CN116040580A - Method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass - Google Patents
Method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 93
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000009834 vaporization Methods 0.000 title claims abstract description 25
- 230000008016 vaporization Effects 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 150000002739 metals Chemical class 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 57
- 238000002309 gasification Methods 0.000 claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000197 pyrolysis Methods 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 239000011591 potassium Substances 0.000 claims abstract description 15
- 238000006057 reforming reaction Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000010902 straw Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- RXCVUXLCNLVYIA-UHFFFAOYSA-N orthocarbonic acid Chemical compound OC(O)(O)O RXCVUXLCNLVYIA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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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
- C01B3/06—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
- C01B3/12—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 by reaction of water vapour with carbon monoxide
- C01B3/16—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 by reaction of water vapour with carbon monoxide using 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
- C01B2203/02—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
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention discloses a method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass, which comprises the following steps: s1, crushing, screening and pickling biomass to obtain biomass powder; s2, soaking the pickled biomass powder in a potassium carbonate solution, and loading organic potassium elements; s3, soaking the biomass powder in nickel nitrate solution, and loading nickel element; s4, placing the biomass powder loaded with the potassium element and the nickel element into a pyrolysis furnace for pyrolysis to obtain biochar, pyrolysis gas and pyrolysis oil; s5, putting the biochar into a pyrolysis furnace, and carrying out gasification reforming reaction with steam to convert the biochar into hydrogen-rich gas and biological ash. According to the method for preparing the hydrogen by the co-catalytic vaporization of the internal and external metals of the biomass, AAEMs and external transition metals in the biomass are utilized to prepare the hydrogen by the co-catalytic vaporization of the biomass steam, so that the problems of serious tar problem and high catalyst cost in the cracking process are solved; has the advantages of high catalytic efficiency and good hydrogen quality.
Description
Technical Field
The invention relates to the technical field of hydrogen production, in particular to a method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass.
Background
Compared with the traditional energy, the hydrogen energy has the advantages of high energy density, high energy conversion efficiency and zero carbon emission. Meanwhile, in the aspect of energy utilization, the hydrogen can perform cogeneration through a fuel cell technology, so that the requirements of distributed industrial electric power and heat are met; in the traffic field, a hydrogen fuel cell car and a lithium battery car jointly push a new energy car to replace a traditional fuel car. Although the traditional fossil energy hydrogen production has the advantages of low cost and mature technology, carbon dioxide emission is difficult to avoid, so the produced hydrogen belongs to ash hydrogen; the economic cost of blue hydrogen generated by combining carbon capture and sequestration technology (CCS) is higher; the hydrogen gas produced from the renewable energy source is green hydrogen. Considering the carbon emission and cost advantages comprehensively, the green hydrogen prepared from biomass has the advantages of low cost and zero carbon emission.
The biomass thermochemical conversion process comprises combustion, pyrolysis, gasification and hydrothermal liquefaction, can convert biomass into high-quality bioenergy sources such as combustible gas, bio-oil, biochar and the like in a shorter time scale, and has the advantages of high carbon conversion rate, high reaction rate, wide fuel adaptability and the like. From the perspective of great potential of hydrogen energy application and hydrogen production comparison technology, the biomass gasification hydrogen production technology has wide application prospect. The biomass gasification hydrogen production is to convert the carbon hydroxide constituting the biomass into H by using gasification medium at high temperature 2 、CO、CO 2 And CH (CH) 4 While tar produced by the biomass reforms into small molecule gas. According to different gasification media, biomass gasification is divided into air, oxygen, water vapor and mixed gas gasification, wherein water vapor gasification is the most reasonable gasification mode for preparing hydrogen-rich fuel gas. The biomass gasification process mainly consists of two stages, namely pyrolysis devolatilization and gasification reaction of pyrolytic carbon (biochar). Pyrolysis devolatilization is an essential step of the overall gasification reaction, in which the organic components of the biomass are converted into gaseous products (CO, H) with increasing temperature 2 、CH 4 、CO 2 Etc.), liquid phase tar and solid phase biochar. Because of the differences in reaction stage, chemical activity and mass transfer resistance, the gasification rate of biochar is much lower than the pyrolysis rate, so gasification of biochar is recognizedIs the rate control step of the entire biomass gasification reaction. In the process of preparing hydrogen by gasifying biomass, reactions and products are complex, volatile matters generated in the pyrolysis stage can be condensed into tar, and then are polymerized into carbon deposit again, so that a pipeline instrument is blocked; the reaction rate of the carbon gasification stage is slow, and the carbon conversion rate is low.
Patent CN101475143B describes a method for producing hydrogen by steam in a biomass fluidized bed, in which steam is introduced into a biomass cracking fluidized bed in a catalytic conversion manner, so that biomass is subjected to rapid thermal cracking in the biomass cracking fluidized bed; biomass is quickly thermally cracked at medium temperature to generate volatile steam, and then steam reforming is carried out to prepare hydrogen. Patent CN112624041a describes a method for producing hydrogen from waste biomass carbon, firstly, the waste biomass is isolated from air, the obtained gas phase product and liquid phase product are respectively utilized, the biomass carbon as a solid product is used as a raw material for producing hydrogen, the biomass carbon and steam are subjected to gasification reforming reaction at 800-1500 ℃ in a gasifier, and the high-temperature gas after the reaction is purified to obtain hydrogen.
The gas production reaction in the biochar gasification process is complex, the catalyst can effectively reduce the reaction temperature and promote C-H 2 The O reaction, the water-gas shift reaction and the like improve the hydrogen yield. Common catalysts for biomass steam gasification include alkali metals, alkaline earth metals, transition metals, and the like. Both alkali metals and alkaline earth metals are collectively referred to as AAEMs. Existing biomass hydrogen production is mainly concentrated on: a/biomass steam gasification hydrogen production has the problems that a gas-liquid-solid three-phase product is complex, and tar problem in the cracking process is serious; b/preparation of the bio-oil reforming catalyst, which has the problems of high catalyst cost, complex preparation and the like.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass, which utilizes AAEMs and external transition metals in biomass to prepare hydrogen by co-catalytic vaporization of biomass steam, and solves the problems of serious tar problem and high catalyst cost in the cracking process.
In order to achieve the aim, the invention provides a method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass, which comprises the following steps:
s1, crushing and screening biomass to obtain biomass powder, and pickling to obtain pickled biomass powder;
s2, soaking the acid-washed biomass powder in a potassium carbonate solution, and then sufficiently filtering and washing with deionized water to enable the biomass powder to be loaded with organic potassium elements;
s3, soaking the biomass powder treated in the S2 with a nickel nitrate solution to enable the biomass powder to be loaded with nickel;
s4, placing the biomass powder loaded with the potassium element and the nickel element into a pyrolysis furnace for pyrolysis under the nitrogen atmosphere, and obtaining biochar, pyrolysis gas and pyrolysis oil after pyrolysis;
s5, putting the biochar obtained in the step S4 into a pyrolysis furnace, and carrying out gasification reforming reaction with steam to convert the biochar into hydrogen-rich gas and biological ash.
Preferably, in the step S1, the particle size of the biomass powder is 150-250 μm.
Preferably, in the step S1, the biomass powder and the 0.2mol/L sulfuric acid solution are stirred and mixed uniformly under the nitrogen atmosphere, the stirring time is 24 hours, and then the biomass powder is washed to be neutral by deionized water.
Preferably, in the step S2, the concentration of the potassium carbonate solution is 0.8mol/L, and the potassium element loaded on the biomass powder is 2% of the mass of the biomass powder.
Preferably, in S3, the nickel element loaded on the biomass powder is 15% of the mass of the biomass powder.
Preferably, in the step S4, the pyrolysis temperature is 600-700 ℃, and the heat preservation time is 30min.
Preferably, in S5, the temperature of the gasification reforming reaction is 600-700 ℃.
The method for preparing hydrogen by the co-catalytic vaporization of the internal and external metals of the biomass has the advantages and positive effects that: the biomass powder is loaded with potassium element and nickel element, and the nickel element is reduced into elemental nickel in the pyrolysis process of the biomass powder. Potassium enhances the catalytic activity of the biochar by increasing the relative proportion of defective oxygen on the surface of the biochar; in the gasification reforming reaction of the biochar and the steam, the potassium can enhance the catalytic gasification etching effect of Ni on the solid-phase biochar to obtain a high-quality hydrogen product, and has the advantages of environmental protection and good social and economic benefits.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for producing hydrogen by co-catalytic vaporization of metals inside and outside biomass according to the present invention;
FIG. 2 is a diagram showing real-time detection of a gas-phase product of a biochar steam gasification process in accordance with an embodiment of a method for producing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to the present invention;
FIG. 3 shows the gasification rate of biomass steam according to an embodiment and a comparative example of a method for producing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to the present invention;
FIG. 4 shows an example of a method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to the invention and a comparative example I D /I G A drawing.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Examples
As shown in fig. 1, the method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, and pickling to obtain pickled straw powder; the grain size of the straw powder is 150-250 mu m. The acid washing is to stir and mix the straw powder and 0.2mol/L sulfuric acid solution uniformly under nitrogen atmosphere for 24 hours, and then rinse the mixture to neutrality by deionized water.
S2, soaking the pickled straw powder in a potassium carbonate solution, and then, sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements. The concentration of the potassium carbonate solution is 0.8mol/L, and the potassium element loaded on the straw powder is 2% of the mass of the straw powder.
S3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel. The nickel element loaded on the straw powder is 15% of the mass of the straw powder.
S4, putting the straw powder loaded with the potassium element and the nickel element into a pyrolysis furnace for pyrolysis under the nitrogen atmosphere, and obtaining the biochar, the pyrolysis gas and the pyrolysis oil after pyrolysis. The pyrolysis temperature is 600-700 ℃, and the heat preservation time is 30min. The reducing atmosphere formed in the pyrolysis process reduces the nickel nitrate loaded by the straw powder into elemental nickel.
S5, putting the biochar obtained in the step S4 into a pyrolysis furnace, and carrying out gasification reforming reaction with steam to convert the biochar into hydrogen-rich gas and biological ash. The temperature of the gasification reforming reaction is 600-700 ℃.
Comparative example
A method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, and pickling to obtain pickled straw powder; the grain size of the straw powder is 150-250 mu m. The acid washing is to stir and mix the straw powder and 0.2mol/L sulfuric acid solution uniformly under nitrogen atmosphere for 24 hours, and then rinse the mixture to neutrality by deionized water.
S2, soaking the straw powder in nickel nitrate solution to enable the straw powder to be loaded with nickel element. The nickel element loaded on the straw powder is 15% of the mass of the straw powder.
And S3, putting the straw powder loaded with the nickel element into a pyrolysis furnace for pyrolysis under a nitrogen atmosphere, and obtaining biochar, pyrolysis gas and pyrolysis oil after pyrolysis. The pyrolysis temperature is 600-700 ℃, and the heat preservation time is 30min.
S4, putting the biochar obtained in the step S3 into a pyrolysis furnace, and carrying out gasification reforming reaction with steam to convert the biochar into hydrogen-rich gas and biological ash. The temperature of the gasification reforming reaction is 600-700 ℃.
The gas phase products of the gasification reforming reaction process of biochar and steam in the examples were detected in real time as shown in fig. 2. The yield of each product peaks at 2min of reaction, with maximum hydrogen production, up to 0.1mmol. The yield of hydrogen was calculated to be 67mmol/g,the volume ratio is 65%, and reaches the theoretical maximum value of the gasification reaction of the one-step method. AAEMs in biomass catalyze biochar-H to transition metal Ni 2 The increased gas yield of the O gasification reaction is mainly shown by the enhancement of CO and H 2 And CO 2 And CH (CH) 4 The yield of (c) does not vary much. The catalytic reaction of AAEMs synergistic transition metal Ni is mainly realized by carbon gasification reaction (C+H) in synergistic gasification reaction 2 O→H 2 +co) to affect gas composition and hydrogen production.
Examples and comparative examples the biomass-steam gasification rates are shown in FIG. 3, ni-1 and Ni-2 represent two comparative examples, and Ni+K-1 represent two examples. The higher the gasification rate, the more complete the reaction. When the biochar is completely gasified, the gasification rate of the biochar is higher than that of the biochar of the comparative example, the potassium can increase the relative proportion of oxygen with surface defects on the biochar, the oxygen with the surface defects obviously increases the electronic charge near the oxygen atoms of the surface lattice, the fluidity of the oxygen is increased, the electron transfer is promoted, the O-H is easier to break, and the catalytic activity of the biochar is enhanced. K can enhance the catalytic gasification etching effect of Ni on solid-phase biochar, and K-Ni synergistically catalyzes and gasifies some of the biochar with poorer activity to carry out gasification reaction.
The samples of the biochar of examples and comparative examples were subjected to Raman analysis, divided into 10 peaks, and the calculated ID/IG represented the amorphous carbon level in the biochar samples, as shown in fig. 4. The higher the value is, the higher the activity is, and it can be seen from fig. 4 that the AAEMs-enhanced transition metal Ni catalytic gasification is mainly realized by enhancing the activity of biochar, so that the biochar is easier to catalyze, and the gasification reaction is easier, thereby enhancing the catalytic hydrogen production effect.
Therefore, the method for preparing hydrogen by the co-catalytic vaporization of the internal and external metals of the biomass utilizes AAEMs and external transition metals in the biomass to prepare hydrogen by the co-catalytic vaporization of the biomass steam, and solves the problems of serious tar problem and high catalyst cost in the cracking process; has the advantages of high catalytic efficiency and good hydrogen quality.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (7)
1. The method for preparing the hydrogen by the co-catalytic vaporization of the inner metal and the outer metal of the biomass is characterized by comprising the following steps of:
s1, crushing and screening biomass to obtain biomass powder, and pickling to obtain pickled biomass powder;
s2, soaking the acid-washed biomass powder in a potassium carbonate solution, and then sufficiently filtering and washing with deionized water to enable the biomass powder to be loaded with organic potassium elements;
s3, soaking the biomass powder treated in the S2 with a nickel nitrate solution to enable the biomass powder to be loaded with nickel;
s4, placing the biomass powder loaded with the potassium element and the nickel element into a pyrolysis furnace for pyrolysis under the nitrogen atmosphere, and obtaining biochar, pyrolysis gas and pyrolysis oil after pyrolysis;
s5, putting the biochar obtained in the step S4 into a pyrolysis furnace, and carrying out gasification reforming reaction with steam to convert the biochar into hydrogen-rich gas and biological ash.
2. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the S1, the particle size of the biomass powder is 150-250 mu m.
3. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the step S1, the biomass powder and the sulfuric acid solution with the concentration of 0.2mol/L are stirred and mixed uniformly in the nitrogen atmosphere, the stirring time is 24 hours, and then deionized water is used for washing until the biomass powder is neutral.
4. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the step S2, the concentration of the potassium carbonate solution is 0.8mol/L, and the potassium element loaded on the biomass powder is 2% of the mass of the biomass powder.
5. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the step S3, the nickel element loaded on the biomass powder is 15% of the mass of the biomass powder.
6. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the step S4, the pyrolysis temperature is 600-700 ℃, and the heat preservation time is 30min.
7. The method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass according to claim 1, which is characterized in that: in the step S5, the temperature of the gasification reforming reaction is 600-700 ℃.
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| CN117208846A (en) * | 2023-11-09 | 2023-12-12 | 中国农业科学院农业环境与可持续发展研究所 | Pyrolysis reforming hydrogen production method by coupling slow pyrolysis and fast pyrolysis |
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| CN117208846A (en) * | 2023-11-09 | 2023-12-12 | 中国农业科学院农业环境与可持续发展研究所 | Pyrolysis reforming hydrogen production method by coupling slow pyrolysis and fast pyrolysis |
| CN117208846B (en) * | 2023-11-09 | 2024-02-02 | 中国农业科学院农业环境与可持续发展研究所 | Pyrolysis reforming hydrogen production method by coupling slow pyrolysis and fast pyrolysis |
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