CN106807387A - A kind of bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming and preparation method thereof - Google Patents
A kind of bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming and preparation method thereof, the active component of the catalyst is Ni, and auxiliary agent is Co, CeO2、MgO、K2At least one of O, carrier is ZrO2Or Al2O3With the compound of CaO；Active component accounts for 5wt%~20wt%, auxiliary agent and accounts for 1wt~15wt%, CaO and accounts for 10wt%~60wt% in the catalyst.The preparation method of catalyst of the present invention is simple, compared with typical catalyst, the bifunctional catalyst is used for the steam reforming reaction of bio oil, the characteristics of promoting reaction balanced sequence using its absorption enhancement, hydrogen of the highest purity more than 95% can not only be obtained, the separation costs of High Purity Hydrogen are enormously simplify, while bio oil conversion ratio and hydrogen manufacturing yield can also be improve, with broader prospects for commercial application.
Description
Technical field
The invention belongs to bio-oil hydrogen making technical field, and in particular to a kind of bio-oil steam reforming system of absorption enhancement
Hydrogen bifunctional catalyst and preparation method thereof.
Background technology
Hydrogen is increasingly valued by people as efficient, clean secondary energy sources, and has obtained wide in all conglomeraties
General application.Producing for hydrogen of major part both is from fossil fuel at present, but fossil fuel utilize the environmental pollution for bringing almost
Cannot reverse.Additionally, current electrolysis water hydrogen producing technology comparative maturity, but its hydrogen manufacturing cost is at a relatively high, and every cube is produced at present
The power consumption of rice hydrogen is 4.5~5.5kW.Therefore, it is increasingly tight for alleviating using regenerative resource such as biomass come hydrogen making
Energy supply and demand problem and problem of environmental pollution there is special meaning, be very attractive and development prospect approach it
One.
Include biomass gasifying hydrogen making, the indirect hydrogen manufacturing of rapidly pyrolysing and liquefying biomass, biology currently with biomass hydrogen preparation
The overcritical reforming hydrogen manufacturing of matter, biohydrogen, hydrogen production by bio-oil steam reforming etc..Wherein hydrogen production by bio-oil steam reforming quilt
It is considered to realize that biomass prepare one of most economical route of hydrogen on a large scale, application prospect is very wide.But people couple
The theoretical research and technological development of hydrogen production by bio-oil steam reforming process are still in the starting stage, and particularly bio-oil is steamed
The research of gas reforming hydrogen-production catalyst still has substantial amounts of exploration space.
At present, be adapted to catalyst for hydrogen production by bio-oil steam reforming is mainly with nickel-base catalyst and noble metal catalyst
It is main, it may be said that they have preferable result, highest on the hydrogen yield and hydrogen selectivity of hydrogen production by bio-oil steam reforming
It is 80% or so to produce hydrogen yield.But due to being limited by reforming reaction thermodynamical equilibrium, want further to improve the receipts of hydrogen
Rate becomes very difficult.While particularly producing hydrogen, about more than 20% CO can be also produced2.If in the reaction using suction
Receive agent removal CO in situ2, thermodynamical equilibrium can not only be broken through, moreover it is possible to greatly improve the purity of hydrogen, the follow-up separation process of simplification.
Directly by absorbent such as calcium oxide, dolomite etc. and reforming catalyst physical mixed, for the bio-oil steam of absorption enhancement
Reformation hydrogen production process is a kind of feasible method, but physical mixed is difficult to reach the uniform of micro-scale, is unfavorable for reaction
Mass transfer and heat transfer.Additionally, the vapor reforming hydrogen production process of absorption enhancement needs to carry out absorbent continuous high-temperature calcination-suction
Regenerative operation is received, to obtain the High Purity Hydrogen stream of stabilization.And absorbent and the mode of catalyst physical mixing are unfavorable for continuous suction
Receive agent regenerative process.This be due to：(1) general absorbent is easy to be sintered in high-temperature calcination-absorption and regeneration operating process, leads
Cause its absorbent properties rapid decrease；(2) granular size of absorbent and catalyst is approached, and separates difficult, the repeatedly suction after circulation
Agent is received to be difficult to upgrade in time and supplement.In view of the above circumstances, activity height, the bifunctional catalyst of good stability are developed, will be absorbed
Agent and reforming catalyst are combined, and for absorption enhancement hydrogen production by bio-oil steam reforming process, improve the stable circulation of its reaction
Property, with important application value, the step of bio oil one can be converted into the hydrogen of high-purity, and obtain the hydrogen stream of stabilization.
The content of the invention
It is an object of the invention to provide a kind of reactivity is high, carbon accumulation resisting ability strong, good stability, for absorption enhancement
The bifunctional catalyst of hydrogen production by bio-oil steam reforming, and for the catalyst provides a kind of preparation method.
Solving the technical scheme that is used of above-mentioned technical problem is：The active component of the catalyst be Ni, auxiliary agent be Co,
CeO2、MgO、K2At least one of O, carrier is ZrO2Or Al2O3With the compound of CaO；Active component accounts for 5wt% in the catalyst
~20wt%, auxiliary agent account for 1wt~15wt%, CaO and account for 10wt%~60wt%.
Above-mentioned auxiliary agent is Co, CeO2、MgO、K2O any one.
3rd, the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1,
It is characterized in that：The ZrO2There is middle species CaZrO with the compound of CaO3。
4th, the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1,
It is characterized in that：The Al2O3There is middle species Ca with the compound of CaO5Al6O14。
5th, according to Claims 1 to 4 any one for the double of absorption enhancement hydrogen production by bio-oil steam reforming
Function catalyst, it is characterised in that：In the described catalyst active component account for 10wt%~20wt%, auxiliary agent account for 5wt~
10wt%, CaO account for 30wt%~60wt%.
6th, the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1,
It is characterized in that：Mass percent according to catalyst is constituted, by soluble zirconates or aluminum nitrate or aluminium isopropoxide and auxiliary agent
Soluble nitrate is dissolved in deionized water, add aqueous citric acid solution, room temperature reaction 2~4 hours, be subsequently adding calcium oxalate or
Solubility calcium saline solution, reacts at 60~80 DEG C, until forming gel, after the gel is dried at 100~120 DEG C,
It is calcined 4~12 hours in 600~750 DEG C, obtains composite oxides；Using equi-volume impregnating, composite oxides are immersed in
In soluble nickel saline solution, through aging, drying, roasting, hydrogen reducing, obtain for absorption enhancement bio-oil steam reforming
The bifunctional catalyst of hydrogen manufacturing.
7th, the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 6,
It is characterized in that：The addition of the citric acid is 1~5 times of soluble zirconates or aluminum nitrate or aluminium isopropoxide mole.
8th, the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 6,
It is characterized in that：After gel is dried at 100~120 DEG C, it is calcined 6 hours in 650 DEG C, obtains composite oxides.
Compared with existing catalyst, the invention has the advantages that：
1st, the present invention directly combines absorbent and reforming catalyst, is prepared for bifunctional catalyst, and the catalyst is used for
Absorption enhancement hydrogen production by bio-oil steam reforming process, be conducive to reaction mass transfer and heat transfer, can obtain purity higher than 95% with
On hydrogen.
2nd, catalyst carbon accumulation resisting ability of the present invention is strong, good stability, bio oil conversion ratio reach more than 90%, hydrogen manufacturing yield
More than 85% is reached, can be used for hydrogen production by bio-oil steam reforming in fixed bed reactors and fluidized-bed reactor.
Brief description of the drawings
Fig. 1 is 15wt%Ni/CeO prepared by embodiment 12-ZrO2The XRD of-CaO bifunctional catalysts.
Fig. 2 is 15wt%Ni/CeO prepared by embodiment 12-ZrO2- CaO bifunctional catalysts are used to absorb at 550 DEG C
The result figure that the reaction of enhanced biological profit vapour reforming hydrogen producing is changed over time.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
15wt%Ni/CeO2-ZrO2The preparation of-CaO bifunctional catalysts
By 2.4g (7.5mmol) ZrOCl2·8H2O and 3.25g (7.5mmol) Ce (NO3)3·6H2O add 200mL go from
In sub- water, 100mL is added dropwise under agitation containing 6g (31.2mmol) lemon aqueous acid, be stirred at room temperature after dripping
Reaction 2 hours；The aqueous solution of the 200mL containing 4.8g (37.5mmol) calcium oxalate is added dropwise over again, is reacted at 80 DEG C after dripping,
Until forming gel；650 DEG C are calcined 4 hours in being placed in muffle furnace after the gel is dried at 110 DEG C, obtain combined oxidation
Thing.Using equi-volume impregnating, gained composite oxides are immersed in the aqueous solution containing 3.3g nickel nitrates, aged at room temperature 24 is small
When, 110 DEG C of dryings, 600 DEG C are calcined 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain biological for absorption enhancement
The bifunctional catalyst 15wt%Ni/CeO of profit vapour reforming hydrogen producing2-ZrO2-CaO.The main shape with CaO of calcium in the catalyst
Formula is present, and its content accounts for 42wt%, ZrO2Except with CeO2Form cerium zirconium sosoloid (CZO) outward, middle species are also formed with CaO
CaZrO3(see Fig. 1).
Comparative example 1
By 2.4g ZrOCl2·8H2O and 3.25g Ce (NO3)3·6H2O is added in 200mL deionized waters, in stirring condition
Under be added dropwise over 100mL lemons containing 6g aqueous acid, after dripping at 80 DEG C react, until formed gel；By the gel
650 DEG C are calcined 4 hours in being placed in muffle furnace after being dried at 110 DEG C, obtain composite oxides.Using equi-volume impregnating, will
Gained composite oxides are immersed in the aqueous solution containing 1.66g nickel nitrates, aged at room temperature 24 hours, 110 DEG C of dryings, 600 DEG C of roastings
Burn 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain Ni/CeO2-ZrO2Catalyst.The Ni/CeO that will be prepared2-
ZrO2Catalyst is directly used in hydrogen production by bio-oil steam reforming reaction.
Comparative example 2
By 2.4g ZrOCl2·8H2O and 3.25g Ce (NO3)3·6H2O is added in 200mL deionized waters, in stirring condition
Under be added dropwise over 100mL lemons containing 6g aqueous acid, after dripping at 80 DEG C react, until formed gel；By the gel
650 DEG C are calcined 4 hours in being placed in muffle furnace after being dried at 110 DEG C, obtain composite oxides.Using equi-volume impregnating, will
Gained composite oxides are immersed in the aqueous solution containing 1.66g nickel nitrates, aged at room temperature 24 hours, 110 DEG C of dryings, 600 DEG C of roastings
Burn 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain Ni/CeO2-ZrO2Catalyst.By 4.8g calcium oxalates 650
DEG C roasting 6 hours, obtain CaO absorbents.The Ni/CeO that will be prepared2-ZrO2Catalyst and CaO absorbents are using physical mixed
Mode is well mixed, used as the mixed catalyst for absorption enhancement hydrogen production by bio-oil steam reforming.
Embodiment 2
20wt%Ni/MgO-ZrO2The preparation of-CaO bifunctional catalysts
By 2.4g (7.5mmol) ZrOCl2·8H2O and 1.2g (8mmol) Mg (NO3)3In addition 200mL deionized waters,
100mL is added dropwise under stirring condition containing 6g (31.2mmol) lemon aqueous acid, rear room temperature stirring reaction 2 is dripped small
When；The aqueous solution of the 200mL containing 4.6g (28mmol) calcium nitrate is added dropwise over again, is reacted at 80 DEG C after dripping, until being formed
Gel；650 DEG C are calcined 4 hours in being placed in muffle furnace after the gel is dried at 110 DEG C, obtain composite oxides.Using etc.
Volume impregnation method, gained composite oxides are immersed in the aqueous solution containing 2.8g nickel nitrates, aged at room temperature 24 hours, 110 DEG C
Dry, 600 DEG C be calcined 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain for absorption enhancement bio-oil steam
The bifunctional catalyst 20wt%Ni/MgO-ZrO of reformation hydrogen production2- CaO, MgO accounts for 10wt% in the catalyst, and calcium is mainly with CaO
Form exist, while also part CaO and ZrO2Species CaZrO in the middle of being formed3, wherein CaO content accounts for 46.5wt%.
Embodiment 3
15wt%Ni/Co-Al2O3The preparation of-CaO bifunctional catalysts
By 1.5g (7.3mmol) aluminium isopropoxides and 0.58g (2mmol) Co (NO3)2·6H2O adds 200mL deionized waters
In, 80mL is added dropwise under agitation containing 3g (15.6mmol) lemon aqueous acid, drip rear room temperature stirring reaction 2
Hour；The aqueous solution of the 250mL containing 7.2g (56.25mmol) calcium oxalate is added dropwise over again, is reacted at 80 DEG C after dripping, until
Form gel；650 DEG C are calcined 4 hours in being placed in muffle furnace after the gel is dried at 110 DEG C, obtain composite oxides.Adopt
With equi-volume impregnating, gained composite oxides are immersed in the aqueous solution containing 3.2g nickel nitrates, aged at room temperature 24 hours,
110 DEG C of dryings, 600 DEG C be calcined 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain for absorption enhancement bio oil
The bifunctional catalyst 15wt%Ni/Co-Al of vapor reforming hydrogen production2O3- CaO, Co accounts for 2.5wt% in the catalyst, and calcium is main
Exist in the form of CaO, while also part CaO and Al2O3Species Ca in the middle of being formed5Al6O14, wherein CaO content accounts for
60wt%.
Embodiment 4
10wt%Ni/K2O-ZrO2The preparation of-CaO bifunctional catalysts
By 3.6g (11.25mmol) ZrOCl2·8H2O and 0.2g (2mmol) K2(NO3)3In addition 200mL deionized waters,
100mL is added dropwise under agitation containing 4g (20.8mmol) lemon aqueous acid, drips rear room temperature stirring reaction 2 small
When；The aqueous solution of the 200mL containing 6.9g (42mmol) calcium nitrate is added dropwise over again, is reacted at 80 DEG C after dripping, until being formed
Gel；650 DEG C are calcined 4 hours in being placed in muffle furnace after the gel is dried at 110 DEG C, obtain composite oxides.Using etc.
Volume impregnation method, gained composite oxides are immersed in the aqueous solution containing 2g nickel nitrates, aged at room temperature 24 hours, and 110 DEG C are done
It is dry, 600 DEG C be calcined 6 hours, then in hydrogen atmosphere 400 DEG C reduce 4 hours, obtain for absorption enhancement bio-oil steam weight
The bifunctional catalyst 10wt%Ni/K of whole hydrogen manufacturing2O-ZrO2- CaO, K in the catalyst2O accounts for 3wt%, and calcium is mainly with the shape of CaO
Formula is present, while also part CaO and ZrO2Species CaZrO in the middle of being formed3, wherein CaO content accounts for 55wt%.
In order to prove beneficial effects of the present invention, the bifunctional catalyst that inventor respectively prepares above-described embodiment 1~4
For the reaction of absorption enhancement hydrogen production by bio-oil steam reforming, the catalyst that will be prepared in comparative example 1 is used for traditional bio oil
Vapor reforming hydrogen production reacts.Specific experiment is：Made catalyst is put into diameter in taking 4.0g bifunctional catalysts or comparative example 1
In for the quartz ampoule of 12mm, in N2400 DEG C are warming up under atmosphere, are heated first half an hour, close nitrogen, then be passed through hydrogen, in
400 DEG C of reductase 12s hour, close hydrogen, and it is 0.05mL/min, the rice husk bio-oil solution being preheating to after 200 DEG C to be passed through flow,
Its water molar equivalent is 8:1, the reaction temperature of beds is controlled at 500~650 DEG C.Product after synthesis under normal pressure passes through gas
Phase chromatogram on-line analysis, are as a result shown in Fig. 2 and Biao 1.The dry gas composition of product is H2、CO、CO2And CH4。
The concentration of hydrogen is expressed as in dry gas component：
The yield of hydrogen is：
The hydrogen yield and hydrogen concentration ＞ of the hydrogen production by bio-oil steam reforming reaction of the catalyst absorption enhancement of the present invention of table 1
90% time for being maintained
| Catalyst | Temperature (DEG C) | Hydrogen yield | The durations of hydrogen concentration ＞ 90% (min) |
| Embodiment 1 | 550 | 85% | 18 |
| Embodiment 2 | 600 | 86% | 25 |
| Embodiment 3 | 500 | 70% | 35 |
| Embodiment 4 | 650 | 85% | 30 |
| Comparative example 1 | 550 | 72% | 0, density of hydrogen stabilization is 68% |
From Figure 2 it can be seen that process typical case is divided into three phases：The incipient first stage is being reacted, because CaO is to CO2
Absorption, mainly based on hydrogen, its concentration has reached more than 95%, CO to product2Concentration maintain it is low-down
Level, the time in the stage maintains 18 minutes.Afterwards with the carrying out of reaction, absorbing reaction is gradually slack-off, the concentration of hydrogen
Decline, less than 90%, CO2Concentration increase.In phase III, the uptake saturation of absorbent, the concentration of hydrogen is maintained
70% or so.From table 1, the bifunctional catalyst prepared by the present invention is used for absorption enhancement hydrogen production by bio-oil steam reforming
Reaction, its hydrogen yield can reach the hydrogen that high-purity can be obtained in 86% or so, and course of reaction, and hydrogen is dense in gaseous product
The duration for spending ＞ 90% is more long, is much better than traditional hydrogen production by bio-oil steam reforming process.
In order to further prove beneficial effects of the present invention, bifunctional catalyst that inventor prepares embodiment 1~4 and
10 circulations that mixed catalyst prepared by comparative example 2 is respectively used to the reaction of absorption enhancement hydrogen production by bio-oil steam reforming are real
Test, specific experimental technique is：Take 4.0g bifunctional catalysts or mixed catalyst is put into the quartz ampoule of a diameter of 12mm,
N2400 DEG C are warming up under atmosphere, are heated first half an hour, close nitrogen, then be passed through hydrogen, in 400 DEG C of reductase 12s hour, closed
Hydrogen, it is 0.05mL/min, the rice husk bio-oil solution being preheating to after 200 DEG C to be passed through flow, and its water molar equivalent is 8:1,
The reaction temperature of beds is controlled at 500~650 DEG C.Reacted product passes through gas-chromatography on-line analysis.When
After monitoring concentration of the hydrogen in exit gas less than 90%, stop charging.And temperature is increased to 750 DEG C, to cause
The absorbability of the material is regenerated, and is that the hydrogen for obtaining high-purity again is prepared.When on-line checking to exit gas
It is middle without CO2After release, 500~650 DEG C are cooled to, it is 0.05mL/min, the rice husk being preheating to after 200 DEG C that flow is passed through again
Bio-oil solution, starts second circulation.So 10 times repeatedly, to evaluate the stability of catalyst, the results are shown in Table 2.
The catalyst of table 2 time that continuously 10 hydrogen concentration ＞ 90% of circulation are maintained
From table 2, the bifunctional catalyst prepared by the present invention is for absorption enhancement hydrogen production by bio-oil steam reforming
Reaction have very excellent circular response performance, it is reproducible, absorbent properties stabilization, catalyst reaction circulate 10 times after,
Remain to obtain for a long time the hydrogen of high-purity, simplify follow-up separation process, reduce the production cost of hydrogen manufacturing, have
Preferable application prospect.
Claims (8)
1. a kind of bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming, it is characterised in that：The catalyst
Active component be Ni, auxiliary agent be Co, CeO2、MgO、K2At least one of O, carrier is ZrO2Or Al2O3With the compound of CaO；
Active component accounts for 5wt%~20wt%, auxiliary agent and accounts for 1wt~15wt%, CaO and accounts for 10wt%~60wt% in the catalyst.
2. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1, it is special
Levy and be：The auxiliary agent is Co, CeO2、MgO、K2O any one.
3. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1, it is special
Levy and be：The ZrO2There is middle species CaZrO with the compound of CaO3。
4. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1, it is special
Levy and be：The Al2O3There is middle species Ca with the compound of CaO5Al6O14。
5. according to Claims 1 to 4 any one for the difunctional of absorption enhancement hydrogen production by bio-oil steam reforming
Catalyst, it is characterised in that：In the described catalyst active component account for 10wt%~20wt%, auxiliary agent account for 5wt~10wt%,
CaO accounts for 30wt%~60wt%.
6. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 1, it is special
Levy and be：Mass percent according to catalyst is constituted, and soluble zirconates or aluminum nitrate or aluminium isopropoxide is solvable with auxiliary agent
Property nitrate be dissolved in deionized water, add aqueous citric acid solution, room temperature reaction 2~4 hours is subsequently adding calcium oxalate or solvable
Property calcium saline solution, reacted at 60~80 DEG C, until forming gel, after the gel is dried at 100~120 DEG C, in 600
~750 DEG C are calcined 4~12 hours, obtain composite oxides；Using equi-volume impregnating, composite oxides are immersed in solubility
In nickel salt aqueous solution, through aging, drying, roasting, hydrogen reducing, obtain for absorption enhancement hydrogen production by bio-oil steam reforming
Bifunctional catalyst.
7. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 6, it is special
Levy and be：The addition of the citric acid is 1~5 times of soluble zirconates or aluminum nitrate or aluminium isopropoxide mole.
8. the bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming according to claim 6, it is special
Levy and be：After gel is dried at 100~120 DEG C, it is calcined 6 hours in 650 DEG C, obtains composite oxides.
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| CN107954881A (en) * | 2017-12-26 | 2018-04-24 | 徐州得铸生物科技有限公司 | A kind of method that aniline synthesizes 4,4 '-MDA |
| CN108322976A (en) * | 2018-04-04 | 2018-07-24 | 宁波伟铄电子科技有限公司 | Fast connecting electronic ballast |
| CN108554418A (en) * | 2017-12-12 | 2018-09-21 | 宁波大学 | Ni-B-La catalyst and preparation method thereof for catalyzing and reforming biologic oil hydrogen manufacturing |
| CN110433811A (en) * | 2019-07-31 | 2019-11-12 | 天津大学 | MgO modified Ni/CaO bifunctional catalyst and preparation method and application |
| CN114160141A (en) * | 2021-12-18 | 2022-03-11 | 太原理工大学 | Adsorption hydrogen production composite catalyst and preparation method thereof |
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| CN114160141A (en) * | 2021-12-18 | 2022-03-11 | 太原理工大学 | Adsorption hydrogen production composite catalyst and preparation method thereof |
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