydride；Described liquid phase is preferably the aqueous solution of alcohol, more preferably ethanol water；In the aqueous solution of described alcohol, alcohol is preferably (1～10) with the volume ratio of water: 1, more preferably (2～8): 1, is further preferably (2～6): 1, most preferably 4:1；Described reaction is preferably carried out under conditions of inert gas shielding；The noble gas that described noble gas is well known to those skilled in the art, there is no special restriction, and the present invention is preferably nitrogen.
The carbon dioxide source that described carbon dioxide source is well known to those skilled in the art, there is no special restriction, the present invention is preferably carbon dioxide, bicarbonate solution and one or more in carbonate solution, more preferably carbon dioxide and/or bicarbonate solution；Described bicarbonate solution is preferably 1～1000mmol/L independently of one another with the molar concentration of carbonate solution, more preferably 1～500mmol/L, it is further preferably 1～300mmol/L, is further preferably 1～200mol/L, it is further preferably 1～100mmol/L, most preferably 10～100mmol/L；The bicarbonate solution that described bicarbonate solution is well known to those skilled in the art, there is no special restriction, is preferably sodium bicarbonate solution and/or potassium bicarbonate solution in the present invention；The carbonate solution that described carbonate solution is well known to those skilled in the art, there is no special restriction, is preferably sodium carbonate liquor and/or solution of potassium carbonate in the present invention.Using bicarbonate solution or carbonate solution as carbon dioxide source, the amount of product is easily controllable, and product is prone to detection.
Described reducing agent is preferably hydrogen and/or hydrazine hydrate；Described reducing agent is preferably greater than or equal to 1.5 with the mol ratio of carbon dioxide source, more preferably (1.5～20): 1, it is further preferably (1.5～10): 1, it is further preferably (1.5～8): 1, it is further preferably (1.5～6): 1, most preferably (2～4): 1.
According to the present invention, described reaction is carried out the most in aqueous；Reaction system is reacted initial pH value and is 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, is more preferably adjusted with hydrochloric acid or sodium hydroxide；The pressure of described reaction is preferably 1.2～1.5 atmospheric pressure；Described reaction is preferably carried out under conditions of vibration；The speed of described vibration is preferably 150～400rpm, and preferably 150～300rpm, be further preferably 180～260rpm, most preferably 200～240rpm；The temperature of described reaction is preferably 25 DEG C～35 DEG C；The described response time is preferably 20～300h, and more preferably 20～200h, be further preferably 20～100h, most preferably 20～80h.
The present invention completes the resource of carbon dioxide with nano nickel for catalyst, and reaction condition is gentle；Catalytic selectivity is high, and product only has formic acid, and it is industrial chemicals, is with a wide range of applications；Catalytic efficiency is higher, and catalysis activity is affected less by pH value, and equipment is simple, and cost is relatively low.
In order to further illustrate the present invention, the method for a kind of Resources of Carbon Dioxide provided the present invention below in conjunction with embodiment is described in detail.
Reagent used in following example is commercially available.
Embodiment 1
By 38g NiCl2·H2O is dissolved in the mixed solution (ethanol is 4:1 with the volume ratio of water) of 500ml ethanol and water, fully proceeds in there-necked flask after mixing；By 14.16g NaBH4Add in 400ml anaerobic water as reducing agent with 1NaOH；15min exposes into N in there-necked flask in advance2To remove NiCl2Oxygen in solution, subsequently while being stirred vigorously, while being slowly added dropwise reducing agent wherein by constant pressure funnel, after to be restored dose drips off, continue to be stirred vigorously 30min, to ensure that reaction is fully, subsequently with anaerobic water and washing with alcohol 5～6 times, put into 65 DEG C of vacuum drying oven dried overnight, obtain nano nickel, save backup in being placed on anaerobism glove box.
Fig. 1 is nano nickel preparation facilities schematic diagram.
Utilize transmission electron microscope that the nano nickel obtained in embodiment 1 is analyzed, obtain 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.
Utilize X-ray diffraction that the nano nickel obtained in embodiment 1 is analyzed, obtain its X ray diffracting spectrum, as shown in Figure 3.From the figure 3, it may be seen that the nano nickel obtained in embodiment 1 is mainly by Ni0Composition, the oxide of small part Ni covers on its surface, i.e. NiO and Ni (OH)2。
Embodiment 2
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6, exposes N in advance210min, with oxygen in removal serum bottle, exposes H after adding the nano nickel of 1g embodiment 1 preparation25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes into a small amount of H2Make the final H of head space2Being 1.2～1.5 atmospheric pressure, experiment has three Duplicate Samples.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shake speed 220rpm, every 24h exposes into a H2Making head space air pressure is 1 atmospheric pressure, and timing detection headspace gas (GC) and liquid component (HPLC), as shown in Figure 4, Fig. 4 is the high-efficient liquid phase chromatogram of liquid component, and end product is defined as formic acid as shown in Figure 4.
Fig. 5 is the cumulant of formic acid and the standard relationship curve chart in response time in embodiment 2, and as shown in Figure 5, along with the increase in response time, the yield of formic acid is continuously increased, and may finally produce the formic acid of crystallization 300mg/L, total carbon percent reduction (CFormic acid/CThe total carbon added× 100) about 65% it is about.The method achieving the resource being catalyzed carbon dioxide at normal temperatures and pressures by nickel catalytic hydrogenation, reaction condition is gentle；Catalytic selectivity is high, and product only has formic acid, and formic acid is industrial chemicals, is with a wide range of applications.
Embodiment 3
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6, exposes N in advance210min, with oxygen in removal serum bottle, exposes H after adding the nano nickel of 1g embodiment 1 preparation25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes 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 in shaking table, temperature control 35 DEG C, shake speed 220rpm, experiment is divided into two groups of A groups and B group, and every 24 h of A group expose into a H2Making head space air pressure is 1 atmospheric pressure, and B group only initially exposes the H into 1.2～1.5 atmospheric pressure2Rear course of reaction no longer exposes into H2, timing two groups of headspace gas (GC) of detection and liquid component (HPLC), obtain two groups of carbon percent reduction time dependent standard relationship curve charts, as shown in Figure 6.
It will be appreciated from fig. 6 that suitable exposure enters H2Carbon percent reduction can be improved, brought up to 65% by 58%, increase formic acid cumulant.
Embodiment 4
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, it is divided into 5 groups, with the NaOH of dilute HCl or 10mmol/L that volume ratio is 5%, pH value is adjusted to 3.79,5.25,6.97,8.71 and 9.84 respectively, exposes N in advance210min, with oxygen in removal serum bottle, exposes H after adding the nano nickel that 1g embodiment 1 is standby25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes into a small amount of H2Make the final H of head space2Being 1.2～1.5 atmospheric pressure, experiment has three Duplicate Samples.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shakes speed 220rpm, by 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6, exposes N in advance210min, with oxygen in removal serum bottle, exposes H after adding nano nickel prepared by 1g25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes 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 in shaking table, temperature control 35 DEG C, shakes speed 220rpm, timing detection headspace gas (GC) and liquid component (HPLC), obtains carbon percent reduction time dependent standard relationship curve chart, as shown in Figure 7.Represented the catalysis activity of nano nickel under different pH value by carbon percent reduction, as shown in Figure 7, catalyst used in the present invention is affected not quite by pH value, and carbon percent reduction is between 48%～58%；PH value is the lowest, and the catalytic effect of the catalyst used is the best, and catalysis activity increases successively along with the reduction of pH value, i.e. pH3.79＞ pH5.25＞ pH6.97＞ pH8.71＞ pH9.84；Thus, the activity of this method hydrogenation catalyst reduction carbon dioxide is affected the least by pH value, and acid-proof alkaline is superior.
Embodiment 5
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6, exposes N in advance2Experiment, with oxygen in removal serum bottle, is divided into five groups by 10min, is separately added into 0.1g, 0.5g, 1g, 2g and exposes H after the nano nickel of 3g embodiment 1 preparation25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes into a small amount of H2Make the final H of head space2Being 1.2～1.5 atmospheric pressure, experiment has three Duplicate Samples.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shake speed 220rpm, every 24h exposes into a H2Making head space air pressure is 1 atmospheric pressure, timing detection headspace gas (GC) and liquid component (HPLC), obtains carbon percent reduction time dependent standard relationship curve chart, as shown in Figure 8.The impact of hydrogenation catalyst reduction carbon dioxide can be represented by different catalysts quality with the carbon percent reduction in Fig. 8.
As shown in Figure 8,2g is optimum catalyst dosage, and in 0.1～2g this range of catalysts, carbon percent reduction increases successively, at NaHCO3In the case of solution is 10mmol/L, sodium bicarbonate percent reduction the highest can close to 100%, but the carbon percent reduction of 3g catalyst and 2g catalyst substantially difference are 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 is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, thus experiment is divided into five groups, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6 respectively, exposes N in advance2Experiment, with oxygen in removal serum bottle, is divided into five groups by 10min, is separately added into 0.1g, 0.5g, 1g, 2g and exposes H after the nano nickel of 3g embodiment 1 preparation25min, makes H2Full serum bottle head space, covers rubber stopper, seals with aluminium lid, more additionally exposes into a small amount of H2Make the final H of head space2Being 1.2～1.5 atmospheric pressure, experiment has three Duplicate Samples.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shakes speed 220rpm, timing detection headspace gas (GC) and liquid component (HPLC), obtains the standard relationship curve chart of product formic acid concentration changes with time, as shown in Figure 9；Obtain carbon percent reduction time dependent standard relationship curve chart, as shown in Figure 10.
As shown in Figure 9, along with the increase of initial bicarbonate na concn, formic acid concn increases successively, reaches as high as 1000mg/L.
As shown in Figure 10, when concentration of carbon is relatively low, carbon percent reduction close to 100%, but can be as sodium bicarbonate concentration and increase, and carbon percent reduction reduces.
It can thus be seen that increase sodium bicarbonate concentration can improve effective catalytic capability of unit catalyst.
Embodiment 7
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, with dilute HCl that volume ratio is 5%, pH value is adjusted to 6, exposes N in advance210min is with oxygen in removal serum bottle, and experiment is divided into two groups of C1 groups and C2 group, adds 0.05mol Yu 0.1mol hydrazine hydrate, cover rubber stopper, seal with aluminium lid after being separately added into the nano nickel of 1g embodiment 1 preparation.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shakes speed 220rpm, timing detection headspace gas (GC) and liquid component (HPLC), obtains the time dependent canonical plotting of carbon percent reduction, as shown in figure 11.
Embodiment 8
By 35ml 10mmol/L NaHCO3Solution is (as CO2Source) load in the serum bottle that cumulative volume is 65ml, by the NaOH solution of 10mmol/L, pH value is adjusted to 9.28, exposes N in advance210min is with oxygen in removal serum bottle, and experiment is divided into two groups of D1 groups and D2 group, adds 0.05mol Yu 0.1mol hydrazine hydrate, cover rubber stopper, seal with aluminium lid after being separately added into the nano nickel of 1g embodiment 1 preparation.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shakes speed 220rpm, timing detection headspace gas (GC) and liquid component (HPLC), obtains the time dependent canonical plotting of carbon percent reduction, as shown in figure 11.
As seen from Figure 11, hydrazine hydrate can substitute high-purity H2For CO2Reduction provide hydrogen source even can obtain higher percent reduction.In acid condition, faster but alkalescence can obtain higher percent reduction to catalysis rate of reduction；Enough hydrazines, percent reduction can be brought up to about 80% by applicable 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, aeration 10min, expose the most inside into mixed gas after gland, making final pressure is 1.5 atmospheric pressure, and bottle is divided into three groups built with 35ml deionized water, experiment, and with the NaOH of dilute HCl or 10mmol/L that volume ratio is 5%, pH value is adjusted to 5.5,8.75 and 10.5 respectively, it is separately added in 1g embodiment 1 nano nickel obtained, covers rubber stopper, seal with aluminium lid.The serum bottle installed is put in shaking table, temperature control 35 DEG C, shakes speed 220rpm, detects formic acid concn, obtain formic acid concn bar diagram, as shown in figure 12 after reaction 115h.
As shown in Figure 12, CO2Can nano nickel be catalyzed under with H2Generate formic acid；When pH value is acid condition, formic acid conversion ratio is the highest, and carbon is with CO2The form existed is more easy to by nano nickel catalysis reduction.
Claims (10)
1. the method for a Resources of Carbon Dioxide, it is characterised in that including:
Under conditions of nano nickel exists, carbon dioxide source is reacted with reducing agent, obtains formic acid.
Method the most according to claim 1, it is characterised in that the particle diameter of described nano nickel is 15～25
nm。
Method the most according to claim 1, it is characterised in that described nano nickel is in accordance with the following methods
It is prepared: in the basic conditions, nickel source is reacted in the liquid phase with sodium borohydride, obtain nano nickel.
Method the most according to claim 1, it is characterised in that described carbon dioxide source is titanium dioxide
Carbon, bicarbonate solution and one or more in carbonate solution.
Method the most according to claim 4, it is characterised in that described bicarbonate solution and carbonic acid
The molar concentration of saline solution is each independently 1～1000mmol/L.
Method the most according to claim 1, it is characterised in that described nano nickel and carbon dioxide source
Mass ratio more than or equal to 3.
Method the most according to claim 1, it is characterised in that described nano nickel and carbon dioxide source
Mass ratio be (3～100): 1.
Method the most according to claim 1, it is characterised in that described reducing agent is hydrogen and/or water
Close hydrazine.
Method the most according to claim 1, it is characterised in that described reducing agent and carbon dioxide source
Mol ratio more than or equal to 1.5.
Method the most according to claim 1, it is characterised in that described reaction is entered in aqueous
OK.
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| CN108499567A (en) * | 2018-04-04 | 2018-09-07 | 中国科学技术大学 | The restoring method of nitrate under a kind of normal temperature and pressure |
| CN113292411A (en) * | 2021-06-16 | 2021-08-24 | 厦门大学 | Application of perovskite catalyst in preparation of formic acid by catalyzing carbon dioxide hydrogenation and preparation method |
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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 |
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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 |
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| CN108499567A (en) * | 2018-04-04 | 2018-09-07 | 中国科学技术大学 | The restoring method of nitrate under a kind of normal temperature and pressure |
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| CN113292411A (en) * | 2021-06-16 | 2021-08-24 | 厦门大学 | Application of perovskite catalyst in preparation of formic acid by catalyzing carbon dioxide hydrogenation and preparation method |
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