CN109201057A - A kind of preparation method of lignin-base carbon supported nano-gold category oxide catalyst - Google Patents
A kind of preparation method of lignin-base carbon supported nano-gold category oxide catalyst Download PDFInfo
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- CN109201057A CN109201057A CN201811189467.XA CN201811189467A CN109201057A CN 109201057 A CN109201057 A CN 109201057A CN 201811189467 A CN201811189467 A CN 201811189467A CN 109201057 A CN109201057 A CN 109201057A
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- lignin
- metal oxide
- oxide catalyst
- based carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 title description 11
- 239000010931 gold Substances 0.000 title description 11
- 229920005610 lignin Polymers 0.000 claims abstract description 119
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 7
- 239000004964 aerogel Substances 0.000 claims abstract 4
- 239000011259 mixed solution Substances 0.000 claims description 34
- 239000012300 argon atmosphere Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 20
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000001994 activation Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000002156 mixing Methods 0.000 description 17
- 239000002105 nanoparticle Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- 239000004966 Carbon aerogel Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- -1 carbon metal oxide Chemical class 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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- 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
- B01J23/745—Iron
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/72—Copper
-
- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种木质素基碳负载纳米金属氧化物催化剂的制备方法，该方法采用木质素作为碳材料前驱体，将木质素配制成溶液并加入金属氧化物前驱体化合物，经冷冻干燥得到气凝胶，然后将气凝胶置于管式炉中热处理，冷却后即得到所述的木质素基碳负载金属氧化物催化剂。本发明通过冷冻干燥与高温热处理的简单方式所制备的金属氧化物催化剂的尺寸为纳米级别，且高效负载于高比表面积的木质素基碳材料表面。其制备过程简单方便，避免了活化过程，有效降低了能耗，避免了环境污染，而且显著提高了木质素产品的科技含量和附加值应用，拓展了木质素资源综合利用的途径，为催化剂载体找到了一种廉价原料，提高了生产率并显著降低了制造成本。The invention discloses a preparation method of a lignin-based carbon-supported nano-metal oxide catalyst. The method adopts lignin as a carbon material precursor, prepares the lignin into a solution, adds a metal oxide precursor compound, and freeze-drying to obtain a solution. The aerogel is then placed in a tube furnace for heat treatment, and the lignin-based carbon supported metal oxide catalyst is obtained after cooling. The size of the metal oxide catalyst prepared by the simple method of freeze-drying and high-temperature heat treatment in the present invention is nano-scale, and is efficiently supported on the surface of the lignin-based carbon material with high specific surface area. The preparation process is simple and convenient, avoids the activation process, effectively reduces energy consumption, avoids environmental pollution, and significantly improves the technological content and value-added application of lignin products, expands the way of comprehensive utilization of lignin resources, and is a catalyst carrier. An inexpensive raw material was found, increasing productivity and significantly reducing manufacturing costs.
Description
Technical field
The present invention relates to catalyst technical fields, urge in particular to a kind of lignin-base carbon supported nano-gold category oxide
The preparation method of agent.
Background technique
Currently, metal oxide oxidation catalyst oxidation technology has been widely used in petrochemical industry, pharmacy, environmental protection, agriculture
The fields such as industry, wherein the metal oxide catalyst of nano-scale has a significant superior catalytic efficiency, however nano-catalytic
Preparing for agent is complex, therefore limited source, and price is more expensive, affect its deeper into and be widely applied.In recent years, porous
Carbon material has biggish specific surface area, unique cellular structure and surface functional group abundant etc. as the carrier of catalyst
Advantage, can effectively improve the catalytic efficiency of catalyst, and improve its catalytic action, cause the extensive concern of scholars, urge
Change field shows great development potentiality.
Although porous carbon materials are widely applied in theoretical research as carrier, the method reported at present
Employed in most of porous carbon materials, often there are some problems in practical catalytic reaction process and need urgent solution
Certainly, it such as needs to be activated using activator, which can generate largely discarded activator, such as potassium hydroxide；Simultaneously
It also needs to clean the carbon material after activation using acid, so that not only energy consumption is high for preparation process, but also pollutes environment.
These problems all seriously limit the extensive use of porous carbon materials loaded catalyst.
Lignin is the second largest biological material that reserves are only second to cellulose on the earth, is to be uniquely based on aromatics in composition
The natural polymer of unit is a kind of important life characterized by being rich in the functional groups such as aromatic group and phenolic hydroxyl group in its structure
Substance carbon source material.There is 3 D stereo mesh space structure simultaneously.In natural timber main component be cellulose, lignin and
Hemicellulose, content are about 2:1:1.During the fining of plant utilizes, since cellulose is easier to extract and converts,
Lignin lays under tribute for a long time, is ignored by people.Therefore, a large amount of wood that workers and peasants' industry especially paper-making industry generates
If quality is not utilized well, the serious wasting of resources and environmental pollution are caused.With the development of society, more and more
Research and facts have proved that waste wood element can be used as a kind of alternate resources and be recycled, increasingly hide in resource weary the present
It, waste wood element gradually causes concern.Alkali lignin is with flue gas (CO2) or acid processing to neutralize soda pulping process boiling useless
The lignin that liquid obtains.Use alkali lignin that there is cost-effectiveness and the feature of environmental protection as catalyst carrier of new generation, meets China
The requirement developed a circular economy meets the policy of China's energy-saving and emission-reduction, comprehensive utilization of resources, becomes the hot spot of future studies.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the present invention is to provide a kind of lignin-base carbon being simple and efficient
The preparation method of supported nano-gold category oxide catalyst solves existing porous carbon load nano-sized metal oxide catalysis
The preparation method of agent there are complicated for operation, load capacity is low, environmental pollution and it is at high cost the problems such as, while it is raw to also solve lignin
The problem of wasting of resources and environmental pollution of physical obsolescence object.
In order to solve the above-mentioned technical problem, present invention employs the following technical solutions: a kind of load of lignin-base carbon is received
The preparation method of rice metal oxide catalyst, comprising the following steps:
1) by lignin preparation lignin liquor soluble in water, then into the lignin liquor metal oxide precursor is added
Compound, stir and be uniformly mixed obtain well dispersed mixed solution, then the mixed solution is freeze-dried, is prepared into
To aeroge；
2) aeroge that step 1) is prepared is placed in tube furnace, and is heat-treated in argon atmosphere, is obtained after cooling
The lignin-base carbon metal oxide supporting catalyst.
On this basis, the lignin after freeze-drying keeps original liquor capacity, and structure is in cellular, effective to increase
Specific surface area is added, to increase the load capacity of metal oxide；Simultaneously because freeze-drying moisture fades away, effectively promote
Into catalyst precursor the surface of solids load.Further, lignin is because also contain some hydrophobic groups in structure, tool
There is surfactant, can promote nano-metal-oxide dispersion, avoid the reunion of nano-metal-oxide.
Further, the concentration of the lignin liquor is 1 ~ 100mg/L.
Concentration by regulating and controlling lignin liquor can realize the regulation to carbon material surface pattern, control preparation sheet load
Carbon material, netted honeycomb load carbon material or threadiness load carbon material, when lignin concentration be greater than 5mg/mL when,
It is main that sheet lignin carbon material is presented, and as concentration increases, material thickness increases, when concentration reaches 100mg/mL,
Netted honeycomb lignin carbon material is then presented；And when lignin concentration is less than 5mg/mL, pattern is fibrous lignin
Carbon material, concentration is lower, and fiber size is smaller.
Further, the additional amount of the metal oxide precursor compound is the 1 ~ 30% of lignin quality.
Further, the metal oxide precursor compound is its nitrate, chlorate, sulfate, carbonate, acetic acid
Salt or nano-oxide.
Further, the freeze-drying then is transferred to freeze-drying the following steps are included: freeze solid in prior to -196 DEG C ~ -20 DEG C
Machine is dry complete.Wherein temperature is -70 ~ -20 DEG C in freeze dryer drying, and the processing time is 24 ~ 72h.
It further, further include continuing the aeroge in pipe under air conditions after being heat-treated in the argon atmosphere
In 200 ~ 400 DEG C of 10 ~ 30min of heat treatment in formula furnace.
For multivalent state metal, due in an inert atmosphere since metal is easy to be reduced, and opposite lower valency gold is obtained
Belong to oxide even metal simple-substance nano particle, material will be obtained and be further heat-treated under low temperature and air conditions, can be made
It is standby to obtain high-valence state metal oxide.
Further, temperature is 200 ~ 1500 DEG C in the heat treatment, and the processing time is 10 ~ 180min.
In this way, the chemical component of load carbon and metal oxide is controlled by adjusting heat treatment temperature, for multivalent state
Metal oxide, at relatively high temperatures be easy generate compared with lower valency metal or metal oxide.
Further, the lignin is water-soluble alkali lignin.
The lignin-base carbon supported nano-gold category oxide catalyst obtained using above-mentioned preparation method.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention using lignin be used as carbon materials material precursor, freeze-drying and high-temperature heat treatment by way of prepared by
The size of metal oxide catalyst is Nano grade, while can regulate and control it according to content of the presoma in lignin liquor
Nano-scale and structure, and high-efficient carrier, in the lignin-base carbon material surface of high-specific surface area, preparation process is simple and convenient, pole
The earth simplifies the preparation of nano-oxide catalytic materials, and nano-metal-oxide catalyst is promoted to make in the load of carbon material surface
With.
2, the present invention is porous pattern using supported catalytic materials prepared by freeze-drying method, has high-ratio surface
Product, avoids the activation step of conventional method, compared to the existing preparation method by the reactivation that is first carbonized, effectively reduces energy
Consumption, avoids environmental pollution.
3, contain the groups such as carboxy hydroxy in lignin structure of the present invention, it is possible to provide oxygen atom promotes metal oxide in height
Metal oxide is converted under temperature, three-dimensional solid netted space structure can improve the load capacity of metal oxide, simultaneously because
Contain hydrophobic and hydrophilic radical in lignin structure simultaneously, can promote the dispersion of metal oxide nanoparticles in the solution, change
Kind catalyst being uniformly distributed in carbon support material.
4, the present invention is according to the three-D space structure of lignin, and using lignin as raw material, reasonable scientific utilization alkali is wooden
Element not only increases the scientific and technological content and added value application of lignin product, avoids lignin and be directly discharged into caused by environment
Pollution behavior has also expanded the approach of biomass Liginon Resource comprehensive utilization, and has found for catalyst carrier a kind of honest and clean
Valence raw material improves productivity and reduces manufacturing cost.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares lignin-base carbon supported nano-gold category oxide catalyst；
Fig. 2 is the scanning electron microscope (SEM) photograph that embodiment 2 prepares lignin-base carbon supported nano-gold category oxide catalyst；
Fig. 3 is the scanning electron microscope (SEM) photograph that embodiment 4 prepares lignin-base carbon supported nano-gold category oxide catalyst；
Fig. 4 is the X-ray diffractogram that embodiment 4 prepares lignin-base carbon supported nano-gold category oxide catalyst；
Fig. 5 is the X-ray diffraction that embodiment 5 prepares lignin-base carbon supported nano-gold category oxide catalyst under an argon atmosphere
Figure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
1) by the lignin lignin liquor soluble in water for preparing 1 mg/L, then into the lignin liquor iron chloride is added,
The dosage of iron chloride is the 5% of lignin quality, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C
It is freezed in liquid nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, the microcosmic catalysis for fibrous lignin-base carbon aerogel load iron and ferroferric oxide nano granules is obtained after cooling
Agent, yield 11.2%, specific surface area 717m2/g。
Embodiment 2
1) by the lignin lignin liquor soluble in water for preparing 5 mg/L, then into the lignin liquor iron chloride is added,
The dosage of iron chloride is lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 750 DEG C for the aeroge that step 1) is prepared
When, the microcosmic catalyst for sheet lignin-base carbon aerogel load iron and ferroferric oxide nano granules is obtained after cooling,
Yield is 34.5%, specific surface area 278m2/g。
Embodiment 3
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor iron chloride is added,
The dosage of iron chloride is lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 600 DEG C and is heat-treated 1 hour,
The microcosmic catalyst for sheet lignin-base carbon aerogel load iron oxide and ferroferric oxide nano granules is obtained after cooling,
Yield is 55.0%, and specific surface area is 143 m2/g。
Embodiment 4
1) by the lignin lignin liquor soluble in water for preparing 20mg/L, then into the lignin liquor iron chloride is added,
The dosage of iron chloride is lignin quality 20%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 48h of -70 DEG C of freeze dryers, aeroge is prepared；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 450 DEG C and is heat-treated 3 hours,
It is to obtain the microcosmic catalyst for sheet lignin-base carbon aerogel load ferric oxide nanometer particle after cooling, yield 70.3%,
Specific surface area is 24 m2/g。
Embodiment 5
1) by the lignin lignin liquor soluble in water for preparing 50 mg/L, then into the lignin liquor iron chloride is added,
The dosage of iron chloride is 30 % of lignin quality, mixed solution is uniformly mixing to obtain, then by the mixed solution in -20 DEG C of ice
It is freezed in case, and -70 DEG C of freeze dryers are dry for 24 hours, and aeroge is prepared；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 750 DEG C and is heat-treated 1 hour,
The microcosmic catalyst for sheet lignin-base carbon aerogel load iron nano-particle is obtained after cooling, yield 50.2% compares table
Area is 47 m2/g；
3) catalyst of lignin-base carbon aerogel load iron nano-particle prepared by step 2 is continued in tubular type stove air
It is heat-treated 10min in atmosphere and 300 DEG C, obtains lignin-base carbon load nanometer ferric oxide particle, yield 21.5% compares table
Area is 105m2/g。
Embodiment 6
1) by the lignin lignin liquor soluble in water for preparing 5mg/L, then manganese nitrate, nitre are added into the lignin liquor
The dosage of sour manganese is lignin quality 10%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid nitrogen
Middle freezing, and the dry 72h of -70 DEG C of freeze dryers, are prepared aeroge；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, microcosmic urging for the mixing nano particle of sheet lignin-base carbon aerogel load mangano-manganic oxide and manganese is obtained after cooling
Agent, yield 18.1%, specific surface area 422m2/g；
3) by the catalysis of lignin-base carbon aerogel load mangano-manganic oxide prepared by step 2 and the mixing nano particle of manganese
Agent continuation is heat-treated 10min in tube furnace air atmosphere and 300 DEG C, obtains lignin-base carbon load nanometer manganese sesquioxide managnic oxide
Grain, yield 10.9%, specific surface area are 685 m2/g。
Embodiment 7
1) by the lignin lignin liquor soluble in water for preparing 5mg/L, then manganese nitrate, nitre are added into the lignin liquor
The dosage of sour manganese is lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -20 DEG C of refrigerators
Freezing, and the dry 72h of -50 DEG C of freeze dryers, are prepared aeroge；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 400 DEG C and is heat-treated 1 hour,
The microcosmic catalysis for sheet lignin-base carbon aerogel load manganese sesquioxide managnic oxide, trimanganese tetroxide nano particle is obtained after cooling
Agent, yield 70.8%, specific surface area are 18 m2/g。
Embodiment 8
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor cerous nitrate is added,
The dosage of cerous nitrate is lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, the microcosmic catalyst for sheet lignin-base carbon aerogel load cerium oxide nanoparticles is obtained after cooling, yield is
25.5%, specific surface area is 375 m2/g。
Embodiment 9
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor zinc chloride is added,
The dosage of zinc chloride is lignin quality 10%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, the microcosmic catalyst for sheet lignin-base loading ZnO nano particles, yield 25.7%, specific surface area are obtained after cooling
For 331 m2/g。
Embodiment 10
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor copper chloride is added,
The dosage of copper chloride is lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 600 DEG C and is heat-treated 1 hour,
It is obtained after cooling microcosmic for sheet lignin-base Supported CuO2The catalyst of nano particle, yield 57.5%, specific surface area are
154 m2/g。
Embodiment 11
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor Na is added2WO4,
Na2WO4Dosage be lignin quality 10%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, it is heat-treated 1 hour, is obtained after cooling microcosmic for sheet lignin-base under the conditions of 300 DEG C after cooling and in air atmosphere
Load WO3The catalyst of nano particle, ultimate yield 13.6%, specific surface area are 611 m2/g。
Embodiment 12
1) by the lignin lignin liquor soluble in water for preparing 10mg/L, then into the lignin liquor bismuth sulfate is added,
The dosage of bismuth sulfate is lignin quality 10%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid
It is freezed in nitrogen, and the dry 72h of -70 DEG C of freeze dryers, aeroge is prepared；
2) aeroge that step 1) is prepared is placed in tube furnace in argon atmosphere under the conditions of 500 DEG C and is heat-treated 1 hour,
It is obtained after cooling microcosmic for sheet lignin-base load Bi2O3The catalyst of nano particle, yield 53.5%, specific surface area are
87 m2/g。。
Embodiment 13
1) by the lignin lignin liquor soluble in water for preparing 10 mg/L, then into the lignin liquor TiO is added2,
TiO2Dosage be lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid nitrogen
Middle freezing, and dry 48 h of -70 DEG C of freeze dryers, aeroge is prepared；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, it is obtained after cooling microcosmic for sheet lignin-base load TiO2The catalyst of nano particle, yield 27.7%, specific surface
Product is 355 m2/g。。
Embodiment 14
1) by the lignin lignin liquor soluble in water for preparing 1 mg/L, then into the lignin liquor TiO is added2,
TiO2Dosage be 1 % of lignin quality, mixed solution is uniformly mixing to obtain, then by the mixed solution in -196 DEG C of liquid nitrogen
Middle freezing, and dry 72 h of -70 DEG C of freeze dryers, are prepared aeroge；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1000 DEG C for the aeroge that step 1) is prepared
When, it is obtained after cooling microcosmic for fibrous lignin-base load TiO2The catalyst of nano particle, yield 13.2% compare table
Area is 709 m2/g。
Embodiment 15
1) by the lignin lignin liquor soluble in water for preparing 100 mg/L, then into the lignin liquor TiO is added2,
TiO2Dosage be lignin quality 5%, mixed solution is uniformly mixing to obtain, then by the mixed solution in -20 DEG C of refrigerators
Slowly freezing, and dry 48 h of -50 DEG C of freeze dryers, are prepared aeroge；
2) it is small to be placed in tube furnace in argon atmosphere heat treatment 1 under the conditions of 1500 DEG C for the aeroge that step 1) is prepared
When, it is obtained after cooling microcosmic for network cell shape lignin-base load TiO2The catalyst of nano particle, yield 6.6%, than
Surface area is 56 m2/g。
Lignin-base carbon aerogel load nano-metal-oxide catalyst prepared by embodiment 1,2 and 4, in scanning electricity
Pattern is observed in mirror, as shown in Fig. 1 ~ 3.
With the reduction of lignin liquor concentration it can be seen from Fig. 1 ~ 3, the carbon material micropore being prepared is also more,
Its specific surface area is bigger, while with the reduction of concentration, carbon material pattern is converted into thin sheet from thick sheet, further
It is converted into fibrous carbon material.This is because when lignin presoma is freeze-dried in the aqueous solution of higher concentration, lignin
Between it is continuously distributed, however when concentration is as low as when then lignin is not enough to support continuous distribution to a certain degree, lignin
It scatter to form threadiness.
The lignin-base carbon aerogel load metallic catalyst that embodiment 4 and 5 is prepared under an argon atmosphere is cooked X-ray to spread out
(XRD) research is penetrated, it is as a result as shown in Figure 4 and Figure 5 respectively.
From fig. 4, it can be seen that it is mainly the characteristic peak of iron oxide, illustrate under 450 DEG C of heat treatment under an argon atmosphere
Oxidation product is the iron oxide of lower valency；It goes as can be seen from Figure 5, is mainly the characteristic peak of iron and ferroso-ferric oxide, explanation
Oxidation product is the ferroso-ferric oxide and fe with respect to lower valency under 750 DEG C of heat treatment under an argon atmosphere first.Continue
It is heat-treated in air atmosphere, the ferroso-ferric oxide of lower valency and fe are oxidized to the di-iron trioxide of high-valence state.
It can be seen that for there may be the metal of different valence state, oxidizing temperature and conditions will greatly affect its oxidation product.Therefore originally
Invention can control the chemical component of load carbon and metal oxide by adjusting heat treatment temperature and atmosphere.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limitation with the present invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
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