CN102489310B - A kind of composite oxide catalysts for bio-oil self-heating recapitalization hydrogen making - Google Patents
A kind of composite oxide catalysts for bio-oil self-heating recapitalization hydrogen making Download PDFInfo
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- CN102489310B CN102489310B CN201110362760.3A CN201110362760A CN102489310B CN 102489310 B CN102489310 B CN 102489310B CN 201110362760 A CN201110362760 A CN 201110362760A CN 102489310 B CN102489310 B CN 102489310B
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
Relate to a kind of composite oxide catalysts for bio-oil water phase components self-heating recapitalization hydrogen making.The present invention is directed to that existing catalyst occurs in bio-oil reforming process that serious carbon deposit, accessory substance are many, active component oxidation, sinter and cause the problem of catalysqt deactivation, a kind of stable configuration, resistance to sintering, anti-carbon deposit, sludge proof new catalyst are provided.The catalyst that the present invention relates to is a kind of composite oxides, standby with co-precipitation legal system, consist of with the percentage by weight of oxide basis: nickel oxide content is 12.9wt%, content of magnesia is 52.9wt%, manganese dioxide content is 21.6wt%, and ferric oxide content is 12.6wt%.This catalyst loads fixed bed reactors, with bio-oil water phase components for raw material, after vaporization, mixes with oxygen or air, under the process conditions such as suitable temperature, pressure, air speed, and the obtained gaseous mixture being rich in hydrogen.
Description
Technical field
The present invention relates to a kind of composite oxide catalysts for bio-oil self-heating recapitalization hydrogen making, more particularly, relate to a kind of Ni-based composite oxide catalysts, be applied to the water phase components of bio-oil for raw material, and in fixed bed reactors, prepare the process of hydrogen.
Background technology
Hydrogen is an important industrial chemicals, and as a clean energy carrier, obtains growing interest.By the traditional resource such as coal and natural gas hydrogen making, the rising of dioxide atmosphere content can be caused.Living beings have abundance, the advantage such as renewable, become the hydrogen feedstock that has better prospect.It is low that the primary biomass energy existed with forms such as cellulose, hemicellulose and lignin also exists energy density, problems such as collecting, lay in, freight is high.By living beings by Rapid Thermal solution, obtain the bio-oil that energy density is large, effectively can solve the problem of primary biomass raw material large scale collection, storage and transport, thus improve the economy of biomass energy.The oil phase component of bio-oil is through being separated or by subsequent processes such as rearrangement, reformations, can obtaining the high value added products such as phenols, aromatic hydrocarbons and ether product; And the water-phase product of remainder, its main component is acetic acid, acetone, ethylene glycol, formic acid, hydroxyl acetaldehyde, glyoxal, formaldehyde etc., then can be used as the raw material of scale hydrogen making.Compared with living beings direct gasification hydrogen making, the hydrogen manufacturing of bio-oil water phase components has higher hydrogen yield, and gas product has higher hydrogen content, is conducive to rear obtained pure hydrogen of purifying.
Bio-oil water phase components hydrogen making, generally can adopt the mode of steam reforming.Steam reforming is a strong endothermic reaction, needs extraneous lasting heat supply, can maintain the carrying out of reaction in process; In addition, bio-oil complicated component, side reaction is many, and Carbon Deposit Phenomenon is serious, covers catalyst surface active position, and reaction tube top can be caused to block, cause rapid catalyst deactivation and reaction terminating.
Self-heating recapitalization process, with bio-oil water phase components and oxygen or air for raw material, include the reforming reaction of heat absorption and the partial oxidation reaction of heat release, by the oxygen content in adjustment unstripped gas, the thermal effect that can adjust overall process easily should be balance or weak exothermic reaction, thus do not need extraneous heat supply and maintain reaction continue carry out.Meanwhile, the introducing of oxygen, will affect reactant molecule in the absorption of catalyst surface and activation process, the generation of induction transiting product and conversion, effectively can suppress the generation of carbon deposit predecessor, and the carbon deposit oxidation being simultaneously easy to be formed is eliminated.
Due to the feature of autothermal reforming reaction, in unstripped gas, there is oxygen, and these oxygen mainly transform in the front end of beds, this bed local temperature can up to 800-1000 degree Celsius, cause the sintering of catalyst carrier and active component to be assembled and become large, cause the minimizing of number of active center; The existence of oxygen, makes the active component of bed front end easily oxidized simultaneously.These two factors, easily cause bed to react the inactivation of local catalyst of front end, thus are not had no progeny in reaction front end to move, finally cause the inactivation of whole beds.Therefore, development structure is stablized, the catalyst of resistance to oxidation and resistance to sintering and anti-carbon deposit is the key issue that bio-oil water phase components autothermal reforming reaction hydrogen making process need solves.
In catalyst composition, magnesia is owing to having stronger alkalescence, and have that fusing point is high, Heat stability is good, stable chemical nature, easily carry out the features such as machining is shaping, therefore magnesia becomes a kind of excellent catalyst carrier, but its specific area is lower.The present invention is directed to reforming catalyst, introducing manganese and iron are as auxiliary agent, prepare the composite oxides of magnesia, manganese oxide and iron oxide, higher specific area and heat endurance can be obtained, and introduce nickel as active component, be applied in bio-oil water phase components self-heating recapitalization process, obtain higher hydrogen yield.
Summary of the invention
Technical problem to be solved by this invention is, for in bio-oil water phase components self-heating reforming hydrogen manufacturing process, the change of existing catalyst structure and the oxidation of active component and Sintering Problem and cause the problem of inactivation, provide a kind of Stability Analysis of Structures, resistance to sintering, anti-carbon deposit, resistance to oxidation, active high new catalyst.
Technical scheme of the present invention:
Composite oxide catalysts of the present invention, its shape is the particle of 0.45-0.84mm, it is characterized in that, described composition is the composite oxides of nickel, magnesium, manganese, iron, its percentage by weight consists of: nickel oxide content is 10-16wt%, content of magnesia is 40-63wt%, and manganese dioxide content is 23-32wt%, and ferric oxide content is 11-26wt%.
In preferred embodiment in the present invention, composition and the composition percentage composition of catalyst are: nickel oxide content is 12.9wt%, and content of magnesia is 52.9wt%, and manganese dioxide content is 21.6wt%, and ferric oxide content is 12.6wt%.
Composite oxide catalysts of the present invention, use continuous co-precipitation method to prepare, detailed process comprises:
1) according to catalyst chemical composition, the mixed solution of preparation nickel nitrate, magnesium nitrate, manganese nitrate and ferric nitrate;
2) be 1: 16 ~ 24 according to carbonate and mol ratio hydroxy, and according to 1) metal cation electric charge summation in described mixed solution and mol ratio hydroxy be 1: (15 ~ 18), the mixed solution of preparation sodium carbonate and NaOH.
3) by step 1) solution prepared and step 2) solution prepared carries out continuous co-precipitation at 60-75 DEG C, and the presoma sediment of obtained composite oxide catalysts, through stirring aging 20-24h.Gained sediment after filtration, wash by deionized water, dry, and through 600-700 DEG C of (preferably 650 DEG C) roasting 3-5 hour, through pulverizing and sieving, the particle of obtained 0.45-0.84mm, its specific area is 133-210m
2/ g, must invent described composite oxide catalysts.
Composite oxide catalysts of the present invention, effectively can be used in bio-oil water phase components self-heating reforming hydrogen manufacturing process: first loaded in fixed bed reactors by 50-200mg catalyst, in H before using
2/ N
2650 DEG C of reduction, 4 hours activation process in gaseous mixture, purge through nitrogen, then the mol ratio passing into 50-200ml/min is the mist of living beings profit phase component/water/oxygen=1/ (2.0-4.0)/(0.2-0.9), reacted by beds, reaction temperature is 400 DEG C-700 DEG C.
Beneficial effect of the present invention:
(1) the present invention adopts co-precipitation legal system for brucite (Mg (OH)
2.mH
2o) layer structure presoma, active component nickel and auxiliary agent manganese and iron are incorporated in layer structure or between layer structure simultaneously, active component and auxiliary agent is impelled to be dispersed on magnesium oxide carrier, simultaneously due to heat endurance and the chemical stability of magnesium oxide carrier, improve the stability of catalyst in self-heating recapitalization process.
(2) catalyst of the present invention introduces iron and manganese auxiliary agent, and the specific area of catalyst is by 110m
2/ g brings up to 160-210m
2/ g scope; Give electronic action simultaneously due to auxiliary agent, improve reproducibility and the stability of active component nickel.
(4) show through bio-oil water phase components autothermal reforming reaction result, catalyst of the present invention is in activity is investigated, show Stability Analysis of Structures, resistance to sintering, anti-carbon deposit, resistance to oxidation, the feature such as activity stabilized, reaction temperature 650 DEG C (under condition, conversion ratio is stabilized in 100%, and in product dry gas, hydrogen volume percentage composition is stabilized between 53.5%-56.2%.
Detailed description of the invention
Reference example 1
Take the Ni (NO of 15.31 grams
3)
26H
2mg (the NO of O and 102.21 gram
3)
26H
2o, adds in the deionized water of 452ml, is mixed with solution #1.Take the Na of 48.13 grams NaOH and 7.97 gram
2cO
3, add in the deionized water of 1278ml, be mixed with solution #2.By solution #2 and #3 in the scope that pH is 10.5 ± 0.5, carry out co-precipitation operation at 70-75 DEG C, and maintain this temperature and stir aging 20-24h.Sediment after filtration, wash, and in 110 DEG C of dry 16h, through 650 DEG C of roasting 4h, the catalyst B IO-ATR-N-01 obtained, the weight of this catalyst consists of: nickel oxide content is 19.7%, and content of magnesia is 80.3% by deionized water.
Bio-oil water phase components autothermal reforming reaction activity rating carries out in continuous fixed bed reactor.By catalyst grinding also compressing tablet, the particle that then broken and screening is 0.45-0.84mm, in loading reactor, in H
2/ N
2650 DEG C of reduction 4h in gaseous mixture.(weight percent consists of preparation bio-oil water phase components: acetic acid: glycolaldehyde: formic acid: glyoxal: formaldehyde: hydroxypropanone-=24.1: 20.2: 17.5: 15.7: 12.4: 10.1), and by mixed solution (bio-oil water phase components/water=1/ (2.0-4.0) of bio-oil water phase components and water, mol ratio) inject vaporizer after vaporization with syringe pump, mixture of oxygen (according to mol ratio being: bio-oil water phase components/oxygen=1/ (0.2-0.9)), and this unstripped gas is imported reaction bed, reaction condition is temperature 400-700 DEG C, normal pressure, air speed 12000-30000h
-1, reaction end gas is to configure the chromatographic of thermal conductivity detector (TCD) and flame ionization ditector and packed column (Porapaq-QS and 5A) and capillary column (Q-Plot).
Catalyst B IO-ATR-N-01 investigates through bio-oil water phase components autothermal reforming reaction, be living beings oil/water/oxygen molar ratio is 1/3.3/0.7, normal pressure, air speed 15000h at temperature 650 DEG C, raw material
-1time, this catalyst has higher activity in initial reaction stage, and bio-oil water phase components total conversion is 100%, and in product dry gas, hydrogen volume content is about 38%.Along with the carrying out of reaction, total conversion and hydrogen content reduce, and react after 30 hours, bio-oil water phase components total conversion drops to 20.6%, and in product dry gas, hydrogen content drops to 6.3%.Reacted catalyst, through characterizing, finds that it exists carbon deposit, active component oxidation and sintering phenomenon.
Embodiment 1
Take the Ni (NO of 10.08 grams
3)
26H
2o, the Mg (NO of 67.30 grams
3)
26H
2o, the Fe (NO of 20.01 grams
3)
39H
2mn (the NO of the 50wt% of O and 17.72 gram
3)
2solution, adds in the deionized water of 396ml, is mixed with solution #1.Take the Na of 31.70 grams NaOH and 5.25 gram
2cO
3, add in the deionized water of 841ml, be mixed with solution #2.Subsequent step, with reference example 1, obtains catalyst B IO-ATR-NMF-01.The percentage by weight of this catalyst consists of: nickel oxide content is 12.9%, and content of magnesia is 52.9%, and manganese dioxide content is 21.5%, and ferric oxide content is 12.6%.
This catalyst, in bio-oil water phase components autothermal reforming reaction, be living beings oil/water/oxygen molar ratio is 1/3.3/0.7, normal pressure, air speed 15000h at temperature 650 DEG C, raw material
-1time, its bio-oil water phase components total conversion is stabilized in 100%, and in product dry gas, hydrogen content maintains between 53.5%-56.2%, does not observe bio-oil water phase components total conversion and decline and degradation deactivation phenomenom under hydrogen content in 30 hours.
Catalytic activity test result shows, and catalyst of the present invention has the features such as conversion ratio is high, product hydrogen content is high, good stability.Meanwhile, reacted catalyst characterization result display, catalyst of the present invention has the features such as Stability Analysis of Structures, resistance to sintering, anti-carbon deposit, resistance to oxidation.
Claims (3)
1. the composite oxide catalysts of bio-oil self-heating recapitalization hydrogen making, is characterized in that: according to catalyst chemical composition, the mixed solution of preparing metal nitrate; Be 1: 16 ~ 24 according to carbonate and mol ratio hydroxy, and metal cation electric charge summation and mol ratio hydroxy are 1: (15 ~ 18), the mixed solution of preparation sodium carbonate and NaOH; Above-mentioned solution is carried out continuous co-precipitation at 60-75 DEG C, and the presoma sediment of obtained composite oxide catalysts, through stirring aging 20-24h; Gained sediment after filtration, deionized water is washed, drying, through 600-700 DEG C of roasting 3-5 hour, through pulverizing and sieving, the particle of obtained 0.45-0.84mm, obtain described composite oxide catalysts, consist of with the percentage by weight of oxide: nickel oxide content is 12.9wt%, content of magnesia is 52.9wt%, manganese dioxide content is 21.6wt%, and ferric oxide content is 12.6wt%.
2. the preparation method of the nickel-base catalyst of bio-oil self-heating recapitalization hydrogen making according to claim 1, is characterized in that: comprise the following steps:
1) according to catalyst chemical composition, the mixed solution of preparation nickel nitrate, magnesium nitrate, manganese nitrate and ferric nitrate;
2) be 1: 16 ~ 24 according to carbonate and mol ratio hydroxy, and according to 1) metal cation electric charge summation in described mixed solution and mol ratio hydroxy be 1: (15 ~ 18), the mixed solution of preparation sodium carbonate and NaOH;
3) by step 1) solution prepared and step 2) solution prepared carries out continuous co-precipitation at 60-75 DEG C, and the presoma sediment of obtained composite oxide catalysts, through stirring aging 20-24h; Gained sediment after filtration, wash by deionized water, dry, and through 600-700 DEG C of roasting 3-5 hour, through pulverizing and sieving, the particle of obtained 0.45-0.84mm, obtains composite oxide catalysts.
3. catalyst described in claim 1 is in the purposes of bio-oil self-heating reforming hydrogen manufacturing process, it is characterized in that: by catalyst according to claim 1 for 50-200mg and the catalyst prepared by preparation method described in claim 2 at H
2/ N
2in gaseous mixture, 650 DEG C are reduced 4 hours, purge through nitrogen, then the mixed solution of a certain amount of bio-oil water phase components and water is injected vaporizer after vaporization with syringe pump, mixture of oxygen, the mol ratio obtaining 50-200ml/min is the mist of living beings profit phase component/water/oxygen=1/ (2.0-4.0)/(0.2-0.9), reacted by beds, reaction temperature is 400 DEG C-700 DEG C.
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| CN102921426B (en) * | 2012-11-05 | 2015-02-18 | 中国科学院过程工程研究所 | Catalyst for catalytic conversion of biological cellulose and preparation method and applications of catalyst |
| CN103657654B (en) * | 2013-12-17 | 2015-05-13 | 成都理工大学 | Olivine nickel-based catalyst for preparing hydrogen through autothermal reforming of acetic acid |
| CN107128875B (en) * | 2016-05-31 | 2021-04-06 | 浙江理工大学 | Hydrogen production catalytic system, hydrogen production system comprising catalytic system and application of catalytic system |
| CN107042111B (en) * | 2017-01-11 | 2020-02-04 | 成都理工大学 | Layered perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen and preparation method thereof |
| CN109225250B (en) * | 2018-09-19 | 2019-10-25 | 成都理工大学 | A kind of Ni-Cr-Mn mesoporous composite oxides catalyst of acetic acid self-heating reforming hydrogen manufacturing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736591A (en) * | 2005-07-15 | 2006-02-22 | 山东大学 | Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor |
| CN101181686A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Hydrotalcite type hydrocracking catalyst and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736591A (en) * | 2005-07-15 | 2006-02-22 | 山东大学 | Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor |
| CN101181686A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Hydrotalcite type hydrocracking catalyst and method for preparing same |
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