CN115466761A - Method and equipment for preparing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalysis coupling - Google Patents
Method and equipment for preparing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalysis coupling Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 230000008878 coupling Effects 0.000 title claims abstract description 21
- 238000010168 coupling process Methods 0.000 title claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229940088598 enzyme Drugs 0.000 claims description 39
- 239000011941 photocatalyst Substances 0.000 claims description 29
- 238000013032 photocatalytic reaction Methods 0.000 claims description 22
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 102000004190 Enzymes Human genes 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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- 239000011148 porous material Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 108010059892 Cellulase Proteins 0.000 claims description 4
- 229910002367 SrTiO Inorganic materials 0.000 claims description 4
- 229940106157 cellulase Drugs 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
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- 239000003795 chemical substances by application Substances 0.000 abstract description 3
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- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
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- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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Abstract
The invention discloses a method and equipment for preparing hydrogen by catalyzing and converting biomass through coupling of membrane-assisted bio-enzyme catalysis. The invention uses cheap biomass as an organic sacrificial agent, obtains hydrogen energy while processing environmental pollutants, can effectively convert waste biomass, realizes waste utilization, has low cost of the filter membrane, realizes bio-enzyme catalysis coupling photocatalysis under the assistance of the filter membrane, has better hydrogen production performance and stability, has simple process, and is suitable for wide popularization and use.
Description
Technical Field
The invention relates to a membrane-assisted bio-enzyme catalysis coupling photocatalytic conversion biomass hydrogen production method and equipment using the hydrogen production method.
Background
Hydrogen energy is a novel clean energy and energy storage material which is distinguished in the 21 st century, and China, america, japan, canada, european Union and the like make a hydrogen energy development plan. At present, china has made various progress in the field of hydrogen energy, is expected to become one of the countries with leading hydrogen energy technology and application in the near future, and is internationally acknowledged as the country which is most likely to take the lead to the realization of the industrialization of hydrogen fuel cells and hydrogen energy automobiles.
The industrial hydrogen production methods mainly include water electrolysis hydrogen production, coal gasification hydrogen production, heavy oil and natural gas steam catalytic conversion hydrogen production and the like, but the energy consumed by the reactions is larger than the energy generated by the reactions, so that the research of cheap large-scale hydrogen production technology is a common concern of scientists in various countries. The hydrogen production by utilizing solar energy to decompose water is a problem recognized worldwide with important research and application prospects, all countries in the world pay attention to and invest in the hydrogen production without any loss, various progress has been made in the aspects of theory and technology, and a large number of theoretical problems and engineering technical problems still exist to be solved urgently.
The sunlight with high efficiency and low cost is taken as a driving force, and the hydrogen production by decomposing water by using the catalysis of the semiconductor photocatalyst is regarded as a very promising renewable energy development technology, however, on one hand, the hydrogen production efficiency by decomposing water by using solar energy and the utilization efficiency of light energy do not meet the requirement of large-scale application yet; on the other hand, the environment is greatly polluted by the biomass such as agricultural production straws, and no ideal pollutant treatment and resource recycling method exists at present. Cellulose and other biomass degradation saccharification to generate soluble sugar micromolecules is a necessary way for biomass conversion and application, but the existing biomass degradation saccharification technology still has many problems, so that the difficulty of further converting sugar substances into high value-added compounds and biological fuels is increased.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen by catalytically converting biomass through catalytic coupling of membrane-assisted bio-enzyme, which has the advantages of low cost, simple process, good and stable hydrogen production performance and capability of realizing utilization of waste biomass.
The first purpose of the invention is realized by the following technical scheme: a membrane-assisted method for preparing hydrogen by catalyzing, coupling and photocatalytic conversion of biomass by biological enzyme is characterized in that the biological enzyme is utilized to depolymerize cellulose to produce sugar, sugar molecules are freely diffused to a photocatalytic reaction tank through a filter membrane to form aqueous solution containing the sugar molecules, the aqueous solution containing the sugar molecules is irradiated by light, and the photocatalyst in the photocatalytic reaction tank decomposes the aqueous solution containing the sugar molecules to generate hydrogen.
The invention uses cheap biomass as an organic sacrificial agent, obtains hydrogen energy while processing environmental pollutants, can effectively convert waste biomass, realizes waste utilization, has low cost of the filter membrane, realizes bio-enzyme catalysis coupling photocatalysis under the assistance of the filter membrane, has better hydrogen production performance and stability, has simple process, and is suitable for wide popularization and use.
The concentration of the photocatalyst in the photocatalytic reaction tank is 0.1-10 mg/mL.
The biological enzyme of the invention is cellulase and the like.
The photocatalyst is TiO deposited by one or more metals or metal sulfides 2 、ZnO、SrTiO 3 CdS or C 3 N 4 It can also be made into other catalysts for photocatalytic decomposition of water to produce hydrogen.
The illumination intensity of the invention is 10mW/cm 2 ~1000mW/cm 2 。
The illumination of the invention adopts ultraviolet light, visible light or near infrared light and the like, and the light source is a xenon lamp, a mercury lamp or sunlight and the like.
The second purpose of the invention is to provide a device for preparing hydrogen by using the membrane-assisted bio-enzyme catalytic coupling photocatalytic conversion biomass.
The second purpose of the invention is realized by the following technical scheme: the equipment is characterized by comprising a reactor and a light source arranged above the reactor, wherein the reactor comprises a closed shell and a first reaction tank arranged on the inner bottom surface of the closed shell, the first reaction tank is an open container, a light-permeable part is arranged on the closed shell corresponding to the irradiation direction of the light source, a second reaction tank is arranged in the closed shell and positioned at the outer space of the first reaction tank, the first reaction tank is communicated with the second reaction tank through a filter membrane on the first reaction tank, one of the first reaction tank and the second reaction tank is an enzymatic reaction tank for producing sugar by depolymerizing cellulose by using biological enzyme, the other reaction tank is a photocatalytic reaction tank capable of receiving light to enable a photocatalyst in the tank to decompose water containing sugar molecules to generate hydrogen, the light-permeable part is arranged on the closed shell corresponding to the irradiation part of the light source, and light irradiated by light rays irradiated from the light-permeable part irradiates the photocatalytic reaction tank.
The filter membrane of the invention can allow glucose molecules to freely diffuse through, but photocatalyst particles cannot diffuse through, and the aperture range of the filter membrane is 10nm-10 mu m. The filter membrane is preferably a glass fiber filter membrane with a pore size of 0.45 μm, and other filter membranes such as filter paper, a micro-pore filter membrane, a PES membrane and the like can also be adopted, and the type, the pore size, the size and the like are not limited.
Compared with the prior art, the invention has the following remarkable effects:
the biomass fuel cell disclosed by the invention utilizes cheap biomass as an organic sacrificial agent, obtains hydrogen energy while treating environmental pollutants, can effectively convert waste biomass, and realizes waste utilization.
The filter membrane used in the invention has low cost, realizes bio-enzyme catalysis coupling photocatalysis under the assistance of the filter membrane, and has better hydrogen production performance and stability.
The photocatalyst of the invention deposits TiO from one or more metals or metal sulfides 2 、ZnO、SrTiO 3 CdS or C 3 N 4 The preparation method has simple synthesis process; the price is low, and the required metal is easy to obtain.
The hydrogen production process is simple, and the hydrogen production equipment is simple in overall structure, low in manufacturing cost and suitable for wide popularization and use.
Drawings
The invention is described in further detail below with reference to the figures and the specific embodiments.
FIG. 1 is a schematic diagram of the hydrogen plant of the present invention;
FIG. 2 is a Cu/Ni-TiO composition of the present invention 2 A photocatalyst hydrogen production effect diagram;
FIG. 3 is a graph showing the effect of transmittance of the filter of the present invention.
Detailed Description
The invention relates to a method for preparing hydrogen by catalyzing and converting biomass through membrane-assisted bio-enzyme catalysis coupling, which comprises the steps of depolymerizing cellulose by using bio-enzyme to produce sugar, freely diffusing sugar molecules into a photocatalytic reaction tank through a filter membrane to form aqueous solution containing sugar molecules, and irradiating the aqueous solution containing sugar molecules by using light, wherein a photocatalyst in the photocatalytic reaction tank decomposes the aqueous solution containing sugar molecules to generate hydrogen.
In this example, the biological enzyme is cellulase, but other biological enzymes may be used. The filter membrane is a glass fiber filter membrane with a pore size of 0.45 μm. The photocatalyst is Cu/Ni loaded TiO 2 Photocatalyst (Cu/Ni-TiO) 2 Photocatalyst) and its preparation method is as follows: preparing Cu/Ni-TiO by chemical reduction method 2 . 1g of TiO 2 The powder (P25) was dispersed in 50mL of Ni (NO) 3 ) 2 ·6H 2 O and Cu (NO) 3 ) 2 ·3H 2 Stirring the mixed solution of O for 30min to obtain metal and TiO 2 The mass ratio of (B) is 1%. 50mL of NaOH (0.5 mol/L) and NaBH were prepared 4 Solution (0.53 mol/L), tiO is slowly injected 2 The mixture was vigorously stirred for 30min. After sufficient chemical reduction, the solid sample was washed with deionized water and centrifuged, and finally dried at 60 ℃ for 12h to obtain the desired material. The materials are respectively marked as Cu according to different Cu/Ni proportions x Ni y /TiO 2 (x and y represent the molar ratios of Ni and Cu in the supported metal, respectively, and x + y =1, x is 0, 0.2, 0.5, 0.8, 1.0).
An apparatus for producing hydrogen by using the above membrane assisted bio-enzyme catalysis coupling photo-catalytic conversion biomass is shown in fig. 1, and comprises a reactor 1 and a light source 2 disposed above the reactor 1, the reactor 1 comprises a closed housing 3 and a first reaction tank 4 disposed on the inner bottom surface of the closed housing 3, the first reaction tank 4 is an open container, in this embodiment, the first reaction tank 4 is an enzyme catalysis reaction tank for depolymerizing cellulose by using bio-enzyme to produce sugar, the space inside the closed housing 3 and outside the first reaction tank 4 is a second reaction tank 5, the second reaction tank 5 is a photo catalysis reaction tank capable of receiving light to make the photo catalyst in the tank decompose water containing sugar molecules to produce hydrogen, the first reaction tank 4 is communicated with the second reaction tank 5 through a filter membrane 6 thereon, and the solution in the second reaction tank 5 cannot be beyond the first reaction tank 4. The portion of the sealed housing 3 corresponding to the light source is a light-permeable portion, and the light emitted from the light-permeable portion irradiates the photocatalytic reaction cell, in this embodiment, the top surface of the sealed housing 3 is a light-permeable portion.
In other embodiments, the first reaction cell is a photocatalytic reaction cell, and the second reaction cell is an enzymatic reaction cell, in which case, the light entering from the light-permeable portion of the closed housing 3 irradiates the opening of the first reaction cell, so that the photocatalytic reaction cell can receive the light to make the photocatalyst in the cell decompose water containing sugar molecules to generate hydrogen.
The specific process of hydrogen production of the invention is as follows: cellulose powder with the initial amount of 0.5g is added into a 30ml enzyme catalysis reaction system of an enzyme catalysis container 4, the adding proportion of the cellulose powder to the cellulose powder is 1 2 In the photocatalytic reaction tank 5, the concentration of the photocatalyst is 1mg/mL, and the hydrogen production amount after 5 hours of photocatalytic reaction is 510. Mu. Mol/g. If only the photocatalyst is added and no enzyme is added, the hydrogen production is 179 mu mol/g after 5h of photocatalytic reaction under the same condition; if only the enzyme is added and no photocatalyst is added, the hydrogen production amount after 5 hours of photocatalytic reaction is 0 under the same conditions.
The principle of the invention is as follows: depolymerizing cellulose by using cellulase in the enzyme catalysis container 4, circulating the solution of the enzyme catalysis container 4 and the solution of the photocatalytic reaction tank 5 through a filter membrane to ensure that sugar produced in the enzyme catalysis container 4 is diffused into the photocatalytic reaction tank 5, and adding Cu/Ni-TiO into the photocatalytic reaction tank 5 2 The photocatalyst is stirred to be in a dispersed state and is separated under the irradiation of ultraviolet lightThe water is decomposed to produce hydrogen, thereby achieving the membrane-assisted hydrogen production by catalyzing and coupling the bio-enzyme and the photocatalysis to transform the biomass.
As shown in FIG. 2, comparing Cu/Ni-TiO at different Cu/Ni loading ratios 2 The hydrogen production effect of the photocatalyst. The initial concentration of glucose in a 100mL enzyme catalysis reaction system is 1mg/mL, a light source 2 in a photocatalysis system is ultraviolet light, and the illumination intensity is 1000mW/cm 2 In the photocatalytic reaction cell 5, the concentration of the photocatalyst is 1mg/mL, the Cu/Ni loading ratios are respectively changed to be 1.
As shown in FIG. 3, the permeability of glucose solution was compared under different kinds of filter. The initial concentration of glucose in a 100mL enzyme catalysis reaction system is 1mg/mL, the types of the filter membranes are respectively changed into a glass fiber filter membrane, a filter paper, a micro-filtration membrane with the pore diameter of 0.2 mu m, a PES membrane, a polypropylene membrane and a micro-filtration membrane with the pore diameter of 0.45 mu m, and the permeability of a glucose solution after 24 hours of reaction is respectively 50%, 25%, 23%, 12%, 0 and 0.
In other embodiments, the photocatalyst is one or more metals (Pt, au, ag, cu, ni, co, etc.) or metal sulfides (NiS, etc.) deposited TiO 2 、ZnO、SrTiO 3 、CdS、C 3 N 4 The photocatalyst can also be other photocatalysts used for producing hydrogen by decomposing water through photocatalysis, and the concentration of the photocatalyst in the photocatalytic reaction tank is 0.1-10 mg/mL.
In other embodiments, the illumination intensity is 10mW/cm 2 ~1000mW/cm 2 (ii) a The illumination adopts ultraviolet light, visible light or near infrared light and the like, and the light source is a xenon lamp, a mercury lamp or sunlight and the like.
In other embodiments, the light source may be disposed on a side of the enclosure, and the side wall of the enclosure corresponding to the light source is a light-permeable portion.
The embodiments of the present invention are not limited thereto, and according to the above-mentioned contents of the present invention, the present invention can be modified, substituted or changed in other various forms without departing from the basic technical idea of the present invention.
Claims (10)
1. A membrane-assisted bio-enzyme catalysis coupling photocatalytic conversion biomass hydrogen production method is characterized in that: depolymerizing cellulose to produce sugar by using biological enzyme, allowing sugar molecules to freely diffuse to a photocatalytic reaction tank through a filter membrane to form aqueous solution containing the sugar molecules, and illuminating, wherein a photocatalyst in the photocatalytic reaction tank decomposes water in the aqueous solution containing the sugar molecules to produce hydrogen.
2. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalytic coupling according to claim 1, wherein the method comprises the following steps: the concentration of the photocatalyst in the photocatalytic reaction tank is 0.1-10 mg/mL.
3. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalysis coupling according to claim 2, wherein the method comprises the following steps: the biological enzyme is cellulase.
4. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalysis coupling according to claim 3, wherein the method comprises the following steps: the photocatalyst is TiO deposited by one or more metals or metal sulfides 2 、ZnO、SrTiO 3 CdS or C 3 N 4 And (4) preparing.
5. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalytic coupling according to claim 4, wherein the method comprises the following steps: the illumination intensity is 10mW/cm 2 ~1000mW/cm 2 。
6. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalysis coupling according to claim 5, wherein the method comprises the following steps: the illumination adopts ultraviolet light, visible light or near infrared light.
7. The method for producing hydrogen by catalytically converting biomass through membrane-assisted bio-enzyme catalytic coupling according to claim 6, wherein the method comprises the following steps: the light source is a xenon lamp, a mercury lamp or sunlight.
8. An apparatus for producing hydrogen by using the membrane-assisted bio-enzyme catalytic coupling photo-catalytic conversion biomass as claimed in claim 1, wherein: the reactor comprises a reactor and a light source arranged outside the reactor, wherein the reactor comprises a closed shell and a first reaction tank arranged on the inner bottom surface of the closed shell, the first reaction tank is an open container, the outer space in the closed shell and positioned in the first reaction tank is a second reaction tank, the first reaction tank is communicated with the second reaction tank through a filter membrane on the first reaction tank, one of the first reaction tank and the second reaction tank is an enzyme catalysis reaction tank which utilizes biological enzyme to depolymerize cellulose to produce sugar, the other reaction tank is a photocatalysis reaction tank which can receive illumination to enable a photocatalyst in the tank to decompose water containing aqueous solution of sugar molecules to produce hydrogen, a light-permeable part is arranged on the closed shell corresponding to the irradiation part of the light source, and the photocatalysis reaction tank is irradiated by light rays emitted from the light-permeable part.
9. The apparatus of claim 8, wherein: the filter membrane is permeable to glucose molecules and impermeable to the photocatalyst particles.
10. The apparatus of claim 9, wherein: the pore size of the filter membrane is 10nm-10 μm.
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