CN108927194A - N doping ruthenium base biology Pd/carbon catalyst and its preparation method and application - Google Patents
N doping ruthenium base biology Pd/carbon catalyst and its preparation method and application Download PDFInfo
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- CN108927194A CN108927194A CN201810730243.9A CN201810730243A CN108927194A CN 108927194 A CN108927194 A CN 108927194A CN 201810730243 A CN201810730243 A CN 201810730243A CN 108927194 A CN108927194 A CN 108927194A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 160
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 80
- 239000003610 charcoal Substances 0.000 claims abstract description 25
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002028 Biomass Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000000802 nitrating effect Effects 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000005456 Pinus sylvestris var mongolica Nutrition 0.000 claims description 5
- 241000114025 Pinus sylvestris var. mongolica Species 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 108010058846 Ovalbumin Proteins 0.000 claims description 2
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940092253 ovalbumin Drugs 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- GUUNMTFSWQFNCZ-UHFFFAOYSA-I C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.[K+].[C+4].C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.[K+].[C+4].C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O.C(C=1C(C(=O)[O-])=CC=CC1)(=O)O GUUNMTFSWQFNCZ-UHFFFAOYSA-I 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000003138 coordinated effect Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 29
- 238000012512 characterization method Methods 0.000 description 15
- 239000003575 carbonaceous material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000004227 thermal cracking Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 206010047505 Visceral leishmaniasis Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
Abstract
The present invention relates to a kind of N doping ruthenium base biology Pd/carbon catalysts and its preparation method and application, and N doping ruthenium base biology Pd/carbon catalyst is using situ Nitrogen Doping charcoal as carrier, using metal Ru as active component；The load capacity of the metal Ru is 0.5~5wt%；The N doping amount is 5~20wt%, and the forms of nitrogen of the N doping includes pyridine nitrogen and pyrroles's nitrogen；The N doping ruthenium base biology Pd/carbon catalyst have micropore with it is mesoporous.By the coordinated effect between carrier and active component, so that catalyst can be improved CO2CO in synthesizing methane reaction2Conversion ratio and CH4Selectivity.
Description
Technical field
The present invention relates to the modifications of biological Pd/carbon catalyst, and in particular to a kind of N doping ruthenium base biology Pd/carbon catalyst and its system
Preparation Method and application.
Background technique
It in recent years, is solution CO2Brought environment and energy two large problems, CO2Recycling recycling be constantly subjected to grind
The extensive concern for the person of studying carefully.The CO that Paul Sabatier etc. was proposed in 19022Methanation technology is current CO2Recycling recycles
One of most practical effective technology.By giving CO2Molecule input high-energy simultaneously provides after electron donor activated, and is added active
Reducing agent H2, methanation reaction can be completed.
And to realize efficient CO2Methanation transformation, high activated catalyst are crucial.Carbon Materials are good with stability, compare
The characteristics of surface area is big and Kong Rong great, therefore be the catalyst of carrier in CO using Carbon Materials2It has been obtained in methanation reaction extensively
Concern.It, in the reaction can the upper limit to a certain degree firstly, its structure is mainly micropore however, Carbon Materials but have some drawbacks
The diffusion and transfer of reactant processed；Secondly, surface-active site is insufficient, causes Active components distribution uneven and be easy to happen reunion
Phenomenon etc..Therefore, the high activity Carbon Materials with hierarchical porous structure and surface chemical property modulation have very big industrial application
Prospect.Studies have shown that micropore is more conducive to being catalyzed with mesoporous coexist than individual microcellular structure for catalyst carrier
Reaction because it can mitigate the diffusion limitation in reaction, and it is mesoporous can serve as channel, allow reactants and products to pass in and out
Catalytic inner, to improve reaction efficiency.
Report that there are the catalyst of nitrogen-atoms is anti-to oxalic acid oxidation in carbon skeleton for the first time from nineteen twenty-six Rideal and Wright
Since the catalytic activity answered has facilitation, nitrogen-atoms mixes the modifying function of Carbon Materials and the nitrogen of active metal support type
Miscellaneous Pd/carbon catalyst causes the extensive concern of scholars in heterogeneous catalytic reaction to the influence of catalytic performance.As Chinese invention is special
Benefit application (108163853 A of CN) discloses a kind of method for preparing high nitrogenous porous carbon material using biomass, by biomass powder
After broken drying, fast pyrogenation is carried out under ammonia atmosphere after evenly mixing with activator, the nitrogen-atoms in ammonia quickly occupies sky
Cave forms active nitrogen-containing functional group (pyridine-N, pyrroles-N, season-N and pyridine-N-oxides) abundant, and then enriched nitrogen
Element is in pyrolytic carbon.Do not continue to be modified high nitrogenous porous carbon material in this method, due to activity no in material
Ingredient catalytic performance is poor.It would therefore be highly desirable to which the N doping Pd/carbon catalyst for developing a kind of active metal support type improves its catalytic
Energy.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of N doping ruthenium base biology Pd/carbon catalyst, lead to
The coordinated effect between carrier and active component is crossed, so that catalyst can be improved CO2CO in synthesizing methane reaction2Turn
Rate and CH4Selectivity.
Technical solution provided by the present invention are as follows:
A kind of N doping ruthenium base biology Pd/carbon catalyst, using situ Nitrogen Doping charcoal as carrier, using metal Ru as active group
Point；The load capacity of the metal Ru is 0.5~5wt%；The N doping amount is 5~20wt%, the nitrogen shape of the N doping
State includes pyridine nitrogen and pyrroles's nitrogen；The N doping ruthenium base biology Pd/carbon catalyst have micropore with it is mesoporous.
N doping ruthenium base biology Pd/carbon catalyst is made of carrier and active component in the present invention.Carrier is raw for situ Nitrogen Doping
Object charcoal, it is modified that biomass passes through functionalization nitrating in situ so that have on carrier different nitrogen form (at least containing pyridine nitrogen and
Pyrroles's nitrogen) and two-stage pore structure (micropore and mesoporous).The introducing of nitrogen changes Electronic Structure in carrier, thus more
Added with the dispersion and fixation conducive to active component ruthenium, while the surface alkalinty of carrier is increased, may advantageously facilitate reactant CO2's
Absorption.
Pyridine nitrogen and pyrroles's nitrogen groups can increase the electronics phase interaction between metal Ru and carrier as electron donor
With, accelerate catalyst system in electronics transfer, to be conducive to the dispersion and fixation of active component ruthenium.Pyridine nitrogen has alkali simultaneously
Property, it is more conducive to CO2Reactant CO in synthesizing methane reaction2It is adsorbed on catalyst and is reacted.Have in catalyst most suitable
Pyridine nitrogen and when pyrroles's nitrogen content, the CO of N doping ruthenium base biology Pd/carbon catalyst in the reaction can be further increased2Conversion
Rate and CH4Selectivity.Preferably, wherein pyridine nitrogen content in surface is total nitrogen content to the N doping ruthenium base biology Pd/carbon catalyst
15~45%, surface pyrroles's nitrogen content be total nitrogen content 25~65%.Further, the N doping amount be 14~
17%, surface pyridine nitrogen content is the 25~40% of total nitrogen content, and surface pyrroles's nitrogen content is the 30~60% of total nitrogen content.Again
Further, the N doping amount is 14~15%, and surface pyridine nitrogen content is the 35~40% of total nitrogen content, surface pyrroles's nitrogen
Content is the 40~50% of total nitrogen content.
Micropore with it is mesoporous coexist than individual microcellular structure be more conducive to catalysis react because it can mitigate in reaction
Diffusion limitation, and it is mesoporous can serve as channel, allow reactants and products to pass in and out catalytic inner, to improve reaction effect
Rate.Preferably, described its specific surface area of N doping ruthenium base biology Pd/carbon catalyst is 50~800m2/ g, wherein the ratio table of micropore
Area accounts for 50~80%, Kong Rongwei, 0.05~0.5cm of total specific surface area3/ g, average pore size are 3~15nm.Further, than
Surface area is 80~110m2/ g, wherein the specific surface area of micropore account for 65~75%, the Kong Rongwei 0.05 of total specific surface area~
0.10cm3/ g, average pore size are 13~15nm.
The present invention provides a kind of preparation method such as above-mentioned N doping ruthenium base biology Pd/carbon catalyst, comprising:
1) biomass material, bicarbonate activator are mixed with nitrogen source, carries out nitrating pyrolysis charring in situ, obtains black
Powder；
2) black powder carries out reflow treatment in dilute nitric acid solution, obtains situ Nitrogen Doping charcoal；
3) situ Nitrogen Doping charcoal is distributed in ruthenium salting liquid, after sonicated and mechanical stirring, then is steamed
It is dry, N2Autoreduction ruthenium is roasted under atmosphere, obtains N doping ruthenium base biology Pd/carbon catalyst.
Preferably, original position nitrating pyrolysis charring includes: by biomass material, bicarbonate activator in the step 1)
It mixes and grinds with nitrogen source 1:1~8:1~10 in mass ratio, in N2Under atmosphere, 450~800 DEG C are warming up to, maintains temperature 0.5
~5h.Situ Nitrogen Doping charcoal can adjust the forms of nitrogen in final product char by adjusting pyrolysis temperature, further
Preferably 500~700 DEG C.
Heretofore described biomass material type has very much, and it is useless to can be selected from timber, crops, herbaceous plant or agricultural
Gurry etc., preferably timber and agriculture and forestry organic waste material.Preferably, biomass material include one of pinus sylvestris var. mongolica, rice husk, Liu An or
It is several.
Need to be added bicarbonate activator before biomass material pyrolysis in the present invention and activate, by biomass material with
Bicarbonate activator is mixed.Preferably, the bicarbonate activator is sodium bicarbonate and/or saleratus；Into
One step is preferably sodium bicarbonate.Activator is decomposed during with biomass material mixing copyrolysis, generates CO2While
Alkaline matter can also be generated and reacted with biomass, the pore structure of the Carbon Materials generated is developed, and then formed micro-
Hole and the mesoporous two-stage pore structure coexisted.
Heretofore described nitrogen source includes one or more of urea, melamine, ovalbumin.Nitrogen source with biology
During matter raw material mixed pyrolysis, wherein nitrogen source can occur to couple in succession with the biomass carbon of formation, and then make N doping in charcoal
Skeleton in, achieve the purpose that modified.
Preferably, reflow treatment includes: that black powder is dispersed in dilute nitric acid solution to stir back in the step 2)
4~8h is flowed, is then rinsed through deionized water to neutrality, obtains situ Nitrogen Doping charcoal after heating, drying；The dust technology is molten
The mass concentration of liquid is 1~20%.Charcoal after pyrolysis is handled with acid solution, can be removed wherein substantial portion of
Ash content, and then influence of the ash content to subsequent reactions can be reduced when being used as catalyst carrier.Dust technology processing can be in Carbon Materials table
Face introduces reactive group, to improve the ability of its load active component.
Ruthenium salt is one or more of ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium in heretofore described step 3)；It is further excellent
It is selected as ruthenic chloride.
The concentration of ruthenium salting liquid is 0.025~0.75mol/L in heretofore described step 3).Preferably, the ruthenium
The concentration of salting liquid is 0.05~0.075mol/L.The concentration of ruthenium salting liquid is proportional to the activation thermal cracking charcoal for being supported on functionalization
On metal Ru amount, if the concentration of ruthenium salting liquid is excessive, the too high levels of metal Ru, dispersion degree can decline, and cause to react
Activity and selectivity decline；If the concentration of ruthenium salting liquid is too small, metal ruthenium content is too low, then optimal catalytic effect is not achieved.
Sonication treatment time is 20~100min in heretofore described step 3), and the mechanical stirring time is 6~12h, N2
It is 1~4h that the autoreduction time is roasted under atmosphere.
The present invention also provides a kind of if above-mentioned N doping ruthenium base biology Pd/carbon catalyst is in CO2Application in synthesizing methane.
Preferably, the N doping ruthenium base biology Pd/carbon catalyst is in CO2Application in synthesizing methane, comprising: mix nitrogen
Miscellaneous ruthenium base biology Pd/carbon catalyst is fitted into reactor, and without reduction process, by CO2、H2With N2Gaseous mixture with 2000~
10000ml·g-1·h-1Feed space velocities be passed through in reactor, reacted under conditions of 200~500 DEG C, 0~5MPa,
H in the gaseous mixture2With CO2Volume ratio be 3~5.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) N doping ruthenium base biology Pd/carbon catalyst is made of carrier and active component, and carrier is situ Nitrogen Doping charcoal,
It is modified that biomass passes through functionalization nitrating in situ, so that on carrier there is different nitrogen form (at least to contain pyridine nitrogen and pyrroles
Nitrogen) and two-stage pore structure (micropore and mesoporous).
(2) nitrogen is introduced in the carrier of N doping ruthenium base biology Pd/carbon catalyst, Electronic Structure is changed, thus more
Added with the dispersion and fixation conducive to active component ruthenium, while the surface alkalinty of carrier is increased, may advantageously facilitate reactant CO2's
Absorption.
(3) N doping ruthenium base biology Pd/carbon catalyst is in CO2It is high with catalytic activity in methanation reaction, selectivity is good excellent
Point, CO2Conversion ratio can achieve 90% or more, CH4Selectivity can achieve 90% or more.
Detailed description of the invention
Fig. 1 is the XPS result figure of 3Ru/4N-ABC1-600 prepared by embodiment 1.
Specific embodiment
Below with reference to specific embodiment, present invention will be explained in further detail.
Embodiment 1
(1) by pinus sylvestris var. mongolica, NaHCO3It mixes with urea according to mass ratio 1:3:4, is put into quartz boat after grinding uniformly,
Tube furnace N2Under atmosphere, 600 DEG C are risen to the rate of 5 DEG C/min and keeps 1h, carry out nitrating pyrolysis charring in situ, obtain black
Thermal cracking carbon powder.
(2) obtained black thermal cracking carbon powder is stirred at reflux 6h in the dilute nitric acid solution that concentration is 6.3%, then
It rinses through deionized water to neutrality, obtains situ Nitrogen Doping charcoal after heating, drying.
(3) 5g situ Nitrogen Doping charcoal obtained above is taken, the ruthenic chloride that 20ml concentration is 0.075mol/L is added to
In solution, after ultrasonication 30min, then mechanical stirring 10h, solvent evaporated is heated, and in N24h is roasted under atmosphere, obtains Ru
Load capacity is the N doping ruthenium base biology Pd/carbon catalyst of 3wt%, is denoted as: 3Ru/4N-ABC1-600.
(4) elemental analysis is carried out for 3Ru/4N-ABC1-600, N doping amount is 14.0wt%.
XPS characterization is carried out for 3Ru/4N-ABC1-600, as shown in Figure 1, its surface pyridine nitrogen content is total nitrogen content
37.7%, surface pyrroles's nitrogen content is the 46.5% of total nitrogen content.
BET characterization, specific surface area 100m are carried out for 3Ru/4N-ABC1-6002/ g, wherein the specific surface area of micropore accounts for
72.5%, the Kong Rongwei 0.1cm of total specific surface area3/ g, average pore size 13.4nm.
(5) the 3Ru/4N-ABC1-600 catalyst for taking the above-mentioned preparation of 1g, is fitted into fixed bed reactors, by CO2、H2With N2
Gaseous mixture be passed through carry out active testing from the upper end of reactor, temperature of reactor is adjusted to 380 DEG C, pressure control in 1MPa,
Raw material (H2With CO2Volume ratio be 4) with 6000h-1Air speed is reacted.Reaction product is through chromatographic, as a result are as follows:
CO2Conversion ratio is 94%, CH4Selectivity is 91%.
Embodiment 2
(1) situ Nitrogen Doping biology high-area carbon is prepared by the same method of embodiment 1 and N doping ruthenium base charcoal is catalyzed
Agent obtains the N doping ruthenium base that Ru load capacity is 2wt% except that the concentration of chlorination ruthenium solution used is 0.05mol/L
Biological Pd/carbon catalyst, is denoted as: 2Ru/4N-ABC1-600.
(2) elemental analysis and XPS characterization are carried out for 2Ru/4N-ABC1-600, N doping amount is 14.4wt%, surface
Pyridine nitrogen content is the 38.0% of total nitrogen content, and surface pyrroles's nitrogen content is the 46.8% of total nitrogen content.
BET characterization, specific surface area 105m are carried out for 2Ru/4N-ABC1-6002/ g, wherein the specific surface area of micropore accounts for
68.2%, the Kong Rongwei 0.1cm of total specific surface area3/ g, average pore size 12.9nm.
(3) catalyst performance is tested according to the same manner as in Example 1, as a result are as follows: CO2Conversion ratio is 90%, CH4Selectivity
It is 83%.
Comparative example 1
(1) biological high-area carbon is prepared by the same method of embodiment 1, except that pinus sylvestris var. mongolica and NaHCO3According to quality
It is mixed than 1:3, is not incorporated into nitrogen source.Catalyst is prepared by the same method of embodiment 2, obtaining Ru load capacity is 2wt%
Ruthenium base biology Pd/carbon catalyst, be denoted as: 2Ru/ABC1-600.
(2) elemental analysis is carried out for 2Ru/ABC1-600, N doping amount is 0wt%.
BET characterization, specific surface area 342m are carried out for 2Ru/ABC1-6002/ g, wherein the specific surface area of micropore accounts for always
76.1%, the Kong Rongwei 0.2cm of specific surface area3/ g, average pore size 8.4nm.
(3) catalyst performance is tested according to the same manner as in Example 1, as a result are as follows: CO2Conversion ratio is 78%, CH4Selectivity
It is 77%.
Embodiment 3
(1) situ Nitrogen Doping biology high-area carbon is prepared by the same method of embodiment 1 and N doping ruthenium base charcoal is catalyzed
Agent, except that pinus sylvestris var. mongolica and NaHCO3And urea is mixed according to mass ratio 1:3:6.Obtain the nitrogen that Ru load capacity is 3wt%
Ruthenium base biology Pd/carbon catalyst is adulterated, is denoted as: 3Ru/6N-ABC1-600.
(2) elemental analysis and XPS characterization are carried out for 3Ru/6N-ABC1-600, N doping amount is 16.8wt%, surface
Pyridine nitrogen content is the 39.3% of total nitrogen content, and surface pyrroles's nitrogen content is the 48.0% of total nitrogen content.
BET characterization, specific surface area 82m are carried out for 3Ru/6N-ABC1-6002/ g, wherein the specific surface area of micropore accounts for
68.3%, the Kong Rongwei 0.08cm of total specific surface area3/ g, average pore size 14.2nm.
(3) catalyst performance is tested according to the same manner as in Example 1, as a result are as follows: CO2Conversion ratio is 92%, CH4Selectivity
It is 90%.
Embodiment 4
(1) situ Nitrogen Doping biology high-area carbon is prepared by the same method of embodiment 1 and N doping ruthenium base charcoal is catalyzed
Agent, except that the temperature of N doping biomass pyrolytic charing is 700 DEG C.Obtain the N doping ruthenium that Ru load capacity is 3wt%
Base biology Pd/carbon catalyst, is denoted as: 3Ru/4N-ABC1-700.
(2) elemental analysis and XPS characterization are carried out for 3Ru/4N-ABC1-700, N doping amount is 14.8wt%, surface
Pyridine nitrogen content is the 26.6% of total nitrogen content, and surface pyrroles's nitrogen content is the 61.8% of total nitrogen content.
BET characterization, specific surface area 620m are carried out for 3Ru/4N-ABC1-7002/ g, wherein the specific surface area of micropore accounts for
71.3%, the Kong Rongwei 0.18cm of total specific surface area3/ g, average pore size 4.2nm.
(3) catalyst performance is tested according to the same manner as in Example 1, except that reaction temperature is 400 DEG C, as a result
Are as follows: CO2Conversion ratio is 88%, CH4Selectivity is 89%.
Embodiment 5
(1) situ Nitrogen Doping biology high-area carbon is prepared by the same method of embodiment 1 and N doping ruthenium base charcoal is catalyzed
Agent, except that the temperature of N doping biomass pyrolytic charing is 500 DEG C.Obtain the N doping ruthenium that Ru load capacity is 3wt%
Base biology Pd/carbon catalyst, is denoted as: 3Ru/4N-ABC1-500.
(2) elemental analysis and XPS characterization are carried out for 3Ru/4N-ABC1-500, N doping amount is 12.5wt%, surface
Pyridine nitrogen content is the 31.4% of total nitrogen content, and surface pyrroles's nitrogen content is the 33.5% of total nitrogen content.
BET characterization, specific surface area 65m are carried out for 3Ru/4N-ABC1-5002/ g, wherein the specific surface area of micropore accounts for
66.1%, the Kong Rongwei 0.06cm of total specific surface area3/ g, average pore size 10.5nm.
(3) catalyst performance is tested according to the same manner as in Example 1, except that reaction temperature is 400 DEG C, as a result
Are as follows: CO2Conversion ratio is 89%, CH4Selectivity is 90%.
Embodiment 6
(1) by rice husk, NaHCO3It mixes, is put into quartz boat after grinding uniformly, in pipe according to mass ratio 1:3:4 with urea
Formula furnace N2Under atmosphere, 600 DEG C are risen to the rate of 5 DEG C/min and keeps 1h, carry out nitrating pyrolysis charring in situ, obtain black fever
Crack carbon powder.
(2) obtained black thermal cracking carbon powder is stirred at reflux 6h in the dilute nitric acid solution that concentration is 10%, then
It rinses through deionized water to neutrality, obtains situ Nitrogen Doping charcoal after heating, drying.
(3) 5g situ Nitrogen Doping charcoal obtained above is taken, it is molten to be added to the nitric acid ruthenium that 20ml concentration is 0.05mol/L
In liquid, after ultrasonication 30min, then mechanical stirring 10h, solvent evaporated is heated, and in N24h is roasted under atmosphere, it is negative to obtain Ru
Carrying capacity is the N doping ruthenium base biology Pd/carbon catalyst of 2wt%, is denoted as: 2Ru/4N-ABC2-600.
(4) elemental analysis and XPS characterization are carried out for 2Ru/4N-ABC2-600, N doping amount is 11.2wt%, surface
Pyridine nitrogen content is the 28.9% of total nitrogen content, and surface pyrroles's nitrogen content is the 36.5% of total nitrogen content.
BET characterization, specific surface area 118m are carried out for 2Ru/4N-ABC2-6002/ g, wherein the specific surface area of micropore accounts for
66.5%, the Kong Rongwei 0.1cm of total specific surface area3/ g, average pore size 12.8nm.
(5) catalyst performance is tested according to the same manner as in Example 1, except that reaction temperature is 400 DEG C, reaction pressure
Power 2MPa, unstrpped gas air speed is with 3000h-1It is reacted.As a result are as follows: CO2Conversion ratio is 88%, CH4Selectivity is 85%.
Embodiment 7
(1) by Liu An, NaHCO3It mixes, is put into quartz boat after grinding uniformly, in pipe according to mass ratio 1:3:4 with urea
Formula furnace N2Under atmosphere, 600 DEG C are risen to the rate of 5 DEG C/min and keeps 1h, carry out nitrating pyrolysis charring in situ, obtain black fever
Crack carbon powder.
(2) obtained black thermal cracking carbon powder is stirred at reflux 6h in the dilute nitric acid solution that concentration is 15%, then
It rinses through deionized water to neutrality, obtains situ Nitrogen Doping charcoal after heating, drying.
(3) 5g situ Nitrogen Doping charcoal obtained above is taken, the nitric acid ruthenium that 20ml concentration is 0.075mol/L is added to
In solution, after ultrasonication 30min, then mechanical stirring 10h, solvent evaporated is heated, and in N24h is roasted under atmosphere, obtains Ru
Load capacity is the N doping ruthenium base biology Pd/carbon catalyst of 3wt%, is denoted as: 3Ru/4N-ABC3-600.
(4) elemental analysis and XPS characterization are carried out for 3Ru/4N-ABC3-600, N doping amount is 14.5wt%, surface
Pyridine nitrogen content is the 32.8% of total nitrogen content, and surface pyrroles's nitrogen content is the 40.2% of total nitrogen content.
BET characterization, specific surface area 106m are carried out for 3Ru/4N-ABC3-6002/ g, wherein the specific surface area of micropore accounts for
66.3%, the Kong Rongwei 0.1cm of total specific surface area3/ g, average pore size 12.8nm.
(5) catalyst performance is tested according to the same manner as in Example 1, as a result are as follows: CO2Conversion ratio is 90%, CH4Selectivity
It is 86%.
Claims (10)
1. a kind of N doping ruthenium base biology Pd/carbon catalyst, which is characterized in that using situ Nitrogen Doping charcoal as carrier, with metal Ru
For active component；The load capacity of the metal Ru is 0.5~5wt%；The N doping amount is 5~20wt%, the N doping
Forms of nitrogen include pyridine nitrogen and pyrroles's nitrogen；The N doping ruthenium base biology Pd/carbon catalyst have micropore with it is mesoporous.
2. N doping ruthenium base biology Pd/carbon catalyst according to claim 1, which is characterized in that wherein surface pyridine nitrogen content
It is the 15~45% of total nitrogen content, surface pyrroles's nitrogen content is the 25~65% of total nitrogen content.
3. N doping ruthenium base biology Pd/carbon catalyst according to claim 1, which is characterized in that its specific surface area be 50~
800m2/ g, wherein the specific surface area of micropore accounts for 50~80%, Kong Rongwei, 0.05~0.5cm of total specific surface area3/ g, average pore size
For 3~15nm.
4. a kind of preparation method of the N doping ruthenium base biology Pd/carbon catalyst as described in claims 1 to 3 is any, feature exist
In, comprising:
1) biomass material, bicarbonate activator are mixed with nitrogen source, carries out nitrating pyrolysis charring in situ, obtains black powder
End；
2) black powder carries out reflow treatment in dilute nitric acid solution, obtains situ Nitrogen Doping charcoal；
3) situ Nitrogen Doping charcoal is distributed in ruthenium salting liquid, after sonicated and mechanical stirring, then is evaporated, N2
Autoreduction ruthenium is roasted under atmosphere, obtains N doping ruthenium base biology Pd/carbon catalyst.
5. the preparation method of N doping ruthenium base biology Pd/carbon catalyst according to claim 4, which is characterized in that the step
1) in situ nitrating pyrolysis charring include: by biomass material, bicarbonate activator and nitrogen source 1:1~8:1 in mass ratio~
10 mix and grind, in N2Under atmosphere, 450~800 DEG C are warming up to, maintains 0.5~5h of temperature.
6. the preparation method of N doping ruthenium base biology Pd/carbon catalyst according to claim 4, which is characterized in that the biology
Matter raw material includes one or more of pinus sylvestris var. mongolica, rice husk, Liu An；The bicarbonate activator is sodium bicarbonate and/or carbon
Potassium hydrogen phthalate；The nitrogen source includes one or more of urea, melamine, ovalbumin.
7. the preparation method of N doping ruthenium base biology Pd/carbon catalyst according to claim 4, which is characterized in that the step
2) reflow treatment includes: and black powder is dispersed in dilute nitric acid solution to be stirred at reflux 4~8h in, then rinses through deionized water
To neutrality, situ Nitrogen Doping charcoal is obtained after heating, drying；The mass concentration of the dilute nitric acid solution is 1~20%.
8. the preparation method of N doping ruthenium base biology Pd/carbon catalyst according to claim 4, which is characterized in that the step
3) ruthenium salt is one or more of ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium in；The concentration of the ruthenium salting liquid be 0.025~
0.75mol/L。
9. the preparation method of N doping ruthenium base biology Pd/carbon catalyst according to claim 4, which is characterized in that the step
3) sonication treatment time is 20~100min in, and the mechanical stirring time is 6~12h, N2Under atmosphere roast the autoreduction time be 1~
4h。
10. a kind of N doping ruthenium base biology Pd/carbon catalyst as described in claims 1 to 3 is any is in CO2Answering in synthesizing methane
With.
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