CN101049909A - Reforming method for making hydrogen by glycerol steam as by-product for producing biological diesel oil - Google Patents
Reforming method for making hydrogen by glycerol steam as by-product for producing biological diesel oil Download PDFInfo
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- CN101049909A CN101049909A CNA2007100573094A CN200710057309A CN101049909A CN 101049909 A CN101049909 A CN 101049909A CN A2007100573094 A CNA2007100573094 A CN A2007100573094A CN 200710057309 A CN200710057309 A CN 200710057309A CN 101049909 A CN101049909 A CN 101049909A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
This invention discloses a method for preparing H2 from byproduct of biodiesel oil production, glycerin, by steam reforming. The method comprises: filling Rh/CeO2-ZrO2 or Pt/CeO2-ZrO2 or Pd/CeO2-ZrO2 catalyst into a reactor, introducing a mixture of 5 vol. % H2 and N2 at a flow rate of 100 mL/min, pre-reducing the catalyst at 500-600 deg.C for 2-3 h, introducing vapor of glycerin aqueous solution at a space velocity of 10000-50000 h-1, and performing steam reforming at 300-700 deg.C under normal pressure to obtain H2. The content of the active component, Rh, Pt or Pd, is 1-5 wt. %. The water and carbon ratio of the vapor of glycerin aqueous solution is (2-9):1. The method has such advantages as recyclable raw material, no pollution, high catalyst activity and selectivity, and high stability.
Description
Technical field
The present invention relates to a kind of method of the reforming by-product glycerin vapor hydrogen with the production biofuel, specifically under certain processing condition and catalyzer, reform by glycerin vapor and to produce hydrogen, belong to the glycerin vapor reforming hydrogen producing technology.
Background technology
Biofuel (be Fatty acid methyl ester---the reaction of vegetable oil or animal grease and methyl alcohol obtains) becomes the New-type fuel that various countries competitively develop with its abundant raw material sources, good recyclability and the advantage of cleanliness without any pollution, its combustionproperty and mineral diesel are close, and can directly apply to diesel engine, be considered to the substitute of mineral diesel.Ester-interchange method production biofuel meeting by-product glycerol, its output accounts for the 10wt% of yield of biodiesel, and the comprehensive utilization of glycerine helps reducing the production cost of biofuel, promotes the popularization of biofuel.
Hydrogen Energy is in light weight, and thermal conductivity and incendivity are good, calorific value is high, combustion cleaning, is to meet the clean energy that Green Chemistry requires.By the research of biodiesel byproduct product glycerin vapor reforming hydrogen producing process, not only, also solved the problem that byproduct utilizes again for the production process of biofuel for the exploitation of hydrogen energy source searches out a stable biomass hydrogen preparation study route.
People such as J.A.Dumesic (Hydrogen from Catalytic Reforming of Biomass-Derived Hydrocarbons inLiquid Water, Nature.2002,418,964; Raney Ni-Sn Catalyst for H
2Production fromBiomass-Derived Hydrocarbons, Science.2003,300,2075) reported that at first glycerine aqueous-phase reforming under catalyst effects such as Pt, Ni produces the process of hydrogen.When adopting 3wt%Pt/Al
2O
3Catalyzer and when being raw material with the glycerine solution of 10wt%, glycerol conversion yield is 77%, hydrogen selective is 70%, but hydrogen-producing speed only is 2 * 10
4μ molg
-1h
-1, suitable with the speed of glucose fermentation hydrogen manufacturing.When adopting the Ni catalyzer of Sn modification, can when keeping good scission of link performance, reduce the selectivity of alkane, and can obtain catalytic stability preferably.Although the aqueous-phase reforming catalyzer can reach certain activity, product alkane content is more, and reaction needed carries out being higher than under the pressure of 2MPa, and is higher to equipment requirements.
People such as E.Chomet (Hydrogen by Catalytic Steam Reforming of Liquid Byproducts from BiomassThermoconversion Processes, Ind.Eng.Chem.Res.2002,41,4209) nickel catalyzator of employing naphtha reforming, under 850 ℃, carry out the experiment of raw glycerine steam reformation, glycerol conversion yield is 91%～100%, and hydrogen yield is 77%.ToshimitsuSuzuki (Production of Hydrogen by Steam Reforming of Glycerin on Ruthenium Catalyst, Energy﹠amp; Fuels.2005,19,1761) activity to glycerin vapor reformation hydrogen production catalysts compares, and the result shows, when loading on La
2O
3In the time of on the carrier, the active order of several metal catalysts is as follows: Ru ≈ Rh＞Ni＞Ir＞Co＞Pt＞Pd＞Fe; When being active ingredient with Ru, the active order that loads on the different carriers is: Y
2O
3＞ZrO
2＞MgO＞Al
2O
3Wherein, charge capacity is the Ru/Y of 3wt%
2O
3Catalyzer can stably catalyzed reaction 24h and glycerine 100% is transformed, and hydrogen yield can reach 87%.
Summary of the invention
The object of the invention is to provide a kind of method of the reforming by-product glycerin vapor hydrogen with the production biofuel, and this procedure is simple, and glycerol conversion yield can reach 100%, and hydrogen selective can reach more than 90%.
The present invention is realized by following technical solution: a kind of method of the reforming by-product glycerin vapor hydrogen with the production biofuel is characterized in that comprising following process:
In reactor, fill Rh/CeO
2-ZrO
2Or Pt/CeO
2-ZrO
2Or Pd/CeO
2-ZrO
2Catalyzer, the charge capacity of catalyst activity component Rh, Pt or Pd is: 1wt%～5wt%.Feed the hydrogen volume mark and be 5% hydrogen and nitrogen mixture in reactor, mixed gas flow 100mL/min carries out prereduction 2～3h to catalyzer under 500～600 ℃, then to reactor with air speed 10000～50000h
-1Feed water molecules and carbon atom number ratio, promptly steam/hydrocarbons ratio is 2: 1～9: 1 an aqueous glycerin solution steam, and at normal pressure, steam reformation is produced hydrogen under 300～700 ℃ the condition.
Said process: aqueous glycerin solution steam water carbon ratio is 3: 1～6: 1; Aqueous glycerin solution steam air speed is 12000～40000h
-1Temperature of reaction is 450～650 ℃.
The invention has the advantages that with the by-product glycerin of production biofuel and produced hydrogen, raw material is easy to get, and is renewable, cleanliness without any pollution.This method both can solve the problem of utilizing of by-product glycerol of biological diesel oil, can open up a new hydrogen again and produce route.The support of the catalyst that adopts prepares with chemical precipitation method, and active constituent loading adopts pickling process, and catalyst preparation process is simple, and is easy to operate.Catalyzer has high reactivity and selectivity, good stability.
Embodiment
By following examples method of the present invention and Preparation of Catalyst are described, but the present invention is not limited to following examples.
Embodiment 1:
Rh/CeO
2-ZrO
2, Pt/CeO
2-ZrO
2And Pd/CeO
2-ZrO
2Preparation of catalysts
Preparation ammonia soln (ammoniacal liquor and water volume ratio 1: 1).Get Ce (NO at 1: 1 by cerium zirconium mol ratio
3)
26H
2O and ZrOCl
28H
2O prepares Ce
3+, Zr
4+Total ion concentration is the mixing solutions of 1.0mol/L.Above-mentioned solution and ammonia soln and drip are added in the there-necked flask, constantly stir, control pH is 9～11, and precipitation is the aging 12h in back fully, with deionized water wash to neutral, 120 ℃ of dry 12h, 800～1000 ℃ of roasting 2～5h obtain CeO
2-ZrO
2Powder; Preparation concentration is the Rh (NO of 0.1mol/L
3)
3And Pt (NO
3)
2The aqueous solution and concentration be the PdCl of 0.1mol/L
2Ammonia soln, be 1wt%～5wt% by rhodium, platinum and palladium charge capacity respectively, the CeO that above-mentioned steps is made
2-ZrO
2Powder impregnated in Rh (NO respectively
3)
3, Pt (NO
3)
2The aqueous solution and PdCl
2Ammonia soln in, remove solvent through 70～80 ℃ of following rotary evaporations, 120 ℃ of vacuum-drying 12h, 600～800 ℃ of roasting 2～4h, the charge capacity that obtains Rh, Pt, Pd is respectively the Rh/CeO of 1wt%～5wt%
2-ZrO
2, Pt/CeO
2-ZrO
2And Pd/CeO
2-ZrO
2Catalyzer.
Rh/CeO with 1wt%
2-ZrO
2The catalyzer 200mg internal diameter of packing into is in the reactor of 6mm, and adopting the hydrogen volume marks down at 600 ℃ is that 5% hydrogen and nitrogen mixture carry out the prereduction of 2h to catalyzer, and mixed gas flow is 100mL/min, at N
2Protection reactor down drops to 500 ℃, subsequently with air speed 12000h
-1With steam/hydrocarbons ratio is that 6: 1 aqueous glycerin solution steam feeds reactor, carries out steam reformation and produces hydrogen.Glycerol conversion yield is 100%, and hydrogen selective is 89.7%.
Embodiment 2:
Adopt the Rh/CeO of the 4wt% that presses the preparation of embodiment 1 method
2-ZrO
2Catalyzer reacts, and investigates reactive behavior.Reaction conditions: normal pressure, 650 ℃, aqueous glycerin solution steam water carbon ratio is 5: 1, aqueous glycerin solution steam air speed is 12000h
-1, other experiment condition is with embodiment 1.Glycerol conversion yield is 100%, and hydrogen selective is 92.9%.
Embodiment 3:
Adopt the Pt/CeO of the 1wt% that presses the preparation of embodiment 1 method
2-ZrO
2Catalyzer reacts, and investigates reactive behavior.Reaction conditions: normal pressure, 450 ℃, aqueous glycerin solution steam water carbon ratio is 3: 1, aqueous glycerin solution steam air speed is 12000h
-1Other experiment condition is with embodiment 1.Glycerol conversion yield is 100%, and hydrogen selective is 88.5%.
Embodiment 4:
Adopt the Pt/CeO of the 3wt% that presses the preparation of embodiment 1 method
2-ZrO
2Catalyzer reacts, and investigates reactive behavior.Reaction conditions: normal pressure, 600 ℃, aqueous glycerin solution steam water carbon ratio is 3: 1, aqueous glycerin solution steam air speed is 12000h
-1Other experiment condition is with embodiment 1.Glycerol conversion yield is 100%, and hydrogen selective is 92.1%.
Embodiment 5:
Adopt the Pd/CeO of the 5wt% that presses the preparation of embodiment 1 method
2-ZrO
2Catalyzer reacts, and investigates reactive behavior.Reaction conditions: normal pressure, 550 ℃, aqueous glycerin solution steam water carbon ratio is 4: 1, aqueous glycerin solution steam air speed is 40000h
-1Other experiment condition is with embodiment 1.Glycerol conversion yield is 100%, and hydrogen selective is 83.1%.
Embodiment 6:
Adopt the Pd/CeO of the 5wt% that presses the preparation of embodiment 1 method
2-ZrO
2Catalyzer reacts, and investigates reactive behavior.Reaction conditions: normal pressure, 600 ℃, aqueous glycerin solution steam water carbon ratio is 6: 1, aqueous glycerin solution steam air speed is 33000h
-1The catalyzer loading level is 300mg, and adopting the hydrogen volume mark is that 5% hydrogen and nitrogen mixture carry out the prereduction of 3h under 500 ℃, and other experiment condition is with embodiment 1.Glycerol conversion yield is 100%, and hydrogen selective is 86.9%.
Claims (2)
1, a kind of method of the reforming by-product glycerin vapor hydrogen with the production biofuel, it is characterized in that comprising following process: the charge capacity of filling Rh, Pt, Pd in reactor is respectively the Rh/CeO of 1wt%～5wt%
2-ZrO
2Or Pt/CeO
2-ZrO
2Or Pd/CeO
2-ZrO
2Catalyzer feeds the hydrogen volume mark and is 5% hydrogen and nitrogen mixture in reactor, mixed gas flow 100mL/min carries out prereduction 2～3h to catalyzer under 500～600 ℃, then to reactor with air speed 10000～50000h
-1Feed water molecules and carbon atom number ratio, promptly steam/hydrocarbons ratio is 2: 1～9: 1 an aqueous glycerin solution steam, and at normal pressure, steam reformation is produced hydrogen under 300～700 ℃ the condition.
2, the method for the reforming by-product glycerin vapor hydrogen with the production biofuel as claimed in claim 1, it is characterized in that: aqueous glycerin solution steam water carbon ratio is 3: 1～6: 1; Aqueous glycerin solution steam air speed is 12000～40000h
-1Temperature of reaction is 450～650 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100573094A CN101049909A (en) | 2007-05-10 | 2007-05-10 | Reforming method for making hydrogen by glycerol steam as by-product for producing biological diesel oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100573094A CN101049909A (en) | 2007-05-10 | 2007-05-10 | Reforming method for making hydrogen by glycerol steam as by-product for producing biological diesel oil |
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|---|---|
| CN101049909A true CN101049909A (en) | 2007-10-10 |
Family
ID=38781547
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009130197A2 (en) * | 2008-04-22 | 2009-10-29 | Basf Se | Method for prereforming ethanol |
| KR101533537B1 (en) * | 2014-11-03 | 2015-07-03 | 성균관대학교산학협력단 | Catalyst platinum loaded in the mixed oxide support comprising ceria-zirconia for aqueous phase reforming |
| CN109052320A (en) * | 2018-08-24 | 2018-12-21 | 上海理工大学 | A kind of method that microalgae alkali extraction heat oil prepares hydrogen |
| CN109081308A (en) * | 2018-09-21 | 2018-12-25 | 华南理工大学 | A method of by glycerol and methane co-producing hydrogen and synthesis gas |
-
2007
- 2007-05-10 CN CNA2007100573094A patent/CN101049909A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009130197A2 (en) * | 2008-04-22 | 2009-10-29 | Basf Se | Method for prereforming ethanol |
| WO2009130197A3 (en) * | 2008-04-22 | 2009-12-17 | Basf Se | Method for prereforming ethanol |
| KR101533537B1 (en) * | 2014-11-03 | 2015-07-03 | 성균관대학교산학협력단 | Catalyst platinum loaded in the mixed oxide support comprising ceria-zirconia for aqueous phase reforming |
| CN109052320A (en) * | 2018-08-24 | 2018-12-21 | 上海理工大学 | A kind of method that microalgae alkali extraction heat oil prepares hydrogen |
| CN109081308A (en) * | 2018-09-21 | 2018-12-25 | 华南理工大学 | A method of by glycerol and methane co-producing hydrogen and synthesis gas |
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