CN106966359A - The method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse - Google Patents
The method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse Download PDFInfo
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- CN106966359A CN106966359A CN201710205263.XA CN201710205263A CN106966359A CN 106966359 A CN106966359 A CN 106966359A CN 201710205263 A CN201710205263 A CN 201710205263A CN 106966359 A CN106966359 A CN 106966359A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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Abstract
The method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse, biomass or house refuse are placed in dilute sulfuric acid, then the sodium vanadate and micro DMSO for adding catalytic amount carry out oxydrolysis, cellulose therein and hemicellulose is quantitatively changed into formic acid and obtain solution A；Added into solution A in NaOH and dilute sulfuric acid to the pH value of solution A is 1.4 2.3, the formic acid release hydrogen then added thereto again in transition metal iridium homogeneous catalyst catalyzing hydrolysis liquid, while the CO produced2Carbonate is transformed into by alkali liquor absorption.The present invention has good compatibility, middle without complicated separation application.Compared with existing homogeneous catalysis technology, hydrogen manufacturing yield >=84%, almost Quantitative yield is H for cellulose and hemicellulose2；Aqueous phase reactions system, participates in without a large amount of organic solvents, reduces cost and environmental pollution.
Description
Technical field
The invention belongs to chemical field, energy conversion field, and in particular to a kind of catalysis of transition metal iridium from biomass and
The method that hydrogen is prepared in the hydrolyzate of house refuse.
Background technology
With the continuous progress and the fast development of industrialization degree of society, human society is all to the demand of the energy and day
Increase.At the same time, during the increasingly depleted of fossil resource and use caused by CO2Discharge capacity increases and air pollution has turned into
Two hang-ups of the most serious that 21 century human society faces.Therefore find largely abundant renewable and clean energy resource has turned into complete
The important scientific issues of World Focusing.The characteristics of hydrogen has fuel value height, combustion product no pollution, is preferable clean energy resource
Carrier.Biomass is one of regenerative resource most abundant on the earth, if carrying out energy using abundant non-grain biomass resource
Source is converted, and therefrom hydrogen making, an effective solution is provided by the sustainable clean energy resource problem for World Focusing.
The technology for carrying out energy conversion currently with biomass mainly includes two aspects：First, it is high in harsh high temperature
Gasified under the conditions of pressure, high temperature pyrolysis or in supercritical water vaporizing system for hydrogen (Toonssen, R.；Woudstra,
N.；Verkooijen,A.H.M.,Exergy analysis of hydrogen production plants based on
biomass gasification.International Journal of Hydrogen Energy 2008,33(15),
4074-4082.Cortright,R.D.；Davda,R.R.；Dumesic,J.A.,Hydrogen from catalytic
reforming of biomass-derived hydrocarbons in liquid water.Nature(London,U.K.)
2002,418(6901)964-967.Azadi,P.；Farnood,R.,Review of heterogeneous catalysts
for sub-and supercritical water gasification of biomass and
Wastes.International Journal of Hydrogen Energy 2011,36 (16), 9529-9541.), still
Harsh reaction condition and a certain amount of CO, CO are generated during the course of the reaction2, CH4And H2Mix and seriously limit this
The application prospect of technology；Second, prepare hydrogen (Woodward, J. in a mild condition using enzyme technology；Mattingly,
S.M.；Danson,M.；Hough,D.；Ward,N.；Adams,M.,In vitro hydrogen production by
glucose dehydrogenase and hydrogenase.Nat Biotech 1996,14(7),872-874.RDO de
Barros,；R.de S Paredes,；Endo,T.；Bon,E.P.；Lee,S.H.,Association of wet disk
milling and ozonolysis as pretreatment for enzymatic saccharification of
Sugarcane bagasse and straw.Bioresource technology 2013,136,288-294.), however it is high
The cost of volume and slow hydrogen manufacturing speed are the bottlenecks of this technology.
Relevant " research prepares hydrogen with homogeneous catalysis technology from biomass " only has two at present., Germany in 2010
Wasserscheid professors group is reported at 150-180 DEG C, uses [(p-cymene) RuCl2]2/ TMEDA catalyst system and catalyzings are from Portugal
H is produced in grape sugar, cellulose2Association CO2Initiative work (Taccardi, N.；Assenbaum,D.；Berger,
M.E.M.；A.；Enzenberger,F.；R.；Neuendorf,S.；Goeke,V.；N.；
Maass,H.J.；Kistenmacher,H.；Wasserscheid,P.,Catalytic production of hydrogen
from glucose and other carbohydrates under exceptionally mild reaction
conditions.Green Chemistry 2010,12(7),1150.).But, continuous 5 additions glucose feed, catalysis
The conversion number of times (TON) of agent accumulation is still less than 200.Author investigation confirms that HCOOH is to produce H in reacting2And CO2It is important in
Mesosome.6mol H are produced according to H element conservation, i.e. 1mol glucose2Calculate, hydrogen manufacturing yield is only 5%.Meanwhile, in reaction also
The ionic liquid for using noncommodity is needed as solvent.
2014, German Beller research groups realized pincer types in a mild condition using ppm ranks
Metal iridium catalyst (IrH2Cl[(i-Pr2PCH2CH2)2] NH) produce hydrogen from saccharide compound, cellulose and biomass.
At 95 DEG C, it is possible to produce H from glucose, fructose, cellobiose2, for glucose and fructose, the TON of catalyst
Exceed 10000；At 120 DEG C, by " one kettle way ", raw material is first passed through into sour water solution, then neutralized with alkali, is added in alkaline environment
Enter catalyst, from cellulose, lignocellulosic, biomass-bamboo willow bits of ecosystem, house refuse-waste and old cigarette filter head
Produce hydrogen (Li, Y.；Sponholz,P.；Nielsen,M.；Junge,H.；Beller,M.,Iridiumcatalyzed
hydrogen production from monosaccharides,disaccharide,cellulose,
andlignocellulose.ChemSusChem 2015,8(5),804-808.).But for monose, the yield of hydrogen
Only 2%, the hydrogen manufacturing yield of other raw materials is less than 1%.And, it is necessary to organic solvent and the NaOH of equivalent.
In summary, " research that energy conversion is carried out using biomass hydrogen preparation " is although in Pintsch process, heterogeneous catalysis
And enzyme catalysis field makes some progress, but significant limitation is still had in actual applications；Using homogeneously
In the research that catalysis technique prepares hydrogen from biomass, although the problem of solving high selectivity at present (only H2And CO2Production
It is raw), but how to promote hydrogen manufacturing efficiently to carry out and show potential application prospect is an extremely challenging problem.
Condition that existing biomass hydrogen preparation technology is present it is harsh (300-1400 DEG C, or>370 DEG C, 230bar), chemistry
Selectivity is not high (to produce substantial amounts of CO and CH4), cost great number (enzyme technology) or low (the homogeneous catalysis technology of hydrogen production efficiency<
5%) the problem of.
The content of the invention
It is catalyzed in a mild condition using transition metal iridium from biomass and life rubbish it is an object of the invention to provide a kind of
The method that hydrogen is prepared in the hydrolyzate of rubbish.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
1) biomass or house refuse are placed in the dilute sulfuric acid that mass concentration is 0.5-1.5%, then add alum acid
Sodium and DMSO are in 2.0-7.0MPa, and 140-170 DEG C of progress oxydrolysis makes cellulose therein and hemicellulose quantitatively change
Solution A is obtained for formic acid；
Wherein press per 1g biomass or house refuse adds 15-45mL dilute sulfuric acids, 0.05-0.15g sodium vanadate and 0-2mL
DMSO；
2) pH value that NaOH neutralisation of sulphuric acid to solution A are added into solution A is 1.4-2.3, is then pressed again per 1g biomass
Or house refuse is added thereto>Formic acid in 15ppm transition metal iridium homogeneous catalyst catalyzing hydrolysis liquid is released at 60-95 DEG C
Hydrogen is put, while the CO produced2Carbonate is transformed into by alkali liquor absorption.
Described biomass uses wheat stalk, maize straw, rice straw or reed rod.
Described house refuse uses bagasse, boxboard or old newsprint.
The step 1) oxydrolysis carried out in oxygen or air.
Described transition metal iridium uses Cp*IrH2O[(4,4’-dihydroxy-2,2’-bipyridine)]·SO4、
Cp*IrH2O[(6-(1H-imidazol-2-yl)pyrimidine-2,4-diol)]·SO4、Cp*IrH2O[6-(4,5-
dihydro-1H-imidazol-2-yl)pyrimidine-2,4-diol]·SO4Or [(Cp*IrCl)2(4,4’,6,6’-
tetramethoxybipyrimidine)]Cl2。
The present invention has good compatibility using the two-step reaction system in " one pot of two-step method ", and centre is without complexity
Separation application.Compared with existing homogeneous catalysis technology, hydrogen manufacturing yield is high, to hydrogen manufacturing yield >=84% of wheat stalk,
Almost Quantitative yield is H for cellulose and hemicellulose2；Aqueous phase reactions system, participates in without a large amount of organic solvents, reduces cost
And environmental pollution.Compared with other Pintsch process with heterogeneous catalysis system, reaction condition it is gentle (2.0-7.0MPa air or
140-170 DEG C is hydrolyzed under Oxygen Condition, 60-95 DEG C of release hydrogen), selectivity height (CO≤30ppm, CH4≤ 2ppm), into
This cheap (only needing ppm grades of catalyst), hydrogen fuel cell can be directly applied to.
Embodiment
Here is four kinds of catalyst transition metal iridium that the present invention is used：
1、Cp*IrH2O[(4,4’-dihydroxy-2,2’-bipyridine)]·SO4(Yuichiro Himeda；
Highly efficient hydrogen evolution by decomposition of formic acid using an
iridium catalyst with 4,4’-dihydroxy-2,2’-bipyridine.Green Chem.,2009,11,
2018-2022.)；
2、Cp*IrH2O[(6-(1H-imidazol-2-yl)pyrimidine-2,4-diol)]·SO4(Wang,W.-
H.et al.Highly robust hydrogen generation by bioinspired Ir complexes for
dehydrogenation of formic acid in water:Experimental and theoretical
mechanistic investigations at different pH.ACS Catalysis,2015,5,5496-5504)；
3、Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)pyrimidine-2,4-diol]·SO4
(Wang,W.-H.et al.Highly robust hydrogen generation by bioinspired Ir
complexes for dehydrogenation of formic acid in water:Experimental and
theoretical mechanistic investigations at different pH.ACS Catalysis,2015,5,
5496-5504)；
4、[(Cp*IrCl)2(4,4’,6,6’-tetramethoxybipyrimidine)]Cl2(Hull,J.F.et
al.Reversible hydrogen storage using CO2and a proton-switchable iridium
catalyst in aqueous media under mild temperatures and pressures.Nature
chem.2012,4,383-388.)
Using different type catalyst transition metal iridium catalysis hydrogen making from wheat stalk：
Embodiment 1：
Catalyst uses transition metal iridium Cp*IrH2O[(4,4’-dihydroxy-2,2’-bipyridine)]·SO4
1) weighed in a glass reactor and crushed the wheat stalk 0.94g of 200 mesh sieves and add mass concentration thereto
For 0.7% dilute sulfuric acid 30mL, 0.08g sodium vanadate and 0.31mL DMSO are then added in magnetic agitation under room temperature condition
Fully dissolved to sodium vanadate, in 3.0MPa, 160 DEG C carry out oxydrolysis in atmosphere, obtain the oxydrolysis liquid of wheat stalk,
Isosorbide-5-Nitrae-dioxane is added thereto as internal standard, is used1It is 18mmol, formic acid yield that H NMR, which determine formic acid content in hydrolyzate,
For 100% (being based on inventory C atom computings)；
2) add into the oxydrolysis liquid of wheat stalk in NaOH and dilute sulfuric acid to wheat stalk oxydrolysis liquid
PH value is 1.4, then adds 208ppm transition metal iridium Cp*IrH thereto again2O[(4,4’-dihydroxy-2,2’-
bipyridine)]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 90 DEG C, while the CO produced2Pass through
Alkali liquor absorption is transformed into carbonate.H is obtained after 4h2For 345mL, correct after room temperature, it is 78%, catalyst turn over number to calculate yield
TON is 3767.CO contents are 30ppm, CH in gas4Content is 2ppm, CO2Content<1%.
Embodiment 2：
Catalyst uses transition metal iridium Cp*IrH2O[(6-(1H-imidazol-2-yl)pyrimidine-2,4-
diol)]·SO4, preparation process be the same as Example 1 obtains H after 1h2For 369mL, correct after room temperature, it is 84% to calculate yield, catalysis
Agent turn over number TON is 4040.CO contents are 16ppm, CH in gas4Content is<2ppm, CO2Content<1%.
Embodiment 3：
Using transition metal iridium Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)pyrimidine-2,
4-diol]·SO4H is obtained after preparation process be the same as Example Isosorbide-5-Nitrae 0min2For 384mL, correct after room temperature, it is 87% to calculate yield,
Catalyst turn over number TON is 4188.CO contents are 23ppm, CH in gas4Content is<2ppm, CO2Content<1%.
Embodiment 4：
Catalyst uses transition metal iridium [(Cp*IrCl)2(4,4’,6,6’-tetramethoxybipyrimidine)]
Cl2, preparation process be the same as Example 1 obtains H after 3h2For 360mL, correct after room temperature, it is 82%, catalyst turn over number to calculate yield
TON is 3932.CO contents are 18ppm, CH in gas4Content is<2ppm, CO2Content<1%.
Following examples use transition metal iridium Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)
pyrimidine-2,4-diol]·SO4It is used as catalyst：
Embodiment 5：
1) the wheat stalk 2.82g for crushing 200 mesh sieves is weighed in a glass reactor, mass concentration is added thereto
For 0.7% 90mL dilute sulfuric acid, then add 0.24g sodium vanadate and 0.93mL DMSO is stirred in magnetic force under room temperature condition
Mix to sodium vanadate and fully dissolve, oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half
Cellulose is quantitatively changed into the oxydrolysis liquid that formic acid obtains wheat stalk；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H
It is 53mmol that NMR, which determines formic acid content in hydrolyzate, and yield is 98% (being based on inventory C atom computings).
2) add into the oxydrolysis liquid of wheat stalk in NaOH and dilute sulfuric acid to wheat stalk oxydrolysis liquid
PH value is 2.3, then adds 69ppm transition metal iridium Cp*IrH thereto again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 90 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 1280mL, after correction room temperature,
It is 97% to calculate yield, and catalyst turn over number TON is 13972.It is 7ppm, CH that gas chromatography, which determines wherein CO contents,4Content
For<2ppm, CO2Content<1%.
Embodiment 6：
1) weighed in a glass reactor and crushed the wheat stalk 4.71g of 200 mesh sieves and add mass concentration thereto
For 0.7% 150mL dilute sulfuric acid, 0.41g sodium vanadate and 1.55mL DMSO are then added in magnetic force under room temperature condition
Stirring fully dissolved to sodium vanadate, oxydrolysis is carried out in 5.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and
Hemicellulose is quantitatively changed into the oxydrolysis liquid that formic acid obtains wheat stalk；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1It is 42mmol that H NMR, which determine formic acid content in hydrolyzate, and yield (is based on inventory C atom computings, the super tuber of stemona point is for 102%
The contribution of other compositions in biomass).
2) add into the oxydrolysis liquid of wheat stalk in NaOH and dilute sulfuric acid to wheat stalk oxydrolysis liquid
PH value is 2.3, then adds 42ppm transition metal iridium Cp*IrH thereto again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 90 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.After 1.0h, H2Volume is 2025mL, after correction room temperature, meter
It is 92% (being based on inventory C atom computings) to calculate yield, and catalyst turn over number TON is 22059.Gas chromatography determines wherein CO
Content is 23ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 7：
1) weighed in a glass reactor and crushed the wheat stalk 9.42g of 200 mesh sieves and add mass concentration thereto
For 0.7% 300mL dilute sulfuric acid, then add 0.81g sodium vanadate and 3.1mL DMSO is stirred in magnetic force under room temperature condition
Mix to sodium vanadate and fully dissolve, oxydrolysis is carried out in 5.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half
Cellulose is quantitatively changed into the oxydrolysis liquid that formic acid obtains wheat stalk；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H
It is 180mmol that NMR, which determines formic acid content in hydrolyzate, and yield is 100% (being based on inventory C atom computings).
2) add into the oxydrolysis liquid of wheat stalk in NaOH and dilute sulfuric acid to wheat stalk oxydrolysis liquid
PH value is 2.3, then adds 63ppm transition metal iridium Cp*IrH thereto again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 90 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.After 1.6h, H2Volume is 3956mL, after correction room temperature, meter
It is 90% (being based on inventory C atom computings) to calculate yield, and catalyst turn over number TON is 14381.Gas chromatography determines wherein CO
Content is 18ppm, CH4Content is<2ppm, CO2Content<1%.
Following examples use transition metal iridium Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)
pyrimidine-2,4-diol]·SO4As catalyst from maize straw, rice straw and reed rod hydrogen making：
Embodiment 8：
1) weighed in a glass reactor and crushed the maize straw 3.03g of 200 mesh sieves and add mass concentration thereto
For 0.7% 90mL dilute sulfuric acid, then add 0.24g sodium vanadate and 0.93mL DMSO is stirred in magnetic force under room temperature condition
Mix to sodium vanadate and fully dissolve, oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half
Cellulose is quantitatively changed into the oxydrolysis liquid that formic acid obtains maize straw；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H
It is 43mmol that NMR, which determines formic acid content in hydrolyzate, and yield is 79% (being based on inventory C atom computings).
2) add into the oxydrolysis liquid of maize straw in NaOH and dilute sulfuric acid to maize straw oxydrolysis liquid
PH value is 2.3, then adds 69ppm transition metal iridium Cp*IrH thereto again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 90 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 937mL, after correction room temperature, meter
It is 71% (being based on inventory C atom computings) to calculate yield, and catalyst turn over number TON is 9650.Gas chromatography determines wherein CO
Content is 12ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 9：
1) weighed in a glass reactor and crushed the rice straw 3.10g of 200 mesh sieves and add mass concentration thereto
For 0.7% 90mL dilute sulfuric acid, then add 0.24g sodium vanadate and 0.93mL DMSO is stirred in magnetic force under room temperature condition
Mix to sodium vanadate and fully dissolve, oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half
Cellulose is quantitatively changed into the oxydrolysis liquid that formic acid obtains rice straw；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H
It is 46mmol that NMR, which determines formic acid content in hydrolyzate, and yield is 86% (being based on inventory C atom computings).
2) add into the oxydrolysis liquid of rice straw in NaOH and dilute sulfuric acid to rice straw oxydrolysis liquid
PH value is 2.3, then adds 69ppm transition metal iridium Cp*IrH thereto again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 90 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 1000mL, after correction room temperature,
It is 76% (being based on inventory C atom computings) to calculate yield, and catalyst turn over number TON is 10174.Gas chromatography is determined wherein
CO contents are 7ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 10：
1) weighed in a glass reactor and crushed the reed rod 3.64g of 200 mesh sieves and add mass concentration thereto and be
0.7% 90mL dilute sulfuric acid, then adds 0.24g sodium vanadate and 0.93mL DMSO in magnetic agitation under room temperature condition
Fully dissolved to sodium vanadate, oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half fibre
Dimension element is quantitatively changed into the oxydrolysis liquid that formic acid obtains reed rod；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H NMR
It is 46mmol to determine formic acid content in hydrolyzate, and yield is 86% (being based on inventory C atom computings).
2) pH value in NaOH with dilute sulfuric acid to the oxydrolysis liquid of reed rod is added into the oxydrolysis liquid of reed rod
For 2.3,69ppm transition metal iridium Cp*IrH is then added thereto again2O[6-(4,5-dihydro-1H-imidazol-2-
yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 90 DEG C, produces simultaneously
Raw CO2Carbonate is transformed into by alkali liquor absorption.After 30min, H2Volume is 1093mL, after correction room temperature, calculates yield and is
83% (being based on inventory C atom computings), catalyst turn over number TON is 10890.Gas chromatography determines wherein CO contents
15ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 11-13 uses transition metal iridium Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)
pyrimidine-2,4-diol]·SO4As catalyst from bagasse, boxboard and old newsprint hydrogen making：
Embodiment 11：
1) weighed in a glass reactor and crushed the bagasse 2.80g of 200 mesh sieves and add mass concentration thereto and be
0.7% 90mL dilute sulfuric acid, then adds 0.24g sodium vanadate and 0.93mL DMSO in magnetic agitation under room temperature condition
Fully dissolved to sodium vanadate, oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, make cellulose therein and half fibre
Dimension element is quantitatively changed into the oxydrolysis liquid that formic acid obtains bagasse；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H NMR
It is 57mmol to determine formic acid content in hydrolyzate, and yield (is based on inventory C atom computings, the super tuber of stemona point is bagasse for 106%
The contribution of middle other compositions).
2) pH value in NaOH with dilute sulfuric acid to the oxydrolysis liquid of bagasse is added into the oxydrolysis liquid of bagasse
For 2.3,69ppm transition metal iridium Cp*IrH is then added thereto again2O[6-(4,5-dihydro-1H-imidazol-2-
yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 90 DEG C, produces simultaneously
Raw CO2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 1235mL, after correction room temperature, calculates yield and is
94% (being based on inventory C atom computings), catalyst turn over number TON is 13473.Gas chromatography determines wherein CO contents
6ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 12：
1) the boxboard 2.60g of crushing is weighed in a glass reactor, and to add mass concentration thereto be 0.7%
90mL dilute sulfuric acid, then adds 0.24g sodium vanadate and 0.93mL DMSO in magnetic agitation under room temperature condition to alum acid
Sodium is fully dissolved, and oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, makes cellulose therein and hemicellulose fixed
Amount ground is changed into the oxydrolysis liquid that formic acid obtains boxboard；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H NMR determine water
It is 49mmol to solve formic acid content in liquid, and yield is 90% (being based on inventory C atom computings).
2) pH value in NaOH with dilute sulfuric acid to the oxydrolysis liquid of boxboard is added into the oxydrolysis liquid of boxboard
For 2.3,69ppm transition metal iridium Cp*IrH is then added thereto again2O[6-(4,5-dihydro-1H-imidazol-2-
yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 90 DEG C, produces simultaneously
Raw CO2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 1065mL, after correction room temperature, calculates yield and is
81% (being based on inventory C atom computings), catalyst turn over number TON is 11611.Gas chromatography determines wherein CO contents
10ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 13：
1) the old newsprint sample 2.89g that crushing is weighed in a glass reactor adds mass concentration for 0.7% thereto
90mL dilute sulfuric acid, then add 0.24g sodium vanadate and 0.93mL DMSO in magnetic agitation under room temperature condition to alum
Sour sodium is fully dissolved, and oxydrolysis is carried out in 3.0MPa, 160 DEG C of oxygen atmosphere, makes cellulose therein and hemicellulose
Quantitatively it is changed into the oxydrolysis liquid that formic acid obtains old newsprint；Isosorbide-5-Nitrae-dioxane is added as internal standard, is used1H NMR are determined
Formic acid content is 46mmol in hydrolyzate, and yield is 86% (being based on inventory C atom computings).
2) pH value in NaOH with dilute sulfuric acid to the oxydrolysis liquid of old newsprint is added into the oxydrolysis liquid of old newsprint
For 2.3,69ppm transition metal iridium Cp*IrH is then added thereto again2O[6-(4,5-dihydro-1H-imidazol-2-
yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 90 DEG C, produces simultaneously
Raw CO2Carbonate is transformed into by alkali liquor absorption.After 24min, H2Volume is 914mL, after correction room temperature, calculates yield and is
69% (being based on inventory C atom computings), catalyst turn over number TON is 9985.Gas chromatography determines wherein CO contents
8ppm, CH4Content is<2ppm, CO2Content<1%.
Embodiment 14：
1) the maize straw sample 1.01g that crushing is weighed in a glass reactor adds mass concentration and is thereto
0.5% 15mL sulfuric acid, then adds 0.08g sodium vanadate and 1mL DMSO in magnetic agitation under room temperature condition to alum
Sour sodium is fully dissolved, and oxydrolysis is carried out in 3MPa, 150 DEG C of air atmosphere, makes cellulose therein and hemicellulose fixed
Amount ground is changed into the oxydrolysis liquid that formic acid obtains maize straw；
2) NaOH neutralisation of sulphuric acid is added into the oxydrolysis liquid of maize straw to the pH of the oxydrolysis liquid of maize straw
It is worth for 1.4, then adds 15ppm Cp*IrH thereto by every 1g biomass or house refuse again2O[(4,4’-
dihydroxy-2,2’-bipyridine)]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 60 DEG C, together
When the CO that produces2Carbonate is transformed into by alkali liquor absorption.
Embodiment 15：
1) the reed rod sample 1.2g of crushing is weighed in a glass reactor, and to add mass concentration thereto be 1.0%
20mL sulfuric acid, then adds 0.05g sodium vanadate and 0.5mL DMSO fills in magnetic agitation under room temperature condition to sodium vanadate
Divide dissolving, oxydrolysis is carried out in 5MPa, 140 DEG C of air atmosphere, cellulose therein and hemicellulose is quantitatively turned
It is changed into the oxydrolysis liquid that formic acid obtains reed rod；
2) NaOH neutralisation of sulphuric acid to the pH value of the oxydrolysis liquid of reed rod is added into the oxydrolysis liquid of reed rod is
1.8, then add 20ppm Cp*IrH thereto by every 1g biomass or house refuse again2O[(6-(1H-imidazol-2-
yl)pyrimidine-2,4-diol)]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 80 DEG C, simultaneously
The CO of generation2Carbonate is transformed into by alkali liquor absorption.
Embodiment 16：
1) the bagasse sample 0.92g that crushing is weighed in a glass reactor adds mass concentration for 1.5% thereto
40mL sulfuric acid, the sodium vanadate for then adding 0.12g fully dissolves in magnetic agitation under room temperature condition to sodium vanadate,
Oxydrolysis is carried out in 7MPa, 170 DEG C of air atmosphere, cellulose therein and hemicellulose is quantitatively changed into formic acid and obtains
To the oxydrolysis liquid of bagasse；
2) NaOH neutralisation of sulphuric acid to the pH value of the oxydrolysis liquid of bagasse is added into the oxydrolysis liquid of bagasse is
2.0, then add 45ppm Cp*IrH thereto by every 1g biomass or house refuse again2O[6-(4,5-dihydro-1H-
imidazol-2-yl)pyrimidine-2,4-diol]·SO4Formic acid in homogeneous catalyst catalyzing hydrolysis liquid is in 85 DEG C of releases
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.
Embodiment 17：
1) the boxboard sample 0.85g that crushing is weighed in a glass reactor adds mass concentration for 1.2% thereto
45mL sulfuric acid, then add 0.15g sodium vanadate and 2.0mL DMSO in magnetic agitation under room temperature condition to sodium vanadate
Fully dissolving, carries out oxydrolysis in 2MPa, 145 DEG C of oxygen or air atmosphere, makes cellulose therein and hemicellulose
Quantitatively it is changed into the oxydrolysis liquid that formic acid obtains boxboard；
2) NaOH neutralisation of sulphuric acid to the pH value of the oxydrolysis liquid of boxboard is added into the oxydrolysis liquid of boxboard is
2.3, then add 30ppm [(Cp*IrCl) thereto by every 1g biomass or house refuse again2(4,4’,6,6’-
tetramethoxybipyrimidine)]Cl2Formic acid in homogeneous catalyst catalyzing hydrolysis liquid discharges hydrogen at 95 DEG C, simultaneously
The CO of generation2Carbonate is transformed into by alkali liquor absorption.
Claims (5)
1. the method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse, it is characterised in that including
Following steps：
1) by biomass or house refuse be placed in mass concentration be 0.5-1.5% dilute sulfuric acid in, then add sodium vanadate and
DMSO makes cellulose therein and hemicellulose quantitatively be changed into first in 2.0-7.0MPa, 140-170 DEG C of progress oxydrolysis
Acid obtains solution A；
Wherein press per 1g biomass or house refuse adds 15-45mL dilute sulfuric acids, 0.05-0.15g sodium vanadate and 0-2mL
DMSO；
2) added into solution A in NaOH and dilute sulfuric acid to the pH value of solution A be 1.4-2.3, then press again per 1g biomass or
House refuse is added thereto>Formic acid in 15ppm transition metal iridium homogeneous catalyst catalyzing hydrolysis liquid is in 60-95 DEG C of release
Hydrogen, while the CO produced2Carbonate is transformed into by alkali liquor absorption.
2. transition metal iridium catalysis according to claim 1 prepares hydrogen from the hydrolyzate of biomass and house refuse
Method, it is characterised in that：Described biomass uses wheat stalk, maize straw, rice straw or reed rod.
3. transition metal iridium catalysis according to claim 1 prepares hydrogen from the hydrolyzate of biomass and house refuse
Method, it is characterised in that：Described house refuse uses bagasse, boxboard or old newsprint.
4. transition metal iridium catalysis according to claim 1 prepares hydrogen from the hydrolyzate of biomass and house refuse
Method, it is characterised in that：The step 1) oxydrolysis carried out in oxygen or air.
5. transition metal iridium catalysis according to claim 1 prepares hydrogen from the hydrolyzate of biomass and house refuse
Method, it is characterised in that：Described transition metal iridium is used
Cp*IrH2O[(4,4’-dihydroxy-2,2’-bipyridine)]·SO4、
Cp*IrH2O[(6-(1H-imidazol-2-yl)pyrimidine-2,4-diol)]·SO4、
Cp*IrH2O[6-(4,5-dihydro-1H-imidazol-2-yl)pyrimidine-2,4-diol]·SO4Or
[(Cp*IrCl)2(4,4’,6,6’-tetramethoxybipyrimidine)]Cl2。
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| CN112390225A (en) * | 2020-11-18 | 2021-02-23 | 云南电网有限责任公司电力科学研究院 | Homogeneous catalytic dehydrogenation method by utilizing interface between aqueous solution and organic liquid hydrogen storage |
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| CN113186562A (en) * | 2021-04-28 | 2021-07-30 | 安徽大学 | Ir @ SC nanoparticle catalyst and preparation and application thereof |
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| CN107799779A (en) * | 2017-10-23 | 2018-03-13 | 清华大学 | Monatomic catalyst of iridium for direct methanoic acid fuel cell and preparation method thereof |
| CN107799779B (en) * | 2017-10-23 | 2021-01-12 | 清华大学 | Iridium monatomic catalyst for direct formic acid fuel cell and preparation method thereof |
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| KR102274756B1 (en) * | 2019-09-18 | 2021-07-08 | 한국에너지기술연구원 | Process for producing hydrogen from biomass at low temperature and low pressure |
| CN111454139A (en) * | 2020-04-29 | 2020-07-28 | 西安交通大学 | Method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis of biomass through trace DMSO (dimethyl sulfoxide) |
| CN111454139B (en) * | 2020-04-29 | 2021-06-11 | 西安交通大学 | Method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis of biomass through trace DMSO (dimethyl sulfoxide) |
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| CN113264504A (en) * | 2021-06-08 | 2021-08-17 | 西安交通大学 | Method for recycling biomass high-efficiency hydrogen production catalytic system |
| CN113264504B (en) * | 2021-06-08 | 2024-02-06 | 西咸新区青氢华屹能源科技有限公司 | Method for recycling biomass efficient hydrogen production catalytic system |
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