CN110562916B - Method for producing hydrogen by absorbing and enhancing lignin black liquor - Google Patents
Method for producing hydrogen by absorbing and enhancing lignin black liquor Download PDFInfo
- Publication number
- CN110562916B CN110562916B CN201910912314.1A CN201910912314A CN110562916B CN 110562916 B CN110562916 B CN 110562916B CN 201910912314 A CN201910912314 A CN 201910912314A CN 110562916 B CN110562916 B CN 110562916B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- black liquor
- catalyst
- lignin black
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Abstract
The invention discloses a method for preparing hydrogen by lignin black liquor adsorption enhanced reforming. The method comprises the following steps: (1)Filling Ni-Ca-Al powder catalyst in a reactor; (2) Inert gas is used as carrier gas, lignin black liquor aqueous solution is injected into a reactor for reforming hydrogen production; (3) When CO 2 After saturation of the adsorption, the catalyst is regenerated in an inert atmosphere. The Ni-Ca-Al catalyst is Ni, caO and Ca 12 Al 14 O 33 Is a mixture of (a) and (b). The invention can prepare high-purity hydrogen with the purity of 96 percent, and the hydrogen yield can reach 0.9mol H 2 /mol C. The Ni-Ca-Al catalyst shows better stability during the cycle.
Description
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a method for preparing hydrogen by absorbing and enhancing lignin black liquor.
Background
In the pulp and paper industry, alkali lyes are generally used to dissolve lignin in raw materials for the purpose of removing it, and the resulting cooking liquor containing inorganic salts and a large amount of lignin, cellulose and hemicellulose is often 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 black liquor combustion heating has been applied in some industrial processes, its thermal efficiency is low and still not satisfactory for large-scale applications. In view of this, how to efficiently use black liquor is an important issue of industrial concern.
Hydrogen is an environmentally friendly energy source with high energy density and the combustion products are only water, which is environmentally friendly. With the increasing exhaustion of traditional fossil energy sources and the gradual tightening of control over carbon emissions, hydrogen energy is expected to be one of the main energy sources driving the world economic development in decades. The hydrogen is prepared by using the black liquor, so that the utilization value of the black liquor is improved, the pollution to the environment caused by direct discharge of the black liquor is avoided, and the dependence of the current hydrogen production process on fossil energy can be relieved to a certain extent. Therefore, the hydrogen preparation by using lignin black liquor has a considerable prospect.
Because of the relatively complex composition of black liquor, few reports on the use of black liquor in hydrogen production are currently available. In the technology of hydrogen production by using black liquor at the present stage, a supercritical water gasification method is most studied. Patent JP2006257577-a reports the co-production of hydrogen and methane by supercritical water gasification of lignin black liquor; cao Changqing et al report that mixing black liquor with coal to produce hydrogen by supercritical water gasification, the hydrogen concentration at 750 ℃ can reach 59.26% (Energy)&Fuels,2017, 31:13585-13592). They also reported that supercritical water gasification is performed to produce hydrogen using wheat straw black liquor, although hydrogen yields can be up to 0.75mol H 2 Permol C, but the purity of the hydrogen is only about 60%, and the gas still contains a large amount of CO 2 、CH 4 And CO (Energy)&Fuels,2017, 31:3970-3978). It can be seen that the black liquor hydrogen production process described above cannot obtain high purity hydrogen and requires operation at a high pressure of 22.1 MPa. If high purity hydrogen is to be obtained, multiple subsequent purification and separation treatments are required, but this would add 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 converting CO during steam reforming 2 The capture can lead the reaction balance to move towards the direction of hydrogen generation, thereby greatly improving the purity and yield of the hydrogen, and the process is called adsorption-enhanced reforming hydrogen production. Patent WO2009115322-A2 reports that the purity of the obtained hydrogen can reach 99.5% by the technology of hydrogen production by adsorption-enhanced reforming of polyalcohol. Patent CN108328574a reports the adsorption-enhanced reforming hydrogen production technology of phenol, and the conversion rate and the hydrogen purity of phenol can reach 99% and 98%, respectively. Chen De et al uses hydrotalcite-based catalyst with Pd as active component to perform adsorption enhanced reforming of bio-oil model compound acetic acid at normal pressure and 525 ℃ with hydrogen concentration and yield up to 99.5% and 90% respectively (ChemSusChem, 2014,7:3063-3077). Yu Hao (Chemical EngneeringJournal,2019, 360:47-53) et al utilized Ni as the catalytically active component and CaO as CO 2 Capture agent, ca 12 Al 14 O 33 The method is characterized in that the adsorption enhancement steam reforming hydrogen production of the biodiesel byproduct glycerol is carried out for the supported bifunctional catalyst, 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 10 cycles of circulating experiments. 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 milder process conditions and simpler and more convenient operation. However, the above reports all use high purity chemicals as raw materials for adsorption-enhanced reforming, so that it is not expected that high purity hydrogen can be obtained even when similar catalysts are used for black liquor hydrogen production, which is far more complicated in composition.
Disclosure of Invention
The invention aims to provide a method for producing hydrogen by absorbing and enhancing lignin black liquor and removing CO generated in the reforming process by absorption 2 Directly obtaining the high-purity hydrogen in one step.
The object of the invention is solved by at least one of the following solutions.
A method for producing hydrogen by lignin black liquor adsorption enhanced reforming, comprising the following steps:
(1) Filling Ni-Ca-Al powder catalyst in a reactor;
(2) Inert gas is used as carrier gas, lignin black liquor aqueous solution is injected into a reactor for reforming hydrogen production;
(3) When CO 2 After saturation of the adsorption, the catalyst is regenerated in an inert atmosphere.
Preferably, the Ni content of the Ni-Ca-Al catalyst in the step (1) is 5-20% by mass, and the catalyst has the functions of catalyzing and absorbing CO 2 Function.
Preferably, in the step (1), the Ni-Ca-Al catalyst is Ni, caO and Ca 12 Al 14 O 33 Is a mixture of (a) and (b).
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 lignin black liquor aqueous solution in step (2) has a concentration of 0.104-0.313g/ml, more preferably 0.156-0.208g/ml.
Preferably, the gas hourly space velocity of the lignin black liquor aqueous solution in the step (2) is 2000-9000 h -1 More preferably 4500 to 7500 hours -1 。
Preferably, the reaction temperature in the step (2) is 400 to 700 ℃, and more preferably 500 to 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 step (3) is 0.1 to 6 hours, more preferably 1 to 2 hours.
Compared with the prior art, the invention has the following advantages:
the invention is applied to the adsorption enhancement reforming process of lignin black liquor, the purity of the obtained hydrogen is higher (up to 96%), and in the 5-circle circulation experiment, the concentration of the hydrogen is maintained above 96%, and the hydrogen yield is maintained at 0.9mol H 2 And/mol C or more. The invention realizes the effective reuse of the black liquor, avoids the pollution to the environment, and compared with the method for preparing hydrogen by using the black liquor in the prior art, the method disclosed by the invention can obtain high-purity hydrogen without working under high pressure and subsequent separation and purification processes, thereby obviously reducing the hydrogen production cost.
Drawings
FIG. 1 is an X-ray diffraction pattern of the Ni-Ca-Al catalyst in example 2.
Detailed Description
The following examples and drawings illustrate the invention in more detail, but the scope of the invention is not limited to the following examples.
The concentration of hydrogen in the following examples was determined by Gas Chromatography (GC) analysis, and the quantification method of GC detection employed an external standard method.
Examples 1 to 4
Take 15.6gCa (NO 3 ) 2 ·4H 2 O、8.8gAl(NO 3 ) 3 ·9H 2 O (molar ratio of Ca to Al 2.8:1) and Ni (NO) in an amount corresponding to the Ni content in Table 1 3 ) 2 ·6H 2 O is dissolved in 50mL of deionized water, and mixed solution I is obtained after uniform stirring; 4.2g NaCO was taken 3 And 2.4g of NaOH are dissolved in 50mL of deionized water, and the mixture is stirred uniformly to obtain a mixed solution II. The mixed solution II was slowly added dropwise to the mixed solution I under magnetic stirring to conduct a coprecipitation reaction. Subsequently, the ph=10.0 of the solution was adjusted with 3mol/L NaOH, and the obtained precipitate was aged at 65 ℃ for 16 hours, and after filtration, washing, drying, pulverizing, further calcined at 800 ℃ for 4 hours, and the obtained powder was treated with hydrogen at 700 ℃ for 1 hour, to obtain the ni—ca—al catalyst. When lignin black liquor adsorption enhanced reforming reaction is carried out, a fixed bed reactor is filled with the Ni-Ca-Al catalyst shown in table 1, nitrogen is taken as carrier gas, and 4500h is carried out -1 The gas hourly space velocity of (2) is introduced with lignin black liquor aqueous solution with the concentration of 0.156g/mL, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction were determined by GC are shown in table 1 below.
The X-ray diffraction pattern of the catalyst in example 2 is shown in FIG. 1. As can be seen from FIG. 1, the catalyst is Ni, caO and Ca 12 Al 14 O 33 Is a mixture of (a) and (b). (the denominator of the hydrogen yield in the table is the amount of carbon element material in the black liquor, and because the black liquor is very complex in composition, the hydrogen yield is usually expressed in terms of the amount of hydrogen material that can be produced per mole of carbon, i.e., molH 2 Mol C
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
Keeping the Ni content at 10wt.%, the Ca (NO) was changed when preparing solution I 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 O was added in an amount to prepare a Ni-Ca-Al catalyst having a molar ratio of Ca to Al as shown in Table 2. Other conditions were the same as in example 2. When lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al shown in table 2 is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500h is carried out -1 The gas hourly space velocity of (2) is introduced with lignin black liquor aqueous solution with the concentration of 0.156g/mL, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction are shown in Table 2.
TABLE 2
Examples 8 to 11
When lignin black liquor adsorption enhanced reforming reaction is carried out, 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 10wt%, nitrogen is used as carrier gas, lignin black liquor water solution with the concentration of 0.156g/mL is fed in at the time of gas time as listed in table 3, and the reaction temperature is 550 ℃. The concentration and yield of hydrogen in the product after 10min of reaction were determined by GC are shown in table 3 below.
TABLE 3 Table 3
| Examples | 8 | 2 | 9 | 10 | 11 |
| Air 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
When lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 weight percent is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500 hours is carried out -1 The gas hourly space velocity of (2) was charged with lignin black liquor aqueous solution of lignin black liquor concentration listed in Table 4 at a reaction temperature of 550 ℃. The concentration of hydrogen in the product after 10min of reaction was measured by GC is shown in table 4 below.
TABLE 4 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
When lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 weight percent is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500 hours is carried out -1 The reaction was carried out at the temperature shown in Table 5 by introducing lignin black liquor aqueous solution having a concentration of 0.156g/mL at the gas hourly space velocity. The concentration of hydrogen in the product after 10min of reaction was measured by GC 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
When lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 weight percent is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500 hours is carried out -1 The gas hourly space velocity of (2) is introduced with lignin black liquor aqueous solution with the concentration of 0.156g/mL, and the reaction temperature is 550 ℃. When CO 2 After adsorption saturation, catalyst regeneration was performed at the temperature shown in table 6 for a regeneration time of 1h. This was cycled 3 times. The concentration of hydrogen in the product after 10min of reaction was measured by GC is shown in table 6 below. At a regeneration temperature of 500 ℃, CO cannot be desorbed 2 The second cycle does not have the adsorption enhancing 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 circle 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-round hydrogen (%) | 68.1 | 91.9 | 98.2 | 95.9 | 91.0 |
| Yield of first circle hydrogen (mol H 2 /mol C) | 0.93 | 0.95 | 1.00 | 0.94 | 0.88 |
| Yield of second Ring Hydrogen (mol H 2 /mol C) | 0.91 | 0.88 | 0.96 | 1.04 | 0.91 |
| Yield of third Hydrogen (mol H) 2 /mol C) | 0.96 | 0.84 | 0.98 | 0.96 | 0.87 |
Examples 27 to 29
When lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 weight percent is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500 hours is carried out -1 The gas hourly space velocity of (2) is introduced with lignin black liquor aqueous solution with the concentration of 0.156g/mL, and the reaction temperature is 550 ℃. When CO 2 After adsorption saturation, catalyst regeneration was performed for the time listed in table 6 at a regeneration temperature of 800 ℃. This was cycled 3 times. The concentration of hydrogen in the product after 10min of reaction was measured by GC is shown in table 7 below.
TABLE 7
| Examples | 27 | 24 | 28 | 29 |
| Regeneration time (h) | 0.1 | 1 | 2 | 6 |
| Purity of first circle 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-round hydrogen (%) | 95.3 | 98.2 | 95.2 | 90.6 |
| Yield of first circle hydrogen (mol H 2 /mol C) | 0.92 | 1.00 | 0.92 | 0.91 |
| Yield of second Ring Hydrogen (mol H 2 /mol C) | 0.89 | 0.96 | 0.91 | 0.87 |
| Yield of third Hydrogen (mol H) 2 /mol C) | 0.90 | 0.98 | 0.87 | 0.87 |
Example 30
Cycling stability experiments: when lignin black liquor adsorption enhanced reforming reaction is carried out, a Ni-Ca-Al catalyst with the molar ratio of Ca to Al of 2.8 and the Ni content of 10 weight percent is filled in a fixed bed reactor, nitrogen is taken as carrier gas, and 4500 hours is carried out -1 The gas hourly space velocity of (2) is introduced with lignin black liquor aqueous solution with the concentration of 0.156g/mL, and the reaction temperature is 550 ℃. When CO 2 After saturation of adsorption, regeneration was carried out at 800℃for 1h. This was cycled 5 times. The concentration of hydrogen in the product after 10min of reaction was measured by GC is shown in table 8 below.
TABLE 8
| Cycle number | 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 examples are merely illustrative of the present invention and are not intended to be a complete limitation of the embodiments. Other variations in form will be apparent to those of ordinary skill in the art in light of the foregoing description, and it is not necessary to present examples of all embodiments herein, but obvious variations are contemplated as falling within the scope of the invention.
Claims (7)
1. The lignin black liquor adsorption enhanced reforming hydrogen production method is characterized by comprising the following steps of:
(1) Filling a reactor with Ni-Ca-Al powder catalyst, wherein the Ni-Ca-Al powder catalyst is Ni, caO and Ca 12 Al 14 O 33 The molar ratio of Ca to Al in the Ni-Ca-Al catalyst is (1.6 to 3.4): 1, a step of;
(2) Inert gas is used as carrier gas, lignin black liquor aqueous solution is injected into a reactor for reforming hydrogen production;
(3) When CO 2 After saturation of adsorption, the catalyst is catalyzed in an inert atmosphereRegenerating the chemical agent.
2. The method according to claim 1, wherein the mass content of Ni in the Ni-Ca-Al catalyst in the step (1) is 5 to 20%.
3. The method according to claim 1, wherein the lignin black liquor in step (2) has a gas hourly space velocity of 2000 to 9000h -1 。
4. The method according to claim 1, characterized in that the lignin black liquor aqueous solution in step (2) has a concentration of 0.104-0.313 g/ml.
5. The process according to claim 1, wherein the reaction temperature in step (2) is 400 to 700 ℃.
6. The method according to claim 1, wherein the regeneration temperature in step (3) is greater than 500 ℃ and less than or equal to 1000 ℃.
7. The method according to claim 1, wherein the regeneration time in the step (3) is 0.1 to 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910912314.1A CN110562916B (en) | 2019-09-25 | 2019-09-25 | Method for producing hydrogen by absorbing and enhancing lignin black liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910912314.1A CN110562916B (en) | 2019-09-25 | 2019-09-25 | Method for producing hydrogen by absorbing and enhancing lignin black liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110562916A CN110562916A (en) | 2019-12-13 |
| CN110562916B true CN110562916B (en) | 2023-04-21 |
Family
ID=68782502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910912314.1A Active CN110562916B (en) | 2019-09-25 | 2019-09-25 | Method for producing hydrogen by absorbing and enhancing lignin black liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110562916B (en) |
Citations (2)
| 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 |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8349289B2 (en) * | 2007-03-05 | 2013-01-08 | 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 |
| 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 |
-
2019
- 2019-09-25 CN CN201910912314.1A patent/CN110562916B/en active Active
Patent Citations (2)
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110562916A (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN111644175B (en) | Ni-gangue ash catalyst, preparation method thereof and application thereof in tar steam reforming reaction | |
| CN113457705B (en) | Catalyst for producing hydrogen from formic acid, and preparation method and application thereof | |
| CN108085032B (en) | Method for preparing gas by catalyzing wood chips through pyrolysis by alkali metal composite salt | |
| CN111760582A (en) | MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst | |
| CN113753855A (en) | Method for producing hydrogen by catalytic reforming of biomass carbon-based catalyst coupled with microwave effect | |
| CN107286006B (en) | Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin | |
| CN114272932A (en) | Nickel-cerium biochar catalyst and preparation method and application thereof | |
| CN110562916B (en) | Method for producing hydrogen by absorbing and enhancing lignin black liquor | |
| CN112108138B (en) | Biomass hydrothermal carbon carrier catalyst and preparation method and application thereof | |
| CN115138392B (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN109627155B (en) | Method for preparing acid by alcohol catalytic dehydrogenation under solvent-free condition | |
| CN106905109A (en) | A kind of method that catalytic hydrogenolysis cellulose produces propane diols | |
| JP5897722B2 (en) | Method for preparing carbon dioxide methanation catalyst | |
| CN114904587B (en) | Preparation method of cesium modified phosphotungstic acid@UiO-66/porous carbon-based composite material | |
| US10717654B2 (en) | Method of preparing mesoporous carbon material with layered structure using humin | |
| CN113509931A (en) | Cu2Preparation of O/CuO @ CA photocatalyst and application thereof in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN102247888A (en) | Preparation method for granular carbon-based solid acid catalyst for producing biological diesel oil | |
| CN114870868B (en) | CdIn 2 S 4 Preparation of composite carbon aerogel photocatalyst and application of composite carbon aerogel photocatalyst in synthesis of xylonic acid by photocatalytic oxidation of xylose | |
| CN115849658B (en) | Water treatment sludge recycling method and application of carbon-based porous material | |
| CN112439405B (en) | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof | |
| CN115197070B (en) | Method for preparing N, N-dimethylaniline by taking wheat straw lignin as raw material | |
| CN107261812A (en) | A kind of method that calcium and magnesium double salt is prepared based on modification dolomite | |
| CN114789047A (en) | Preparation method and application of surface boron-doped nickel oxide catalyst | |
| CN115178285A (en) | Catalyst for isomerizing glucose into fructose and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |