阅读说明：本技术 一种水生植物微波化学链气化制备高氢合成气方法和系统 (Method and system for preparing high-hydrogen synthesis gas by microwave chemical chain gasification of aquatic plants ) 是由 王晓佳 陈德露 金保昇 沈德魁 于 2021-09-10 设计创作，主要内容包括：本发明提供一种水生植物微波化学链气化制备高氢合成气方法和系统,制方法包括：步骤10)在冷态下向石英反应器中加入载氧体,并向石英反应器中持续通入氮气；步骤20)加热石英反应器,使石英反应器的温度达到并维持在预设温度；步骤30)向石英反应器中加入水生植物,水生植物与载氧体混合进行生物质气化,产生生物质合成气；步骤40)将生物质合成气依次经过去焦油、水洗和干燥后,得到高氢合成气。本发明的水生植物微波化学链制备高氢合成气方法和系统,以克服常规生物质化学链气化系统中需要额外蒸汽反应器和蒸汽发生装置,以及传统加热方式易导致受热不均的问题。(The invention provides a method and a system for preparing high-hydrogen synthesis gas by microwave chemical chain gasification of aquatic plants, wherein the method comprises the following steps: step 10) adding an oxygen carrier into the quartz reactor in a cold state, and continuously introducing nitrogen into the quartz reactor; step 20), heating the quartz reactor to enable the temperature of the quartz reactor to reach and be maintained at a preset temperature; step 30) adding aquatic plants into the quartz reactor, mixing the aquatic plants with the oxygen carrier to gasify biomass, and generating biomass synthesis gas; and step 40) sequentially carrying out tar removal, water washing and drying on the biomass synthesis gas to obtain the high-hydrogen synthesis gas. The method and the system for preparing the high-hydrogen synthesis gas by the aquatic plant microwave chemical looping disclosed by the invention are used for overcoming the problems that an additional steam reactor and a steam generating device are required in a conventional biomass chemical looping gasification system, and the traditional heating mode is easy to cause uneven heating.)

1. A method for preparing high-hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants is characterized by comprising the following steps:

step 10) adding an oxygen carrier into the quartz reactor (3) in a cold state, and continuously introducing nitrogen into the quartz reactor (3);

step 20), heating the quartz reactor (3) to enable the temperature of the quartz reactor (3) to reach and be maintained at a preset temperature;

step 30) adding aquatic plants into the quartz reactor (3), mixing the aquatic plants with the oxygen carrier to gasify the biomass, and generating biomass synthesis gas;

and step 40) sequentially carrying out tar removal, water washing and drying on the biomass synthesis gas to obtain the high-hydrogen synthesis gas.

2. The method for preparing the high-hydrogen synthetic gas by the microwave chemical looping gasification of the aquatic plants according to claim 1, wherein in the step 20), the quartz reactor is heated by microwave heating.

3. The method for preparing high-hydrogen synthesis gas by aquatic plant microwave chemical looping gasification according to claim 1, further comprising:

and 50) introducing oxygen into the quartz reactor (3) to reoxidize the reduced oxygen carrier.

4. The method for preparing high-hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants as claimed in claim 1, wherein the preset temperature is 850-.

5. The utility model provides an aquatic plant microwave chemistry chain gasification preparation high hydrogen synthetic gas system, its characterized in that, includes heating furnace (6), quartz reactor (3), feeder (1), intake pipe (2), tail gas processing apparatus and gas collection device (12) that are used for adding aquatic plant, quartz reactor (3) set up in heating furnace (6), feeder (1), intake pipe (2) and tail gas processing apparatus all are connected with quartz reactor (3), gas collection device (12) are connected with tail gas processing apparatus.

6. The system for preparing the high-hydrogen synthetic gas by the microwave chemical looping gasification of the aquatic plants as claimed in claim 5, wherein the heating furnace (6) adopts a microwave heating mode.

7. The system for preparing the high-hydrogen synthetic gas by the microwave chemical-looping gasification of the aquatic plants according to claim 5, wherein the tail gas treatment device comprises an isopropanol washing gas cylinder (9), a water washing gas cylinder (10) and a dry silica gel washing gas cylinder (11) which are sequentially connected through a gas pipe, the isopropanol washing gas cylinder (9) is connected with the quartz reactor (3), and the dry silica gel washing gas cylinder (11) is connected with the gas collection device (12).

Technical Field

The invention belongs to a method for preparing synthesis gas in the field of gasification combustion, and particularly relates to a method and a system for preparing high-hydrogen synthesis gas by microwave chemical chain gasification of aquatic plants.

Background

While fossil fuels meet human energy needs, the "by-products" produced during their processing and utilization have also severely affected the environment on which we live. In recent years, with the increasing consumption of fossil energy and the emission of greenhouse gases such as CO2, people are receiving more attention to the search for a clean and efficient alternative energy source.

Hydrogen has high energy density and the combustion product is water, so that the hydrogen is clean and pollution-free and is one of the best substitutes for fossil fuel. Currently, the hydrogen production modes include steam reforming, electrolytic water, and coal gasification; the SMR process for preparing hydrogen by reforming methane steam is mature, has higher economic competitiveness, and is a main mode for preparing hydrogen on a large scale. However, in the steam reforming process of the SMR process, a large amount of methane needs to be combusted to provide heat for reforming, and greenhouse gas CO is used₂The emissions are still high and the subsequent purification of hydrogen is also a highly energy consuming process. Therefore, it is of great significance to find a hydrogen production way with high efficiency, low energy consumption and low carbon emission.

Chemical looping techniques with internal separation of CO₂Low loss, low NOx emissions, have received widespread attention. Chemical Looping Combustion (CLC) is firstly proposed by Ritcher and Knoche, fuel does not directly contact with oxygen in the CLC process, generally metal oxide is used as an oxygen carrier, and the fuel and the oxygen carrier react in a fuel reactor to realize that the fuel does not contain N₂Burning under the environment, condensing and dehydrating the flue gas to obtain high-purity CO₂CLC can be used for near-zero emission combustion and enables low-cost CO₂And (4) trapping. The chemical looping technology is also very important in hydrogen production, and the application of the chemical looping technology has important significance in preparing high-hydrogen synthesis gas. So far, the research on chemical-looping preparation of high-hydrogen synthesis gas by using biomass as fuel is still in an exploration stage, and has a plurality of problems, including the following aspects:

(a) the traditional chemical-looping gasification technology needs an additional steam reactor and a steam generator matched with the additional steam reactor, the whole system is complex, and the investment and operation cost is high.

(b) The biomass gasification reaction needs to be carried out under a certain temperature condition, and the requirement on heating temperature control is high. In the conventional heating process, heat is transferred from the surface of the sample to the inside, and a large temperature gradient is generated due to the fact that the surface temperature is higher than the central temperature, so that the temperature rise speed is limited, and the submicron tissue energy can be uneven.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the method and the system for preparing the high-hydrogen synthesis gas by the microwave chemical looping gasification of the aquatic plants are provided, so that the problems that an additional steam reactor and a steam generating device are needed in a conventional biomass chemical looping gasification system, and the traditional heating mode is easy to cause uneven heating are solved.

In order to solve the technical problem, in one aspect, an embodiment of the present invention provides a method for preparing high hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants, including the following steps:

step 10) adding an oxygen carrier into the quartz reactor in a cold state, and continuously introducing nitrogen into the quartz reactor;

step 20), heating the quartz reactor to enable the temperature of the quartz reactor to reach and be maintained at a preset temperature;

step 30) adding aquatic plants into the quartz reactor, mixing the aquatic plants with the oxygen carrier to gasify biomass, and generating biomass synthesis gas;

and step 40) sequentially carrying out tar removal, water washing and drying on the biomass synthesis gas to obtain the high-hydrogen synthesis gas.

As a further improvement of the embodiment of the present invention, in the step 20), the quartz reactor is heated by microwave heating.

As a further improvement of the embodiment of the present invention, the method further includes:

and 50) introducing oxygen into the quartz reactor, and reoxidizing the reduced oxygen carrier.

As a further improvement of the embodiment of the present invention, the preset temperature is 850-.

On the other hand, the embodiment of the invention also provides a system for preparing high-hydrogen synthesis gas by the microwave chemical looping gasification of aquatic plants, which comprises a heating furnace, a quartz reactor, a feeder for adding the aquatic plants, an air inlet pipe, a tail gas treatment device and a gas collection device, wherein the quartz reactor is arranged in the heating furnace, the feeder, the air inlet pipe and the tail gas treatment device are all connected with the quartz reactor, and the gas collection device is connected with the tail gas treatment device.

As a further improvement of the embodiment of the invention, the heating furnace adopts a microwave heating mode.

As a further improvement of the embodiment of the invention, the tail gas treatment device comprises an isopropanol washing cylinder, a water washing cylinder and a dry silica gel washing cylinder which are sequentially connected through a gas pipe, wherein the isopropanol washing cylinder is connected with the quartz reactor, and the dry silica gel washing cylinder is connected with the gas collection device.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

according to the method and the system for preparing the high-hydrogen synthesis gas through the microwave chemical looping gasification of the aquatic plants, the aquatic plants are used as biomass raw materials, and the biomass gasification is carried out on the aquatic plants and the oxygen carrier at the preset temperature to generate the synthesis gas containing hydrogen. The method and the system of the embodiment of the invention directly utilize a large amount of water contained in the aquatic plants, and compared with the traditional method of utilizing a chemical chain to prepare the synthesis gas, the method and the system of the embodiment of the invention omit an external steam generating device and a process of introducing steam into a reaction device, so that the synthesis process and the synthesis system have simple structures, and the hydrogen content in the synthesis gas is improved. The method and the system of the embodiment of the invention fully utilize the aquatic plants, can effectively solve the problem that the aquatic plants are difficult to treat, and have great benefits for environmental protection.

Drawings

FIG. 1 is a schematic structural diagram of a system for preparing high-hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants according to an embodiment of the invention.

The figure shows that: feeder 1, intake pipe 2, quartz reactor 3, thermocouple 4, control panel 5, heating furnace 6, outlet duct 7, silica gel hose 8, isopropyl alcohol gas washing bottle 9, washing gas cylinder 10, dry silica gel gas washing bottle 11, gas collection device 12, aquatic plant A, oxygen carrier B.

Detailed Description

The technical solution of the present invention will be explained in detail below.

The embodiment of the invention provides a method for preparing high-hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants, which comprises the following steps:

and step 10) adding an oxygen carrier into the quartz reactor 3 in a cold state, and continuously introducing nitrogen into the quartz reactor 3 to ensure that an inert atmosphere is kept in the gasification process.

Step 20) heating the quartz reactor 3 to make the temperature of the quartz reactor 3 reach and maintain the preset temperature.

And step 30) adding the aquatic plant A into the quartz reactor 3, mixing the aquatic plant A with the oxygen carrier B, and gasifying the biomass to generate biomass synthesis gas.

And step 40) sequentially carrying out tar removal, water washing and drying on the biomass synthesis gas to obtain the high-hydrogen synthesis gas.

According to the method for preparing the high-hydrogen synthesis gas through the microwave chemical looping gasification of the aquatic plants, the aquatic plants are used as biomass raw materials, and the biomass gasification is carried out with the oxygen carrier at the preset temperature, so that the synthesis gas containing hydrogen is generated. The method provided by the embodiment of the invention directly utilizes a large amount of water contained in the aquatic plants, and compared with the traditional method of utilizing a chemical chain to produce hydrogen, the method saves an external steam generating device and a process of gasifying water and then introducing steam into the device, so that the synthesis process is simplified, and the hydrogen content in the synthesis gas is improved. The method of the embodiment of the invention fully utilizes the aquatic plants, can effectively solve the problem that the aquatic plants are difficult to treat, and has great benefit for environmental protection.

Preferably, the oxygen carrier is lean iron ore. The lean iron ore which is low in price, easy to obtain and good in cycle performance is used as the oxygen carrier, so that the operation efficiency and H of the system are improved₂The preparation rate and the equipment investment and the operation cost are saved.

Preferably, in step 20), the quartz reactor 3 is heated by microwave heating. The embodiment of the invention adopts a microwave heating mode to heat the quartz reactor 3, has the advantages of heating instantaneity, uniformity, energy conservation, selectivity, good heating controllability and non-thermal effect, and combines the selection of the iron ore with good microwave absorption effect as the oxygen carrier, so that the heating speed is higher, the energy consumption is less and the hydrogen production efficiency is higher.

Preferably, the method according to the embodiment of the present invention further includes:

step 50) oxygen is introduced into the quartz reactor 3 to reoxidize the reduced oxygen carrier.

After the synthesis gas containing hydrogen is prepared, oxygen is directly introduced into the quartz reactor, and the reduced oxygen carrier is re-oxidized, so that the cyclic utilization of the oxygen carrier is realized.

Preferably, the preset temperature is 850-. In the method of the embodiment, the temperature interval is beneficial to improving the hydrogen component, and the preparation of the high-hydrogen synthesis gas is realized.

The embodiment of the invention also provides a system for preparing high-hydrogen synthesis gas by microwave chemical looping gasification of aquatic plants, which comprises a heating furnace 6, a quartz reactor 3, a feeder 1, an air inlet pipe 2, a tail gas treatment device and a gas collection device 12, as shown in figure 1. The quartz reactor 3 is arranged in the heating furnace 6, and the feeder 1 and the gas inlet pipe 2 are both connected with the quartz reactor 3. The quartz reactor 3 is connected with a tail gas treatment device sequentially through an air outlet pipe 7 and a silica gel hose 8, and the tail gas treatment device is connected with a gas collection device 12. Wherein, the tail gas processing device is used for cleaning and collecting gasification products, and the feeder 1 is used for adding aquatic plants into the quartz reactor 3. The heating furnace 6 is provided with a control panel 5, the quartz reactor 3 is internally provided with a thermocouple 4, and the thermocouple 4 is connected with the control panel 5. The thermocouple 4 measures the temperature in the quartz reactor 3 and transmits the measured data to the control panel 5, which controls the heating furnace 6 to heat the quartz reactor 3 so that the temperature of the quartz reactor reaches and is maintained at a preset temperature.

According to the system for preparing the high-hydrogen synthesis gas through the microwave chemical looping gasification of the aquatic plants, the aquatic plants are used as biomass raw materials and are gasified with the oxygen carrier at the preset temperature to generate the synthesis gas containing hydrogen. The system provided by the embodiment of the invention directly utilizes a large amount of water contained in the aquatic plants, and compared with the traditional method of utilizing a chemical chain to produce hydrogen, an external steam generating device and a process of gasifying water and introducing steam into the device are omitted, so that the synthesis process and the synthesis system are simple in structure, and the hydrogen content in the synthesis gas is improved. The system provided by the embodiment of the invention fully utilizes the aquatic plants, can effectively solve the problem that the aquatic plants are difficult to treat, and has great benefit on environmental protection.

Preferably, the heating furnace 6 adopts a microwave heating mode. The embodiment of the invention adopts a microwave heating mode to heat the quartz reactor 3, has the advantages of heating instantaneity, uniformity, energy conservation, selectivity, good heating controllability and non-thermal effect, and combines the selection of the iron ore with good microwave absorption effect as the oxygen carrier, so that the heating speed is higher, the energy consumption is less and the hydrogen production efficiency is higher.

Preferably, the tail gas treatment device comprises an isopropanol washing bottle 9, a washing bottle 10 and a drying silica gel washing bottle 11 which are sequentially connected through a gas pipe, the isopropanol washing bottle 9 is connected with the quartz reactor 3, and the drying silica gel washing bottle 11 is connected with the gas collection device 12. The biomass synthesis gas generated by the quartz reactor 3 absorbs tar through an isopropanol gas washing bottle 9, a water washing bottle 10 is positioned at the rear end of the isopropanol gas washing bottle and used for removing isopropanol, removing some impurities such as dust and the like mixed in the gas, and finally drying the gas through a dry silica gel gas washing bottle 11 to obtain the high-H gas₂The biomass gasification syngas of the content is input into the gas collecting device 12.

The working process of the system for preparing the high-hydrogen synthesis gas by the microwave chemical looping gasification of the aquatic plants in the preferred embodiment is as follows:

oxygen carrier B is added to the quartz reactor 3 in the cold state. N is introduced into a quartz reactor 3 through an air inlet pipe 2₂The remaining gas in the quartz reactor 3 is purged to maintain an inert atmosphere in the quartz reactor 3. The quartz reactor 3 is heated by microwave heating, so that the temperature of the quartz reactor 3 reaches and is maintained at a preset temperature. The aquatic plant a is fed into the quartz reactor 3 through the feeder 1. Contacting the aquatic plant A with the oxygen carrier B at high temperatureThe biomass is pyrolyzed and gasified to generate CO and H₂And CH₄And the combustible components are the main synthetic gas. The water in the aquatic plant A is evaporated to generate a large amount of water vapor to participate in gasification reaction, so that H in the synthesis gas is increased₂And (4) content. The generated synthesis gas passes through an isopropanol gas washing bottle 9 to absorb tar, a water gas washing bottle 10 removes impurities such as isopropanol and dust mixed in the gas, and a dry silica gel gas washing bottle 11 is dried, so that the high H gas can be obtained₂Content of biomass gasification syngas. Then introducing O into a quartz reactor 3 through an inlet pipe 2₂And re-oxidizing the reduced oxygen carrier for preparing the high hydrogen synthetic gas next time.

3 specific examples are provided below.

Example 1

The aquatic plant adopts water hyacinth, the oxygen carrier adopts certain lean iron ore (Fe)₂O₃ 44.16wt％)。

5g of iron-poor ore was added to the quartz reactor 3 at room temperature. N is introduced into a quartz reactor 3 through an air inlet pipe 2₂The remaining gas in the quartz reactor 3 is purged to maintain an inert atmosphere in the quartz reactor 3. The quartz reactor 3 is heated by microwave heating, so that the temperature of the quartz reactor 3 reaches and is maintained at 800 ℃. 5g of water hyacinth was added to the quartz reactor 3 via the feeder 1. The water hyacinth is contacted with the lean iron ore to generate a biomass pyrolysis gasification reaction to generate CO and H₂And CH₄Syngas with combustible components. The water in the water hyacinth is evaporated to generate a large amount of water vapor to participate in the gasification reaction, so that the H content in the synthesis gas is increased₂And (4) content. The generated synthesis gas passes through an isopropanol gas washing bottle 9 in sequence to absorb tar, the water gas washing bottle 10 removes impurities such as isopropanol and dust mixed in the gas, and a dry silica gel gas washing bottle 11 is dried to obtain the high H₂Content of biomass gasification syngas. Then introducing O into a quartz reactor 3 through an inlet pipe 2₂And the temperature lasts for 30min and is 200 ℃, and the reduced oxygen carrier is re-oxidized for preparing the high hydrogen synthesis gas next time.

Example 2

The aquatic plant adopts water hyacinth as carrierThe body adopts a certain lean iron ore (Fe)₂O₃ 44.16wt％)。

5g of iron-poor ore was added to the quartz reactor 3 at room temperature. N is introduced into a quartz reactor 3 through an air inlet pipe 2₂The remaining gas in the quartz reactor 3 is purged to maintain an inert atmosphere in the quartz reactor 3. The quartz reactor 3 is heated by microwave heating, so that the temperature of the quartz reactor 3 reaches and is maintained at 900 ℃. 5g of water hyacinth was added to the quartz reactor 3 via the feeder 1. The water hyacinth is contacted with the lean iron ore to generate a biomass pyrolysis gasification reaction to generate CO and H₂And CH₄Syngas with combustible components. The water in the water hyacinth is evaporated to generate a large amount of water vapor to participate in the gasification reaction, so that the H content in the synthesis gas is increased₂And (4) content. The generated synthesis gas passes through an isopropanol gas washing bottle 9 in sequence to absorb tar, the water gas washing bottle 10 removes impurities such as isopropanol and dust mixed in the gas, and a dry silica gel gas washing bottle 11 is dried to obtain the high H₂Content of biomass gasification syngas. Then introducing O into a quartz reactor 3 through an inlet pipe 2₂And the temperature lasts for 30min and is 200 ℃, and the reduced oxygen carrier is re-oxidized for preparing the high hydrogen synthesis gas next time.

Example 3

The aquatic plant adopts water hyacinth, the oxygen carrier adopts certain lean iron ore (Fe)₂O₃ 44.16wt％)。

5g of iron-poor ore was added to the quartz reactor 3 at room temperature. N is introduced into a quartz reactor 3 through an air inlet pipe 2₂The remaining gas in the quartz reactor 3 is purged to maintain an inert atmosphere in the quartz reactor 3. The quartz reactor 3 is heated by microwave heating, so that the temperature of the quartz reactor 3 reaches and is maintained at 950 ℃. 5g of water hyacinth was added to the quartz reactor 3 via the feeder 1. The water hyacinth is contacted with the lean iron ore to generate a biomass pyrolysis gasification reaction to generate CO and H₂And CH₄Syngas with combustible components. The water in the water hyacinth is evaporated to generate a large amount of water vapor to participate in the gasification reaction, so that the H content in the synthesis gas is increased₂And (4) content. The generated synthetic gas passes through an isopropanol gas washing bottle 9 in sequence to absorb tar and is washed by waterThe gas cylinder 10 removes impurities such as isopropanol and dust mixed in the gas, and the dry silica gel gas washing cylinder 11 is dried to obtain the high H₂Content of biomass gasification syngas. Then introducing O into a quartz reactor 3 through an inlet pipe 2₂And the temperature lasts for 30min and is 200 ℃, and the reduced oxygen carrier is re-oxidized for preparing the high hydrogen synthesis gas next time.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to further illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the claims and their equivalents.