CN106807387B - A kind of bifunctional catalyst and preparation method thereof for absorption enhancement hydrogen production by bio-oil steam reforming - Google Patents
A kind of bifunctional catalyst and preparation method thereof for absorption enhancement hydrogen production by bio-oil steam reforming Download PDFInfo
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Abstract
The bifunctional catalyst and preparation method thereof that the invention discloses a kind of for absorption enhancement hydrogen production by bio-oil steam reforming, the active component of the catalyst are Ni, auxiliary agent Co, CeO2、MgO、K2At least one of O, carrier ZrO2Or Al2O3With the compound of CaO；Active component accounts for 5wt%~20wt% in the catalyst, auxiliary agent accounts for 1wt~15wt%, CaO accounts for 10wt%~60wt%.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, the hydrogen that highest purity is greater than 95% can not only be obtained, the separation costs of High Purity Hydrogen are enormously simplified, while bio oil conversion ratio and hydrogen manufacturing yield can also be improved, there is broader prospects for commercial application.
Description
Technical field
The invention belongs to bio-oil hydrogen making technical fields, and in particular to a kind of bio-oil steam reforming system of absorption enhancement
Hydrogen bifunctional catalyst and preparation method thereof.
Background technique
Hydrogen is increasingly valued by people as secondary energy sources efficiently, clean, and has been obtained extensively in all conglomeraties
General application.Producing for major part hydrogen both is from fossil fuel at present, but fossil fuel utilize bring environmental pollution almost
It can not reverse.In addition, current electrolysis water hydrogen producing technology comparative maturity, but its hydrogen manufacturing cost is quite high, produces every cube at present
The power consumption of rice hydrogen is 4.5~5.5kW.Therefore, increasingly tight for alleviating using renewable energy 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.
It 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 one of the most economical route of biomass large scale preparation hydrogen, application prospect is very wide.However people couple
The theoretical research and technological development of hydrogen production by bio-oil steam reforming process are still in the starting stage, especially steam to bio-oil
The research of gas reforming hydrogen-production catalyst still has a large amount of exploration space.
Currently, being adapted to catalyst for hydrogen production by bio-oil steam reforming and being mainly with nickel-base catalyst and noble metal catalyst
It is main, it may be said that they have preferable as a result, highest on the hydrogen yield of hydrogen production by bio-oil steam reforming and hydrogen selectivity
Producing hydrogen yield is 80% or so.But due to being limited by reforming reaction thermodynamical equilibrium, to further increase the receipts of hydrogen
Rate becomes very difficult.While especially producing hydrogen, about 20% or more CO can be also generated2.If utilizing suction in the reaction
It receives agent and removes CO in situ2, thermodynamical equilibrium can not only be broken through, moreover it is possible to greatly improve the purity of hydrogen, simplify subsequent separation process.
Bio-oil steam directly by absorbent such as calcium oxide, dolomite etc. and reforming catalyst physical mixed, for 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.In addition, the vapor reforming hydrogen production process of absorption enhancement needs to carry out continuous high-temperature calcination-suction to absorbent
Regenerative operation is received, to obtain stable High Purity Hydrogen stream.And absorbent and the mode of catalyst physical mixing are unfavorable for continuously inhaling
Receive agent regenerative process.This is because: (1) general absorbent is easy to be sintered in high-temperature calcination-absorption and regeneration operating process, lead
Cause its absorbent properties rapid decrease；(2) granular size of absorbent and catalyst is close, and separation is difficult, repeatedly the suction after circulation
Agent is received to be not easy to timely update and supplement.In view of the above circumstances, the bifunctional catalyst that exploitation activity is high, stability is good, will absorb
Agent and reforming catalyst combination, are used for absorption enhancement hydrogen production by bio-oil steam reforming process, improve the stable circulation of its reaction
Property, there is important application value, one step of bio oil can be converted to the hydrogen of high-purity, and obtain stable hydrogen stream.
Summary of the invention
That the purpose of the present invention is to provide a kind of reactivities is high, have strong anti-carbon capacity, stability is good, for absorption enhancement
The bifunctional catalyst of hydrogen production by bio-oil steam reforming, and a kind of preparation method is provided for the catalyst.
Solve above-mentioned technical problem used by technical solution be: the active component of the catalyst be Ni, auxiliary agent Co,
CeO2、MgO、K2At least one of O, carrier ZrO2Or Al2O3With the compound of CaO；Active component accounts for 5wt% in the catalyst
~20wt%, auxiliary agent account for 1wt~15wt%, CaO accounts for 10wt%~60wt%.
Above-mentioned auxiliary agent is Co, CeO2、MgO、K2O any one.
3, the bifunctional catalyst according to claim 1 for absorption enhancement hydrogen production by bio-oil steam reforming,
It is characterized by: the ZrO2There are intermediate species CaZrO with the compound of CaO3。
4, the bifunctional catalyst according to claim 1 for absorption enhancement hydrogen production by bio-oil steam reforming,
It is characterized by: the Al2O3There are intermediate species Ca with the compound of CaO5Al6O14。
5, according to claim 1~4 described in 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%.
6, the bifunctional catalyst according to claim 1 for absorption enhancement hydrogen production by bio-oil steam reforming,
It is characterized by: according to the mass percentage composition of catalyst, by soluble zirconates or aluminum nitrate or aluminium isopropoxide and auxiliary agent
Soluble nitrate is dissolved in deionized water, be added aqueous citric acid solution, react at room temperature 2~4 hours, then be added calcium oxalate or
Solubility calcium saline solution reacts at 60~80 DEG C, until forming gel, by the gel at 100~120 DEG C after drying,
It is roasted 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 the steam reforming of absorption enhancement bio-oil
The bifunctional catalyst of hydrogen manufacturing.
7, the bifunctional catalyst according to claim 6 for absorption enhancement hydrogen production by bio-oil steam reforming,
It is characterized by: the additional amount of the citric acid is 1~5 times of soluble zirconates or aluminum nitrate or aluminium isopropoxide mole.
8, the bifunctional catalyst according to claim 6 for absorption enhancement hydrogen production by bio-oil steam reforming,
It is characterized by: after drying, roasting 6 hours at 100~120 DEG C, obtaining composite oxides gel in 650 DEG C.
Compared with existing catalyst, the invention has the following advantages:
1, the present invention directly combines absorbent and reforming catalyst, is prepared for bifunctional catalyst, which 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.
2, catalyst of the present invention has strong anti-carbon capacity, stability is good, bio oil conversion ratio reaches 90% or more, hydrogen manufacturing yield
Reach 85% or more, can be used for hydrogen production by bio-oil steam reforming in fixed bed reactors and fluidized-bed reactor.
Detailed description of the invention
Fig. 1 is 15wt%Ni/CeO prepared by embodiment 12-ZrO2The XRD diagram of-CaO bifunctional catalyst.
Fig. 2 is 15wt%Ni/CeO prepared by embodiment 12-ZrO2- CaO bifunctional catalyst is at 550 DEG C for absorbing
Enhanced biological grease vapour reforming hydrogen producing reacts the result figure 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 catalyst
By 2.4g (7.5mmol) ZrOCl2·8H2O and 3.25g (7.5mmol) Ce (NO3)3·6H2O be added 200mL go from
In sub- water, the aqueous solution that 100mL contains 6g (31.2mmol) citric acid is added dropwise under agitation, is stirred at room temperature after dripping
Reaction 2 hours；The aqueous solution that 200mL contains 4.8g (37.5mmol) calcium oxalate is added dropwise again, is reacted at 80 DEG C after dripping,
Until forming gel；By the gel, dry be placed in muffle furnace is roasted 4 hours for 650 DEG C at 110 DEG C, obtains combined oxidation
Object.Using equi-volume impregnating, gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 3.3g, aged at room temperature 24 is small
When, 110 DEG C of dryings, 600 DEG C roast 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, obtain for absorption enhancement biology
The bifunctional catalyst 15wt%Ni/CeO of grease vapour reforming hydrogen producing2-ZrO2-CaO.Calcium is mainly with the shape of CaO in the catalyst
Formula exists, and content accounts for about 42wt%, ZrO2It removes and CeO2It forms cerium zirconium sosoloid (CZO) outside, also forms intermediate species 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 water, in stirring condition
Under the aqueous solution of 100mL citric acid containing 6g is added dropwise, reacted at 80 DEG C after dripping, until forming gel；By the gel
Dry be placed in muffle furnace roasts 4 hours for 650 DEG C at 110 DEG C, obtains composite oxides.It, will using equi-volume impregnating
Gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 1.66g, and aged at room temperature 24 hours, 110 DEG C of dryings, 600 DEG C of roastings
It burns 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, obtains Ni/CeO2-ZrO2Catalyst.By the Ni/CeO of preparation2-
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 water, in stirring condition
Under the aqueous solution of 100mL citric acid containing 6g is added dropwise, reacted at 80 DEG C after dripping, until forming gel；By the gel
Dry be placed in muffle furnace roasts 4 hours for 650 DEG C at 110 DEG C, obtains composite oxides.It, will using equi-volume impregnating
Gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 1.66g, and aged at room temperature 24 hours, 110 DEG C of dryings, 600 DEG C of roastings
It burns 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, obtains Ni/CeO2-ZrO2Catalyst.By 4.8g calcium oxalate 650
DEG C roasting 6 hours, obtain CaO absorbent.By the Ni/CeO of preparation2-ZrO2Catalyst and CaO absorbent are using physical mixed
Mode is uniformly mixed, as the mixed catalyst for absorption enhancement hydrogen production by bio-oil steam reforming.
Embodiment 2
20wt%Ni/MgO-ZrO2The preparation of-CaO bifunctional catalyst
By 2.4g (7.5mmol) ZrOCl2·8H2O and 1.2g (8mmol) Mg (NO3)3It is added in 200mL deionized water,
The aqueous solution that 100mL contains 6g (31.2mmol) citric acid is added dropwise under stirring condition, dripping rear room temperature, to be stirred to react 2 small
When；The aqueous solution that 200mL contains 4.6g (28mmol) calcium nitrate is added dropwise again, is reacted at 80 DEG C after dripping, until being formed
Gel；By the gel, dry be placed in muffle furnace is roasted 4 hours for 650 DEG C at 110 DEG C, obtains composite oxides.Using etc.
Gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 2.8g by volume impregnation method, and aged at room temperature 24 hours, 110 DEG C
Dry, 600 DEG C roast 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, 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 there are also part CaO and ZrO2Form intermediate species CaZrO3, wherein CaO content accounts for about 46.5wt%.
Embodiment 3
15wt%Ni/Co-Al2O3The preparation of-CaO bifunctional catalyst
By 1.5g (7.3mmol) aluminium isopropoxide and 0.58g (2mmol) Co (NO3)2·6H2200mL deionized water is added in O
In, the aqueous solution that 80mL contains 3g (15.6mmol) citric acid is added dropwise under agitation, drips rear room temperature and is stirred to react 2
Hour；The aqueous solution that 250mL contains 7.2g (56.25mmol) calcium oxalate is added dropwise again, is reacted at 80 DEG C after dripping, until
Form gel；By the gel, dry be placed in muffle furnace is roasted 4 hours for 650 DEG C at 110 DEG C, obtains composite oxides.It adopts
With equi-volume impregnating, gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 3.2g, aged at room temperature 24 hours,
110 DEG C of dryings, 600 DEG C roast 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, 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 there are also part CaO and Al2O3Form intermediate species Ca5Al6O14, wherein CaO content accounts for about
60wt%.
Embodiment 4
10wt%Ni/K2O-ZrO2The preparation of-CaO bifunctional catalyst
By 3.6g (11.25mmol) ZrOCl2·8H2O and 0.2g (2mmol) K2(NO3)3It is added in 200mL deionized water,
The aqueous solution that 100mL contains 4g (20.8mmol) citric acid is added dropwise under agitation, dripping rear room temperature, to be stirred to react 2 small
When；The aqueous solution that 200mL contains 6.9g (42mmol) calcium nitrate is added dropwise again, is reacted at 80 DEG C after dripping, until being formed
Gel；By the gel, dry be placed in muffle furnace is roasted 4 hours for 650 DEG C at 110 DEG C, obtains composite oxides.Using etc.
Gained composite oxides are immersed in the aqueous solution of the nickel nitrate containing 2g by volume impregnation method, and aged at room temperature 24 hours, 110 DEG C dry
Dry, 600 DEG C roast 6 hours, then 400 DEG C reduction 4 hours in hydrogen atmosphere, 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 exists, while there are also part CaO and ZrO2Form intermediate species CaZrO3, wherein CaO content accounts for about 55wt%.
In order to prove beneficial effects of the present invention, the bifunctional catalyst that inventor respectively prepares above-described embodiment 1~4
It is reacted for absorption enhancement hydrogen production by bio-oil steam reforming, the catalyst prepared in comparative example 1 is used for traditional bio oil
Vapor reforming hydrogen production reaction.Specific experiment are as follows: made catalyst in 4.0g bifunctional catalyst or comparative example 1 is taken to be put into diameter
For in the quartz ampoule of 12mm, in N2It is warming up to 400 DEG C under atmosphere, first heating half an hour, closes nitrogen, then be passed through hydrogen, in
400 DEG C of reductase 12 hours close hydrogen, are passed through the rice husk bio-oil solution after flow is 0.05mL/min, is preheating to 200 DEG C,
Its water molar equivalent is 8:1, and the reaction temperature of catalyst bed is controlled at 500~650 DEG C.Product after synthesis under normal pressure passes through gas
Phase chromatography on-line analysis, is as a result shown in Fig. 2 and table 1.The dry gas group of product becomes H2、CO、CO2And CH4。
The concentration of hydrogen indicates in dry gas component are as follows:
The yield of hydrogen are as follows:
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% maintained time
| Catalyst | Temperature (DEG C) | Hydrogen yield | 90% duration of hydrogen concentration > (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 is stablized 68% |
From Figure 2 it can be seen that process typical case is divided into three phases: the incipient first stage is being reacted, since CaO is to CO2
Absorption, for reaction product mainly based on hydrogen, concentration has reached 95% or more, CO2Concentration maintain it is low-down
Level, the time in the stage maintain 18 minutes.Later with the progress of reaction, absorbing reaction is gradually slack-off, the concentration of hydrogen
Decline is lower than 90%, CO2Concentration increase.In the phase III, the uptake of absorbent is saturated, and the concentration of hydrogen maintains
70% or so.Seen from table 1, the bifunctional catalyst prepared by the present invention is used for absorption enhancement hydrogen production by bio-oil steam reforming
Reaction, hydrogen yield can reach 86% or so, and the hydrogen of high-purity can be obtained in reaction process, and hydrogen is dense in gaseous product
The duration for spending > 90% is longer, 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 Examples 1 to 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
It tests, specific experimental method are as follows: take 4.0g bifunctional catalyst or mixed catalyst to be put into the quartz ampoule that diameter is 12mm,
N2It is warming up to 400 DEG C under atmosphere, first heating half an hour, closes nitrogen, then be passed through hydrogen, in 400 DEG C of reductase 12 hours, closes
Hydrogen is passed through the rice husk bio-oil solution after flow is 0.05mL/min, is preheating to 200 DEG C, and water molar equivalent is 8:1,
The reaction temperature of catalyst bed is controlled at 500~650 DEG C.Product after reaction passes through gas-chromatography on-line analysis.When
After monitoring concentration of the hydrogen in exit gas less than 90%, stop charging.And 750 DEG C are raised the temperature to, so that
The absorbability of the material is regenerated, and is prepared to obtain the hydrogen of high-purity again.When on-line checking to exit gas
Middle no CO2After release, 500~650 DEG C are cooled to, is passed through flow again as 0.05mL/min, the rice husk being preheating to after 200 DEG C
Bio-oil solution starts second circulation.10 times repeatedly, to evaluate the stability of catalyst, it the results are shown in Table 2.
2 catalyst of table continuously recycles the maintained time of 10 hydrogen concentration > 90%
As can be seen from Table 2, 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 stablize, catalyst reaction recycle 10 times after,
The hydrogen for obtaining high-purity for a long time is remained to, subsequent separation process is simplified, the production cost of hydrogen manufacturing is reduced, has
Preferable application prospect.
Claims (6)
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 Co, CeO2、MgO、K2At least one of O, carrier ZrO2Or Al2O3With the compound of CaO,
Wherein ZrO2There are intermediate species CaZrO with the compound of CaO3, Al2O3There are intermediate species Ca with the compound of CaO5Al6O14；
Active component accounts for wt % of 5 wt%~20 in the catalyst, auxiliary agent accounts for wt % of 1 wt~15, CaO accounts for 10 wt of wt %~60 %.
2. the bifunctional catalyst according to claim 1 for absorption enhancement hydrogen production by bio-oil steam reforming, special
Sign is: the auxiliary agent is Co, CeO2、MgO、K2O any one.
3. the bifunctional catalyst according to claim 1 or 2 for absorption enhancement hydrogen production by bio-oil steam reforming,
Be characterized in that: active component accounts for wt % of 10 wt%~20 in the catalyst, auxiliary agent accounts for wt % of 5 wt~10, CaO accounts for 30 wt
The wt of %~60 %.
4. a kind of preparation of the bifunctional catalyst described in claim 1 for absorption enhancement hydrogen production by bio-oil steam reforming
Method, it is characterised in that: according to the mass percentage composition of catalyst, by soluble zirconates or aluminum nitrate or aluminium isopropoxide with help
The soluble nitrate of agent is dissolved in deionized water, and aqueous citric acid solution is added, and reacts at room temperature 2~4 hours, oxalic acid is then added
Calcium or solubility calcium saline solution, react at 60~80 DEG C, until forming gel, the gel is dry at 100~120 DEG C
Afterwards, it is roasted 4~12 hours in 600~750 DEG C, obtains composite oxides；Using equi-volume impregnating, composite oxides are impregnated
In soluble nickel saline solution, through aging, drying, roasting, hydrogen reducing, obtain for absorption enhancement bio-oil steam weight
The bifunctional catalyst of whole hydrogen manufacturing.
5. the preparation of the bifunctional catalyst according to claim 4 for absorption enhancement hydrogen production by bio-oil steam reforming
Method, it is characterised in that: the additional amount of the citric acid is the 1~5 of soluble zirconates or aluminum nitrate or aluminium isopropoxide mole
Times.
6. the preparation of the bifunctional catalyst according to claim 4 for absorption enhancement hydrogen production by bio-oil steam reforming
Method, it is characterised in that: gel after drying, is roasted 6 hours in 650 DEG C at 100~120 DEG C, obtains composite oxides.
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| CN108554418B (en) * | 2017-12-12 | 2020-10-30 | 宁波大学 | Ni-B-La catalyst for hydrogen production by catalytic reforming of bio-oil and preparation method thereof |
| CN107954881B (en) * | 2017-12-26 | 2020-05-19 | 余浩 | Method for synthesizing 4, 4' -MDA from aniline |
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| CN110433811B (en) * | 2019-07-31 | 2022-04-19 | 天津大学 | MgO modified Ni/CaO bifunctional catalyst, preparation method and application |
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