CN214327720U - Biomass hydrogen production device - Google Patents

Abstract

A biomass hydrogen production device belongs to the technical field of solid waste treatment. The device consists of a pretreatment system, a hydrogen-producing and acid-producing system, a methane-producing system, a desulfurization system, a natural gas hydrogen-producing system, a gas holder, a hydrogen purification system, a solid-liquid separation system and a biogas liquid pool. The device firstly utilizes the biological fermentation action of the hydrogen-producing acid-producing system and the methane-producing system to produce hydrogen and methane, then the produced methane is further sent into the natural gas hydrogen-producing system to produce hydrogen, and finally the raw material hydrogen is sent into the hydrogen purification system to be further purified to obtain a hydrogen product. The utility model discloses hydrogen production raw materials adopts living beings renewable energy, and the source is abundant, low cost. Meanwhile, the device combines a biological hydrogen production technology and a chemical hydrogen production technology, and provides a new way for producing hydrogen from biomass.

Description

Biomass hydrogen production device

Technical Field

The utility model relates to a biomass hydrogen production device, which belongs to the technical field of solid waste treatment.

Background

More than 70 hundred million tons of biomass waste is generated in rural areas of China every year, and comprises 10 million tons of crop straws, 62 million tons of livestock and poultry manure and 1.2 million tons of domestic garbage in villages and small towns. Agricultural organic waste has the characteristics of green, low carbon, cleanness, reproducibility and the like as an important biomass resource, and China has always paid great attention to resource utilization of the agricultural organic waste, and the current utilization modes mainly include composting, methane production through fermentation, power generation, biomass fuel preparation and the like. The method for producing the biogas by fermenting the organic wastes is a key development direction in China, and a certain scale of green low-carbon biogas industry is primarily formed by 2020 according to the thirteen-five programming of biomass energy development. At present, the natural gas industry mainly recycles methane generated in the straw fermentation process, and hydrogen is generated in the biomass fermentation process, and the generation amount is about 50-100 mL/g (VS). Compared with methane, the combustion only produces water and does not produce CO₂Greenhouse gas is a clean energy source. Meanwhile, the combustion value of the hydrogen is 121061kJ/Kg, which is higher than 50054kJ/Kg of methane and is 2.4 times of the combustion value of the methane, so that the hydrogen has a very wide future application prospect.

At present, a plurality of researches on hydrogen production by organic matter fermentation are carried out at home and abroad, and the first industrial demonstration project adopting organic matter fermentation in the world is the productivity demonstration project of the organic wastewater fermentation method biological hydrogen production technology of Harbin industrial university. Although the industrial demonstration is already completed in the field of hydrogen production from organic wastewater, the research on hydrogen production by biomass fermentation is still in the small test stage and the middle test stage at present, and has the disadvantages of strict requirements on environmental conditions, low hydrogen production quantity, low biomass utilization rate and long distance from large-scale application. The technology for producing hydrogen from natural gas is successfully applied for more than 20 years in China, the production technology is mature, and the selectivity of the production scale is large (400 m under the standard state)³/h～200000m³/h)。The invention aims to provide a biomass hydrogen production device combining a biological method and a chemical method.

Disclosure of Invention

Aiming at the problems in the biomass fermentation hydrogen production technology, the invention provides a biomass hydrogen production device, which comprises the following specific implementation modes:

a biomass hydrogen production device comprises: the system is provided with a pretreatment system, a hydrogen-producing and acid-producing system, a methane-producing system, a desulfurization system, a natural gas hydrogen-producing system, a gas holder, a hydrogen purification system, a solid-liquid separation system and a biogas liquid pool which are communicated with one another.

The pretreatment system (1) is connected with the hydrogen-producing acid-producing system (2), the gas outlet of the hydrogen-producing acid-producing system (2) is connected with a gas holder (7), the solid-liquid outlet of the hydrogen-producing acid-producing system (2) is connected with the methane-producing system (3), the gas outlet of the methane-producing system (3) is sequentially connected with a desulfurization system (4), a steam reforming unit (5), a CO conversion unit (6) and the gas holder (7), the gas holder (7) is connected with a hydrogen purification system (8), the solid-liquid outlet of the methane-producing system (3) is connected with a solid-liquid separation system (9), the liquid outlet of the solid-liquid separation system (9) is connected with a biogas slurry tank (10), and the biogas slurry tank (10) is connected with the pretreatment system (1) through a biogas slurry reflux pump (16); the steam reforming unit (5) and the CO conversion unit (6) are combined into a natural gas hydrogen production system; the pretreatment system (1) is provided with a sodium hydroxide feed inlet and a biomass feed inlet.

Further, the biomass was pretreated in a pretreatment system with 2 wt% concentration of sodium hydroxide for 1 d.

Further, the pretreated biomass enters a hydrogen-producing acid-producing system for fermentation, hydrogen-producing acid-producing bacteria are inoculated in the hydrogen-producing acid-producing system, the temperature is controlled to be 35-38 ℃, the pH is controlled to be 5-6, the fermentation time is 2-3d, and the hydrogen-producing bacteria utilize the biomass for fermentation to produce H₂，CO₂And acetic acid production.

Further, the biomass fermented by the hydrogen-producing and acid-producing system enters a methane-producing system, methane-producing bacteria are inoculated in the methane-producing system, the temperature is controlled to be 55-50 ℃, the pH is controlled to be 7-8, the fermentation time is 25-30d, and the methane-producing bacteria ferment the biomass to produce methane.

Further, the marsh gas generated by the methane generating system enters a desulfurization system, the desulfurization system preferentially adopts dry desulfurization, the desulfurizer adopts ferric oxide, the pH value is 8-9 (the pH value is 50g of the pH value of the aqueous solution when the desulfurizer is soaked in 200-300ml of water for stabilization), and the flow rate of the marsh gas in the desulfurization tower is 0.1-0.3 m/s.

Further, the desulfurized biogas is pressurized to 3-4MPa and enters a steam reforming unit in a natural gas hydrogen production system, and the pressure of the desulfurized biogas is controlled at 850-: 1, with Ni-Al₂O₃/SiO₂As catalyst to carry out reforming reaction of methane and steam and convert into mixed gas H₂CO and CO₂。

Further, H₂CO and CO₂The mixed gas enters a CO conversion unit in a natural gas hydrogen production system, and is subjected to CO conversion reaction under the conditions of 2.2-2.6MPa and 300-350 ℃ and under the action of an iron-cobalt catalyst to be converted into H₂And CO₂。

Further, the hydrogen produced by the natural gas hydrogen production system₂And CO₂Cooling the mixed gas to 35-45 deg.C, introducing into a gas holder, and producing hydrogen and acid to obtain H₂And CO₂Also enters a gas holder, and the volume of the gas holder is 50-60% of the total gas production per day.

Further, the mixed gas in the gas holder enters a hydrogen purification system for purification to obtain a hydrogen product, and the preferred hydrogen purification system adopts a pressure swing adsorption system.

Further, fermentation residues from the methane production system enter a solid-liquid separation system to separate biogas residues from biogas slurry.

Furthermore, one part of the separated biogas slurry flows back to the pretreatment system through the reflux pump and is mixed with the biomass to adjust the feeding concentration, and one part of the separated biogas slurry enters the biogas slurry pool to be stored.

The utility model has the advantages that:

(1) the hydrogen production raw material adopts biomass renewable energy sources instead of non-renewable energy sources such as coal, petroleum and the like, and has rich sources and low cost.

(2) The two-phase anaerobic fermentation technology is adopted to ferment the biomass, so that the stability of methane production by fermentation of the system can be ensured, and part of hydrogen can be recycled in the hydrogen-producing acid-producing system.

(3) The method combines the biological hydrogen production technology and the chemical hydrogen production technology, and provides a new method for producing hydrogen for biomass.

Drawings

FIG. 1 is a diagram of a biomass hydrogen production process device

Wherein: a-natural gas hydrogen production system

1-pretreatment system, 2-hydrogen production and acid production system, 3-methane production system, 4-desulfurization system, 5-steam reforming unit,

6-CO conversion unit, 7-gas holder, 8-hydrogen purification system, 9-solid-liquid separation system, 10-biogas slurry storage pool,

11-biomass, 12-sodium hydroxide, 13-hydrogen product, 14-biogas residue, 15-biogas slurry and 16-biogas slurry reflux pump.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

1. The crushed corn straws (11) and the biogas slurry (15) returned by the biogas slurry return pump (16) are mixed in the pretreatment system (1), the concentration of TS (total solid) after mixing is about 8%, because wood fibers in the corn straws (11) are difficult to ferment anaerobically, in order to improve the gas production rate, sodium hydroxide (12) is added to ensure that the concentration of the wood fibers reaches 2%, the corn straws (11) are pretreated by alkaline hydrolysis, the solubility of organic matters in the straws is improved, and the pretreatment time is 1 d.

2. The pretreated straws (11) are sent into a hydrogen-producing acid-producing system (2), anaerobic sludge treated at the high temperature of 100 ℃ is inoculated in the system, the inoculation amount is 10g/L, the pH value is controlled to be about 5.5, the retention time is controlled to be 2d, and the temperature is controlled to be 35 ℃. H produced after fermentation₂And CO₂The mixed gas enters a gas holder (7).

3. The fermented corn straws (11) enter a methane production system (3) for further fermentation, anaerobic sludge is inoculated in the methane production system (3), the inoculation amount is 15g/L, the temperature is controlled at 55 ℃, the pH is controlled at about 7, the fermentation time is 30d, and methane-producing bacteria ferment the corn straws to produce methane.

4. Hydrogen sulfide gas is generated in the fermentation process, so that the risk of corroding equipment and pipelines exists, and therefore, the biogas needs to be subjected to desulfurization treatment. The biogas generated by the methane generating system (3) enters a dry desulfurization device (4), ferric oxide is used as a desulfurizer in the dry desulfurization system, and the pH value of the desulfurizer is 8-9. Desulfurization was carried out using the following chemical reaction:

Fe₂O₃·H₂O+3H₂S＝Fe₂S₃·H₂O+3H₂ O

5. pressurizing the desulfurized biogas to 3-4MPa, feeding the biogas into a steam reforming unit (5) in a natural gas hydrogen production system (A), and performing steam reforming at the temperature of 850-: 1, with Ni-Al₂O₃/SiO₂As catalyst to carry out reforming reaction of methane and steam and convert into mixed gas H₂CO and CO₂. The reaction process is as follows:

CH₄+H₂O＝CO+3H₂

CO+H₂O＝CO₂+H₂

6. mixed gas H₂CO and CO₂Enters a CO conversion unit (6) of a natural gas hydrogen production system (A), and is converted into H by CO conversion reaction under the conditions of 2.2-2.6MPa and 300-350 ℃ and under the action of an iron-cobalt catalyst₂And CO₂. The reaction process is as follows:

CO+H₂O＝CO₂+H₂

h produced by CO conversion unit (6)₂And CO₂The mixed gas is cooled to 40 ℃ and then enters a gas holder (7) for storage, and the volume of the gas holder (7) is 50 percent of the total gas production per day.

8. The gas in the gas holder (7) enters a pressure swing adsorption system (8) for purification, and the concentration of the purified hydrogen product (13) reaches 99.9 percent.

9. Fermentation residues from the methane production system (3) enter a cyclone separation solid-liquid separation system (9) to separate biogas residues (14) and biogas slurry (15).

10. One part of the biogas slurry (15) enters a biogas slurry storage pool (10) for storage, and the other part of the biogas slurry flows back to the pretreatment system (1) through a biogas slurry reflux pump (16) to be mixed with the corn straws (11).

Claims (5)

1. A biomass hydrogen production device is characterized by being provided with a pretreatment system, a hydrogen-producing acid-producing system, a methane-producing system, a desulfurization system, a natural gas hydrogen production system, a gas holder, a hydrogen purification system, a solid-liquid separation system and a biogas slurry pool which are communicated with one another;

the pretreatment system (1) is connected with the hydrogen-producing acid-producing system (2), the gas outlet of the hydrogen-producing acid-producing system (2) is connected with a gas holder (7), the solid-liquid outlet of the hydrogen-producing acid-producing system (2) is connected with the methane-producing system (3), the gas outlet of the methane-producing system (3) is sequentially connected with a desulfurization system (4), a steam reforming unit (5), a CO conversion unit (6) and the gas holder (7), the gas holder (7) is connected with a hydrogen purification system (8), the solid-liquid outlet of the methane-producing system (3) is connected with a solid-liquid separation system (9), the liquid outlet of the solid-liquid separation system (9) is connected with a biogas slurry tank (10), and the biogas slurry tank (10) is connected with the pretreatment system (1) through a biogas slurry reflux pump (16); the steam reforming unit (5) and the CO conversion unit (6) are combined into a natural gas hydrogen production system; the pretreatment system (1) is provided with a sodium hydroxide feed inlet and a biomass feed inlet.

2. The biomass hydrogen production plant according to claim 1, wherein hydrogen-producing acid-producing bacteria are inoculated in the hydrogen-producing acid-producing system.

3. The biomass hydrogen plant according to claim 1, wherein the methanogenic system is inoculated with methanogenic bacteria.

4. The biomass hydrogen plant according to claim 1, wherein the desulfurization system preferentially adopts dry desulfurization, and the desulfurizing agent adopts ferric oxide.

5. A biomass hydrogen plant according to claim 1, characterized in that the gas holder volume is 50-60% of the total gas production per day.

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