CN110562916A - Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming - Google Patents

Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming Download PDF

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CN110562916A
CN110562916A CN201910912314.1A CN201910912314A CN110562916A CN 110562916 A CN110562916 A CN 110562916A CN 201910912314 A CN201910912314 A CN 201910912314A CN 110562916 A CN110562916 A CN 110562916A
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hydrogen
black liquor
catalyst
adsorption
lignin
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CN110562916B (en
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余皓
李函珂
吴世杰
党成雄
彭峰
王红娟
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention discloses a method for producing hydrogen by adsorption-enhanced reforming of lignin black liquor. The method comprises the following steps: (1) filling a Ni-Ca-Al powder catalyst in a reactor; (2) injecting lignin black liquor aqueous solution into a reactor by taking inert gas as carrier gas to carry out reforming hydrogen production; (3) when CO is present2After the adsorption of (a) is saturated, the catalyst is regenerated in an inert atmosphere. The Ni-Ca-Al catalyst is Ni, CaO and Ca12Al14O33A mixture of (a). The invention can prepare high-purity hydrogen with the purity of 96 percent and the hydrogen yield of 0.9mol H2Per mol of C. The Ni-Ca-Al catalyst shows better stability in the circulating process.

Description

Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a method for producing hydrogen by adsorption-enhanced reforming of lignin black liquor.
Background
In the pulp and paper industry, alkali liquor is commonly used to dissolve the lignin in the raw material for its removal, and the resulting cooking liquor containing inorganic salts and large amounts of lignin, cellulose and hemicellulose is commonly referred to as black liquor. The direct discharge of black liquor not only causes serious ecological damage and environmental pollution, but also is a great waste of biomass resources. Although the heat supply by black liquor combustion is applied to some industrial processes, the thermal efficiency is low, and the requirement of large-scale application cannot be met. In view of this, how to utilize black liquor efficiently is an important issue of industrial concern.
The hydrogen is an environment-friendly energy source, the energy density is high, and the combustion product only contains water, so that the environment is not polluted. With the increasing exhaustion of traditional fossil energy and the tightening of control on carbon emission, hydrogen energy is expected to become one of the main energy sources driving the economic development of the world in decades. The method for preparing hydrogen by using black liquor not only improves the utilization value of the black liquor, avoids the pollution to the environment caused by direct discharge of the black liquor, but also relieves the dependence of the existing hydrogen production process on fossil energy to a certain extent. Therefore, the prospect of preparing hydrogen by using the lignin black liquor is considerable.
because the composition of black liquor is complex, reports of its use for hydrogen production are still less. In the present technology of hydrogen production by using black liquor, the supercritical water gasification method is studied most. Patent JP2006257577-a reports the co-production of hydrogen and methane by supercritical water gasification of lignin black liquor; cao Changqing et al reported that the hydrogen production by supercritical water gasification by mixing black liquor and coal, the hydrogen concentration can reach 59.26% at 750 deg.C (Energy)&Fuels,2017,31: 13585-13592). They also report that supercritical water gasification of wheat straw black liquor is used to produce hydrogen, although the hydrogen yield can reach 0.75mol H at most2Per mol C, but the hydrogen purity is only about 60 percent, and the gas still contains a large amount of CO2、CH4And CO (Energy)&Fuels,2017,31: 3970-3978). Can be used forIt is seen that the above black liquor hydrogen production process cannot obtain high purity hydrogen and needs to be operated at a high pressure of 22.1 MPa. If high purity Hydrogen is to be obtained, multiple subsequent purification and separation processes are required, but this adds significantly to the cost of Hydrogen production (International Journal of Hydrogen Energy,2009,34: 2350-2360).
Steam reforming hydrogen production is a widely used hydrogen production technology in industry by introducing CO into the steam reforming process2The capture can move the reaction equilibrium to the direction of hydrogen generation, thereby greatly improving the purity and yield of the hydrogen, and the process is called as adsorption enhanced reforming hydrogen production. Patent WO2009115322-A2 reports that the purity of the obtained hydrogen can reach 99.5% by using the adsorption enhanced reforming hydrogen production technology of polyhydric alcohol. Patent CN108328574A reports that the conversion rate of phenol and the purity of hydrogen can reach 99% and 98%, respectively. Chen De et al, using a hydrotalcite-based catalyst with Pd as the active component, performed adsorption-enhanced reforming of bio-oil model compound acetic acid at 525 ℃ at normal pressure with hydrogen concentration and yield up to 99.5% and 90%, respectively (ChemSusChem,2014,7: 3063-3077). Yu Hao (chemical Engneeering journal,2019,360:47-53) et al utilize Ni as the catalytically active component and CaO as CO2Trapping agent, Ca12Al14O33The dual-function catalyst as a carrier is used for absorbing and enhancing the glycerol as the by-product of the biodiesel to reform steam to prepare hydrogen, the reaction is carried out at 550 ℃ and the desorption is carried out at 700 ℃ respectively under normal pressure, and the hydrogen concentration is maintained to be more than 98% in a 10-circle cycle experiment. The reports show that the adsorption enhanced reforming technology can prepare high-purity hydrogen, and compared with the supercritical water gasification technology, the technology has the advantages of mild process conditions and simple and convenient operation. However, the above reports all use high purity chemical reagents as the feedstock for adsorption enhanced reforming, and it is not expected that a similar catalyst will be used for hydrogen production from black liquor, which is far more complex in composition, to obtain high purity hydrogen.
Disclosure of Invention
The invention aims to provide a method for producing hydrogen by adsorption-enhanced reforming of lignin black liquor, which removes CO generated in the reforming process through adsorption2One step directlyHigh-purity hydrogen is obtained.
The object of the invention is solved by at least one of the following solutions.
A method for producing hydrogen by adsorption-enhanced reforming of lignin black liquor comprises the following steps:
(1) Filling a Ni-Ca-Al powder catalyst in a reactor;
(2) Injecting lignin black liquor aqueous solution into a reactor by taking inert gas as carrier gas to carry out reforming hydrogen production;
(3) When CO is present2after the adsorption of (a) is saturated, the catalyst is regenerated in an inert atmosphere.
Preferably, the mass content of Ni in the Ni-Ca-Al catalyst in the step (1) is 5-20%, and the catalyst has the functions of catalyzing and absorbing CO2And (4) performing functions.
Preferably, in the step (1), the Ni-Ca-Al catalyst is Ni, CaO and Ca12Al14O33A mixture of (a).
Preferably, the molar ratio of Ca to Al in the Ni-Ca-Al catalyst in the step (1) is 1.6-3.4: 1.
Preferably, the concentration of the lignin black liquor aqueous solution in the step (2) is 0.104-0.313g/ml, and more preferably 0.156-0.208 g/ml.
Preferably, the gas hourly space velocity of the lignin black liquor aqueous solution in the step (2) is 2000-9000 h-1more preferably 4500-7500 h-1。
Preferably, the reaction temperature in the step (2) is 400-700 ℃, and more preferably 500-650 ℃.
Preferably, the regeneration temperature in the step (3) is more than 500 ℃ and less than or equal to 1000 ℃; further preferably 750 to 850 ℃.
Preferably, the regeneration time in the step (3) is 0.1-6 h, and more preferably 1-2 h.
Compared with the prior art, the invention has the following advantages:
The purity of the hydrogen obtained by the adsorption-enhanced reforming process applied to the lignin black liquor is high (up to 96%), and in a 5-circle cycle experiment, the hydrogen is obtainedThe concentration is maintained above 96 percent, and the hydrogen yield is maintained at 0.9mol H2More than/mol C. The method realizes effective reutilization of the black liquor, avoids pollution to the environment, and can obtain high-purity hydrogen without working under high pressure and subsequent separation and purification processes compared with the method for preparing hydrogen by using the black liquor in the prior art, thereby obviously reducing the cost of hydrogen preparation.
Drawings
FIG. 1 is an X-ray diffraction pattern of the Ni-Ca-Al catalyst of example 2.
Detailed Description
The following examples and drawings further illustrate the embodiments of the present invention, but the scope of the present invention is not limited to the following embodiments.
the hydrogen concentration in the following examples was determined by Gas Chromatography (GC) analysis, and the GC assay was quantified using an external standard method.
Examples 1 to 4
Take 15.6gCa (NO)3)2·4H2O、8.8gAl(NO3)3·9H2O (molar ratio of Ca to Al 2.8: 1) and a certain amount of Ni (NO) according to the Ni content in Table 13)2·6H2Dissolving O in 50mL of deionized water, and uniformly stirring to obtain a mixed solution I; taking 4.2g of NaCO3And 2.4g of NaOH are dissolved in 50mL of deionized water, and the mixture is uniformly stirred to obtain a mixed solution II. The mixed solution II was slowly added dropwise to the mixed solution I under magnetic stirring to perform a coprecipitation reaction. And then, adjusting the pH value of the solution to 10.0 by using 3mol/L NaOH, aging the obtained precipitate at 65 ℃ for 16h, filtering, washing, drying, crushing, calcining at 800 ℃ for 4h, and treating the obtained powder at 700 ℃ for 1h by using hydrogen to obtain the Ni-Ca-Al catalyst. During the lignin black liquor adsorption enhanced reforming reaction, the Ni-Ca-Al catalyst in the table 1 is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500h is carried out-1The lignin black liquor aqueous solution with the concentration of 0.156g/mL is introduced at the gas hourly space velocity, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction, as determined by GC, are shown in Table 1 below.
Practice ofThe X-ray diffraction pattern of the catalyst in example 2 is shown in fig. 1. As can be seen from FIG. 1, the catalysts are Ni, CaO and Ca12Al14O33A mixture of (a). (the denominator of the hydrogen yield in the table is the amount of carbon species in the black liquor, and since the black liquor composition is quite complex, the hydrogen yield is usually expressed in terms of the amount of hydrogen species that can be produced per mole of carbon, i.e. molH2In mol C represents
TABLE 1
Examples 1 2 3 4
Content of Ni (wt.%) 5 10 15 20
Purity of hydrogen (%) 97.9 98.3 98.3 98.8
Yield of hydrogen (mol H)2/mol C) 0.71 1.00 0.92 0.95
Examples 5 to 7
Changing Ca (NO) while preparing solution I, keeping Ni content at 10 wt.%3)2·4H2O and Al (NO)3)3·9H2O, Ni-Ca-Al catalysts were prepared with the Ca to Al molar ratios listed in Table 2. The other conditions were the same as in example 2. During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al in the table 2, nitrogen is used as a carrier gas, and 4500h is carried out-1The lignin black liquor aqueous solution with the concentration of 0.156g/mL is introduced at the gas hourly space velocity, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction, as determined by GC, are shown in Table 2.
TABLE 2
Examples 8 to 11
During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as carrier gas, lignin black liquor aqueous solution with the concentration of 0.156g/mL is introduced at the gas hourly space velocity listed in Table 3, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction, as determined by GC, are shown in Table 3 below.
TABLE 3
Examples 8 2 9 10 11
Gas hourly space velocity (h)-1) 2000 4500 6000 7500 9000
Purity of hydrogen (%) 97.2 98.3 97.7 97.0 94.2
Yield of hydrogen (mol H)2/mol C) 1.16 1.00 0.91 0.85 0.77
examples 12 to 15
During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as a carrier gas, and 4500h is carried out-1gas hourly space velocity ofThe aqueous solution of lignin black liquor having a lignin black liquor concentration as listed in Table 4 was introduced, and the reaction temperature was 550 ℃. The concentration of hydrogen in the product after 10min of reaction was determined by GC and is shown in Table 4 below.
TABLE 4
Examples 12 2 13 14 15
Lignin black liquor concentration (g/mL) 0.104 0.156 0.171 0.208 0.313
Purity of hydrogen (%) 96.7 98.3 97.9 97.4 95.9
Yield of hydrogen (mol H)2/mol C) 1.20 1.00 0.97 0.93 0.75
Examples 16 to 21
During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as a carrier gas, and 4500h is carried out-1The lignin black liquor aqueous solution with a concentration of 0.156g/mL was introduced at the gas hourly space velocity of (2) and the reaction was carried out at the temperature listed in Table 5. The concentration of hydrogen in the product after 10min of reaction was determined by GC and is shown in Table 5 below.
TABLE 5
Examples 16 17 18 2 19 20 21
Reaction temperature (. degree.C.) 400 450 500 550 600 650 700
Purity of hydrogen (%) 85.2 93.3 98.8 98.3 94.4 84.9 78.2
Yield of hydrogen (mol H)2/mol C) 0.37 0.45 0.62 1.00 0.94 0.95 0.91
Examples 22 to 26
During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as a carrier gas, and 4500h is carried out-1The lignin black liquor aqueous solution with the concentration of 0.156g/mL is introduced at the gas hourly space velocity, and the reaction temperature is 550 ℃. When CO is present2After saturation of the adsorption, the catalyst was regenerated at the temperature listed in Table 6 for 1 hour. The cycle is repeated 3 times. The concentration of hydrogen in the product after 10min of reaction was determined by GC and is shown in Table 6 below. At a regeneration temperature of 500 ℃, CO can not be desorbed2The second cycle does not have the adsorption enhancement effect, so the hydrogen concentration is greatly reduced
TABLE 6
Examples 22 23 24 25 26
Regeneration temperature (. degree.C.) 500 750 800 850 1000
Purity of first-round hydrogen (%) 97.5 97.8 98.3 97.9 98.5
Purity of second ring hydrogen (%) 66.9 93.3 97.6 96.4 93.2
purity of third Ring Hydrogen (%) 68.1 91.9 98.2 95.9 91.0
First cycle hydrogen yield (mol H)2/mol C) 0.93 0.95 1.00 0.94 0.88
Second cycle hydrogen yield (mol H)2/mol C) 0.91 0.88 0.96 1.04 0.91
Yield of hydrogen (mol H) for the third cycle2/mol C) 0.96 0.84 0.98 0.96 0.87
Examples 27 to 29
During the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as a carrier gas, and 4500h is carried out-1The gas hourly space velocity of (2) is introduced into the wood with the concentration of 0.156g/mLThe reaction temperature of the aqueous solution of the black liquor is 550 ℃. When CO is present2After saturation of the adsorption, the catalyst was regenerated at a regeneration temperature of 800 ℃ for the times listed in Table 6. The cycle is repeated 3 times. The concentration of hydrogen in the product after 10min of reaction was determined by GC and is shown in Table 7 below.
TABLE 7
Examples 27 24 28 29
Regeneration time (h) 0.1 1 2 6
Purity of first-round hydrogen (%) 98.4 98.3 98.1 98.6
Purity of second ring hydrogen (%) 95.4 97.6 96.4 92.2
Purity of third Ring Hydrogen (%) 95.3 98.2 95.2 90.6
First cycle hydrogen yield (mol H)2/mol C) 0.92 1.00 0.92 0.91
Second cycle hydrogen yield (mol H)2/mol C) 0.89 0.96 0.91 0.87
Yield of hydrogen (mol H) for the third cycle2/mol C) 0.90 0.98 0.87 0.87
Example 30
Cycle stability experiments: during the lignin black liquor adsorption enhanced reforming reaction, a fixed bed reactor is filled with a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 wt%, nitrogen is used as a carrier gas, and 4500h is carried out-1The lignin black liquor aqueous solution with the concentration of 0.156g/mL is introduced at the gas hourly space velocity, and the reaction temperature is 550 ℃. When CO is present2After saturation of the adsorption, regeneration is carried out at 800 ℃ for 1 h. The cycle is repeated for 5 times. The concentration of hydrogen in the product after 10min of reaction was determined by GC and is shown in Table 8 below.
TABLE 8
Number of cycles 1 2 3 4 5
Purity of hydrogen (%) 97.8 97.5 96.7 96.6 96.8
Yield of hydrogen (mol H)2/mol C) 0.91 0.93 0.92 0.96 0.90
It should be emphasized that the above-described embodiments are merely examples for clearly illustrating the present invention and are not to be considered as a complete limitation of the embodiments. Other variants will be apparent to those skilled in the art on the basis of the foregoing description, and it is not necessary to exemplify all the embodiments herein, but obvious variations are nevertheless within the scope of the invention.

Claims (9)

1. A method for producing hydrogen by adsorption-enhanced reforming of lignin black liquor is characterized by comprising the following steps:
(1) Filling a Ni-Ca-Al powder catalyst in a reactor;
(2) Injecting lignin black liquor aqueous solution into a reactor by taking inert gas as carrier gas to carry out reforming hydrogen production;
(3) When CO is present2After the adsorption of (a) is saturated, the catalyst is regenerated in an inert atmosphere.
2. The method according to claim 1, wherein in the step (1), the Ni-Ca-Al catalyst is Ni, CaO and Ca12Al14O33A mixture of (a).
3. The method according to claim 1, wherein the mass content of Ni in the Ni-Ca-Al catalyst in the step (1) is 5-20%.
4. The method according to claim 1, wherein the molar ratio of Ca to Al in the Ni-Ca-Al catalyst in the step (1) is 1.6-3.4: 1.
5. the method according to claim 1, wherein the gas hourly space velocity of the lignin black liquor in the step (2) is 2000 ~ 9000h-1 。
6. the method according to claim 1, wherein the concentration of the lignin black liquor aqueous solution in the step (2) is 0.104 ~ 0.313 g/ml.
7. The method according to claim 1, wherein the reaction temperature in the step (2) is 400 to 700 ℃.
8. the method of claim 1, wherein the regeneration temperature in step (3) is greater than 500 ℃ and less than or equal to 1000 ℃.
9. the method according to claim 1, wherein the regeneration time in the step (3) is 0.1 ~ 6 h.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257577A (en) * 2005-03-17 2006-09-28 Tomoegawa Paper Co Ltd Method for gasifying kraft pulp black liquor and method for producing hydrogen
US20080237542A1 (en) * 2007-03-05 2008-10-02 Regents Of The University Of Minnesota Reactive flash volatilization of fluid fuels
CN103769107A (en) * 2014-02-24 2014-05-07 南京理工大学 Biomass hydrogen production composite difunctional particle and preparation method and application thereof
CN108328574A (en) * 2018-01-31 2018-07-27 华南理工大学 A kind of method of Adsorption of Phenol enhancing reformation hydrogen production
CN110252319A (en) * 2019-07-15 2019-09-20 广东石油化工学院 A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257577A (en) * 2005-03-17 2006-09-28 Tomoegawa Paper Co Ltd Method for gasifying kraft pulp black liquor and method for producing hydrogen
US20080237542A1 (en) * 2007-03-05 2008-10-02 Regents Of The University Of Minnesota Reactive flash volatilization of fluid fuels
CN103769107A (en) * 2014-02-24 2014-05-07 南京理工大学 Biomass hydrogen production composite difunctional particle and preparation method and application thereof
CN108328574A (en) * 2018-01-31 2018-07-27 华南理工大学 A kind of method of Adsorption of Phenol enhancing reformation hydrogen production
CN110252319A (en) * 2019-07-15 2019-09-20 广东石油化工学院 A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof

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