CN108212165B - A kind of catalyst and preparation method thereof for biomass low temperature gasification high-purity hydrogen - Google Patents
A kind of catalyst and preparation method thereof for biomass low temperature gasification high-purity hydrogen Download PDFInfo
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- CN108212165B CN108212165B CN201810054507.3A CN201810054507A CN108212165B CN 108212165 B CN108212165 B CN 108212165B CN 201810054507 A CN201810054507 A CN 201810054507A CN 108212165 B CN108212165 B CN 108212165B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002309 gasification Methods 0.000 title claims abstract description 30
- 239000002028 Biomass Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000006703 hydration reaction Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000006722 reduction reaction Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 8
- 239000000292 calcium oxide Substances 0.000 claims abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 150000002815 nickel Chemical class 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000001913 cellulose Substances 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2203/02—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
A kind of preparation method of the catalyst for biomass low temperature gasification high-purity hydrogen, load weighted soluble calcium salt and nickel salt are dissolved in deionized water, it stirs, gained mixed solution is placed in precooling in refrigerator and freezes completely to solution, sample is placed in low-temperature vacuum drying in vacuum freeze drier and forms uniform solid powder after freezing, it is calcined in Muffle furnace, by product grind into powder after calcining, it is subsequently placed in tube furnace, first carry out reduction reaction: at a certain temperature, the hydrogen for being passed through certain volume score is reduced to nickel simple substance to nickel oxide completely；Carry out hydration reaction again: being passed through vapor makes calcium oxide be fully converted to calcium hydroxide.Catalyst of the present invention is suitable for biomass pyrolytic gasification under the conditions of low-temperature atmosphere-pressure and produces hydrogen, and the H of small molecule is converted mainly into after biomass pyrogenation gasification2, CO and a small amount of carbon distribution.With traditional biomass gasify produce hydrogen catalyst compared with it is low using temperature, catalytic activity is high, it is at low cost, be easy to be industrially used.
Description
Technical field
The invention belongs to new material and its applied technical fields, are related to biomass preparing high purity hydrogen under low-temperature atmosphere-pressure
Method, in particular to a kind of catalyst and preparation method thereof for biomass low temperature gasification high-purity hydrogen.
Background technique
It is a low-carbon using biomass waste hydrogen manufacturing, green and sustainable technology sends out environmental protection and society
Exhibition has great strategic significance.The current common usual reaction temperature of pyrolytic gasification technique using biomass hydrogen preparation is higher than 800
℃.And biomass waste higher for moisture content, it is necessary to it is anti-just to can be effectively carried out pyrolytic gasification after desiccation pre-processes
It answers, the CO or CO of higher concentration furthermore can be mixed in hydrogen made from such technique2, to aggravate the negative of gas separation unit
Load.In order to reduce reaction temperature, the gas producing efficiency and purity of hydrogen are improved, such technique generallys use nickel-base catalyst, is urging
The yield of hydrogen is improved under the action of change reforming reaction.Or using calcium-base absorbing agent to the CO generated in reaction process2It is caught
Collection promotes the yield of steam reaction raising hydrogen to improve the purity of hydrogen.Or during the reaction simultaneously using Ni-based
Catalyst and calcium-base absorbing agent realize the purpose of the hydrogen for obtaining higher degree at a lower reaction temperature.However nickel catalyst
Agent and calcium-base absorbing agent individualism increase the difficulty of material sorting, and there are problems that sintering deactivation, poor circulation.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide one kind to be used for biomass low temperature gasification
Active Ni is equably carried on Ca (OH) by the catalyst and preparation method thereof of high-purity hydrogen2On, Ni/Ca is made
(OH)2It is composite porous.The catalyst has the advantages that high catalytic efficiency, Yi Huishou, recyclable regenerative.Institute in preparation method
The prices of raw materials are cheap, and are easily obtained.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of the catalyst for biomass low temperature gasification high-purity hydrogen, with calcium acetate and nickel nitrate
Or other calcics, nickeliferous soluble-salt specifically comprise the following steps: as catalyst precursors
(1) predecessor mixed solution is prepared
Load weighted soluble calcium salt and nickel salt are dissolved in a certain amount of deionized water, stirred.
In particular, the molar ratio range of Ni and Ca is 1:1.5-6 in the solution of preparation described in step (1), preferably
For 1:3.
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator and carries out precooling and is freezed completely to solution, then will be after freezing
Sample is placed in the progress enough long-times of low-temperature vacuum drying in vacuum freeze drier, forms uniform solid powder.
In particular, precooling temperature described in step (2) be preferably -80 DEG C, cooling time be 4-8 hours, preferably 6
Hour, freeze-drying temperature should be -50 DEG C -- and 70 DEG C, preferably -60 DEG C, pressure are preferably 8.0Pa, and drying time should be 12-
48 hours, preferably 24 hours.
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined in Muffle furnace.After calcining, by product grind into powder.
In particular, the calcination time in Muffle furnace should be 0.5-2.0 hours, preferably 1 hour, temperature should be 750 DEG C-
850 DEG C, preferably 800 DEG C, heating rate should be 5-15 DEG C/min, preferably 10 DEG C/min, and mortar should be agate material.
(4) atmosphere reduction and hydration reaction
Step (3) obtained solid sample is placed in tube furnace, reduction reaction is first carried out: at a certain temperature, being passed through one
The hydrogen for determining volume fraction is reduced to nickel simple substance to nickel oxide completely.Carry out hydration reaction again: being passed through vapor keeps calcium oxide complete
It is converted into calcium hydroxide entirely.
In particular, reduction temperature range is 500-800 DEG C, preferable temperature is 700 DEG C.It is preferred that hydrogen volume score is 5%,
Gas flow range 100-300ml/min, preferably flow are 200ml/min, and the recovery time is preferably 1 hour.Hydration reaction temperature
Spending range is 50 DEG C -200 DEG C, and preferable temperature is 150 DEG C, and vapor flow range is 20-60ml/min, and preferably flow is
200ml/min, hydration reaction time are preferably 1 hour.
Especially suitable for biomass, pyrolytic gasification under the conditions of low-temperature atmosphere-pressure produces hydrogen to catalyst of the present invention.Pyrolysis gas of biomass
The H of small molecule is converted mainly into after change2, CO and a small amount of carbon distribution.Compared with traditional gasification of biomass produces the catalyst of hydrogen
It is low using temperature, catalytic activity is high, cost is relatively low, is easy to be industrially used.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention selection Ca (OH)2Active component with Ni as catalyst both has cheap and catalysis
The advantages of high-efficient, recyclable regenerative.
(2) of the invention by active component Ca (OH)2It is effectively combined with Ni, realizes the concerted catalysis effect of two kinds of active components
It answers.In the catalyst, Ca (OH)2It can be used as carrier and big carrier surface be provided, and the burning of active constituent Ni can be prevented
Knot, makes the stability of catalyst be guaranteed；Ca (OH) simultaneously2Performing catalytic pyrolysis on tar is also had both, catches carbon heat release compensation body in situ
It is heat demand, promotes steam reaction to improve the effect of the yield and purity of hydrogen.
(3) of the invention by active component Ca (OH)2Integrated material is formed in conjunction with Ni, can pass through simple magnetic separation
Technique separates the lime-ash formed after biomass pyrogenation gasification with catalyst, and catalyst after the recovery can be recycled by calcium and be carried out again
It is raw, realize the recycling of catalyst.Avoiding leads to the loss of catalyst because lime-ash is separated with single component catalyst difficulty.
(4) its oxide form can be used in composite catalyst of the invention during real reaction, is further simplified and urges
The preparation process of agent.And hydration reaction can be realized using the water contained by biomass waste, generating has higher active Ca
(OH)2。
Detailed description of the invention
Fig. 1 is the XRD diagram of catalyst activity component in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of catalyst activity component in the embodiment of the present invention 1.
Fig. 3 varies with temperature figure for cellulose pyrolytic gasification gas production rate for catalyst in the embodiment of the present invention 1.
Fig. 4 is that catalyst is used for the cellulose pyrolytic gasification warming-up section production total spirogram of gas in the embodiment of the present invention 1.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.
Ca used in embodiment (OH)2Predecessor calcium acetate be analytical reagents, purity 99.9%.Ni simple substance
Predecessor Nickelous nitrate hexahydrate crystal is analytical reagents, purity 99.9%.
Embodiment 1:
(1) predecessor mixed solution is prepared
Weigh 4.362g Nickelous nitrate hexahydrate crystal and 7.911g acetic acid calcium powder, by the two be dissolved in it is a certain amount of go from
In sub- water, stir.
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator and is freezed 6 hours at -80 DEG C, then the sample after freezing is set
In temperature be -60 DEG C in vacuum freeze drier, pressure be 8.0Pa under the conditions of dry 24 hours, form uniform solid powder
End.
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined 1 hour in Muffle furnace.Calcination temperature is 800 DEG C, heating rate 10
℃/min.Product agate mortar grind into powder after calcining.
(4) atmosphere reduction and hydration reaction
Step (3) obtained solid sample is placed in tube furnace, reduction reaction is first carried out: being passed through hydrogen keeps nickel oxide complete
It is reduced to nickel simple substance.The hydrogen volume score being passed through is 5%, flow 200ml/min, and reduction temperature is 700 DEG C, the time 1
Hour.Carry out hydration reaction again: being passed through vapor makes calcium oxide be fully converted to calcium hydroxide.Being passed through vapor flow is
200ml/min, hydration reaction temperature are 150 DEG C, and the time is 1 hour.
The catalyst prepared is subjected to relevant characterization analysis, wherein XRD diffraction analysis results are as shown in Figure 1, from Fig. 1
It can be seen that the active constituent of catalyst is Ca (OH)2With Ni.SEM Electronic Speculum result is as shown in Fig. 2, as can be seen from Figure 2: straight
The white particulate material of diameter about 50-100nm is more evenly dispersed in the solids surface of porosity and looseness；It is determined by elemental analysis
White particulate material Ni, the solids of porosity and looseness are Ca (OH)2。
By cellulose with the composite catalyst prepared and by C6H5O6: Ca molar ratio is that 1:6 is sufficiently mixed, will
Mixed sample is placed in progress cellulose pyrolytic gasification reaction in thermogravimetric analysis-mass spectrometer small crucible.Reaction process
In, using flow for 500mL/min argon gas as carrier gas, temperature programming be 40 DEG C/min to 600 DEG C.According to mass spectrum on-line checking
Each gas component concentrations signal calculates the generating rate (as shown in Figure 3) that it is varied with temperature and the temperature rise period produces gas total amount (such as
Shown in Fig. 4).As can be seen from Figure 3, the main generation temperature range of hydrogen is 350 DEG C -450 DEG C.The catalyst in this temperature range
Active highest.When temperature rises to 400 DEG C, Ca (OH) 2 starts to decompose, and temperature resolves into CaO when rising to 600 DEG C completely.It can from Fig. 4
Know, the mass percent for the hydrogen that cellulose pyrolytic gasification generates is 77%, it can be seen that the association of active component Ca (OH) 2 and Ni
Same-action greatly inhibits the generation of carbon monoxide and carbon dioxide.Experimental result is listed in table 1.
Embodiment 2:
(1) predecessor mixed solution is prepared
Weigh 4.362g Nickelous nitrate hexahydrate crystal and 3.955g acetic acid calcium powder, by the two be dissolved in it is a certain amount of go from
In sub- water, stir.
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator and is freezed 6 hours at -80 DEG C, then the sample after freezing is set
In temperature be -60 DEG C in vacuum freeze drier, pressure be 8.0Pa under the conditions of dry 24 hours, form uniform solid powder
End.
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined 1 hour in Muffle furnace.Calcination temperature is 800 DEG C, heating rate 10
℃/min.Product agate mortar grind into powder after calcining.
(4) atmosphere reduction and hydration reaction
Step (3) obtained solid sample is placed in tube furnace, reduction reaction is first carried out: being passed through hydrogen keeps nickel oxide complete
It is reduced to nickel simple substance.The hydrogen volume score being passed through is 5%, flow 200ml/min, and reduction temperature is 700 DEG C, the time 1
Hour.Carry out hydration reaction again: being passed through vapor makes calcium oxide be fully converted to calcium hydroxide.Being passed through vapor flow is
200ml/min, hydration reaction temperature are 150 DEG C, and the time is 1 hour.
By cellulose and the catalyst prepared by C6H5O6: Ca molar ratio is progress pyrolytic gasification reaction after 1:6 mixing.
Experimental result is listed in table 1.
Embodiment 3:
(1) predecessor mixed solution is prepared
0.8724g Nickelous nitrate hexahydrate crystal and 3.955g acetic acid calcium powder are weighed, the two is dissolved in a certain amount of go
In ionized water, stir.
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator and is freezed 6 hours at -80 DEG C, then the sample after freezing is set
In temperature be -60 DEG C, pressure 8.0Pa in vacuum freeze drier, under the conditions of dry 24 hours, form uniform solid powder
End.
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined 1 hour in Muffle furnace.Calcination temperature is 800 DEG C, heating rate 10
℃/min.Product agate mortar grind into powder after calcining.
(4) atmosphere reduction and hydration reaction
Step (3) obtained solid sample is placed in tube furnace, reduction reaction is first carried out: being passed through hydrogen keeps nickel oxide complete
It is reduced to nickel simple substance.The hydrogen volume score being passed through is 5%, flow 200ml/min, and reduction temperature is 700 DEG C, the time 1
Hour.Carry out hydration reaction again: being passed through vapor makes calcium oxide be fully converted to calcium hydroxide.Being passed through vapor flow is
200ml/min, hydration reaction temperature are 150 DEG C, and the time is 1 hour.
By cellulose and the catalyst prepared by C6H5O6: Ca molar ratio is progress pyrolytic gasification reaction after 1:6 mixing.
Experimental result is listed in table 1.
Embodiment 4:
(1) predecessor mixed solution is prepared
Weigh 4.362g Nickelous nitrate hexahydrate crystal and 7.911g acetic acid calcium powder, by the two be dissolved in it is a certain amount of go from
In sub- water, stir.
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator and is freezed 6 hours at -80 DEG C, then the sample after freezing is set
In temperature be -60 DEG C in vacuum freeze drier, pressure be 8.0Pa under the conditions of dry 24 hours, form uniform solid powder
End.
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined 1 hour in Muffle furnace.Calcination temperature is 800 DEG C, heating rate 10
℃/min.Product agate mortar grind into powder after calcining.
(4) atmosphere reduction and hydration reaction
Step (3) obtained solid sample is placed in tube furnace, reduction reaction is first carried out: being passed through hydrogen keeps nickel oxide complete
It is reduced to nickel simple substance.The hydrogen volume score being passed through is 5%, flow 200ml/min, and reduction temperature is 700 DEG C, the time 1
Hour.Carry out hydration reaction again: being passed through vapor makes calcium oxide be fully converted to calcium hydroxide.Being passed through vapor flow is
200ml/min, hydration reaction temperature are 150 DEG C, and the time is 1 hour.
By cellulose and the catalyst prepared by C6H5O6: Ca molar ratio is progress pyrolytic gasification reaction after 1:3 mixing.
Experimental result is listed in table 1.
The optimum mole ratio of cellulose, calcium hydroxide and nickel is 1:6:2 as shown in Table 1.
Table 1: embodiment 1-4 biomass pyrogenation gasification hydrogen output experimental result
| Catalyst | C6H5O6: Ca:Ni (molar ratio) | Hydrogen output (mL ﹒ g-1) |
| Embodiment 1 | 1:6:2 | 813.82 |
| Embodiment 2 | 1:6:1 | 726.31 |
| Embodiment 3 | 1:6:4 | 630.25 |
| Embodiment 4 | 1:3:1 | 511.97 |
Claims (9)
1. a kind of preparation method of the catalyst for biomass low temperature gasification high-purity hydrogen, which is characterized in that including such as
Lower step:
(1) predecessor mixed solution is prepared
Load weighted soluble calcium salt and nickel salt are dissolved in a certain amount of deionized water, stirred, wherein Ni with
The molar ratio range of Ca is 1:(1.5-6)；
(2) freeze-drying of mixed solution
Mixed solution obtained by step (1) is placed in refrigerator precooling to freeze completely to solution, then the sample after freezing is placed in
The enough long-times of low-temperature vacuum drying are carried out in vacuum freeze drier, form uniform solid powder；
(3) high temperature solid state reaction
Step (2) resulting dried powder is calcined in Muffle furnace, after calcining, by product grind into powder；
(4) atmosphere reduction and hydration reaction
Powder sample obtained by step (3) is placed in tube furnace, reduction reaction is first carried out: at a certain temperature, being passed through certain body
The hydrogen of fraction is reduced to nickel simple substance to nickel oxide completely；Carry out hydration reaction again: being passed through vapor turns calcium oxide completely
Turn to calcium hydroxide.
2. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is, in the predecessor mixed solution that the step (1) is prepared, the molar ratio of Ni and Ca are 1:3.
3. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that precooling temperature is -80 DEG C in the step (2), and cooling time is 4-8 hours, and freeze-drying temperature is -50 DEG C
~-70 DEG C, pressure 8.0Pa, drying time is 12-48 hours.
4. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that cooling time is 6 hours in the step (2), and freeze-drying temperature is -60 DEG C, and drying time is 24 hours.
5. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that calcination time is 0.5-2.0 hours in the step (3), and temperature is 750 DEG C -850 DEG C, and heating rate should be 5-15
℃/min。
6. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that calcination time is 1 hour in the step (3), and temperature is 800 DEG C, and heating rate is 10 DEG C/min, and mortar is agate
Material.
7. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that reduction temperature range is 500-800 DEG C in the step (4), and hydrogen volume score is 5%, gas flow range
100-300ml/min, recovery time are 1 hour；Hydration reaction temperature range is 50 DEG C -200 DEG C, and vapor flow range is
20-60ml/min, hydration reaction time are 1 hour.
8. the preparation method for the catalyst of biomass low temperature gasification high-purity hydrogen according to claim 1, special
Sign is that reduction temperature is 700 DEG C in the step (4), and hydrogen volume score is 5%, gas flow 200ml/min, goes back
The former time is 1 hour；Hydration reaction temperature is 150 DEG C, vapor flow 200ml/min, the hydration reaction time 1 hour.
9. the catalyst for biomass low temperature gasification high-purity hydrogen that preparation method described in claim 1 is prepared.
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