阅读说明：本技术 一种醇基燃料低温液相重整制h2及ch4燃气工艺 (Process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel ) 是由 沈吉兆 夏永奎 于 2019-10-24 设计创作，主要内容包括：本发明属于制气工艺方法技术领域,尤其为一种醇基燃料低温液相重整制H2及CH4燃气工艺,所述制H2及CH4燃气工艺采用一步法低温液相重整制气与纯化耦合工艺,所述一步法低温液相重整制气与纯化耦合工艺包括如下步骤：醇基燃料按设定流量连续送入液相重整制氢反应器。本发明不仅解决锅炉受热面腐蚀问题,在促进改技术与设备的规模化应用,显著降低锅炉燃烧污染物排放,改善大气环境的同时,将锅炉烟气余热与甲醇化学能结合,提高了锅炉产汽能力,且突破了低温液相重整制气的非贵金属催化剂水热服役稳定性问题,大幅度降低了催化剂成本,从而使得低温液相重整制气技术具有显著的经济效益和社会效益。(The invention belongs to the technical field of gas making process methods, and particularly relates to a process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein the process for preparing H2 and CH4 fuel gas adopts a one-step low-temperature liquid-phase reforming gas making and purification coupling process, and the one-step low-temperature liquid-phase reforming gas making and purification coupling process comprises the following steps: the alcohol-based fuel is continuously fed into the liquid phase reforming hydrogen production reactor according to the set flow. The invention not only solves the corrosion problem of the heating surface of the boiler, promotes the large-scale application of the reforming technology and equipment, obviously reduces the emission of combustion pollutants of the boiler, improves the atmospheric environment, simultaneously combines the waste heat of the flue gas of the boiler with the chemical energy of methanol, improves the steam production capability of the boiler, breaks through the problem of the hydrothermal service stability of a non-noble metal catalyst for preparing gas by low-temperature liquid phase reforming, and greatly reduces the cost of the catalyst, thereby leading the low-temperature liquid phase reforming gas preparation technology to have obvious economic benefit and social benefit.)

1. A process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel adopts a one-step low-temperature liquid-phase reforming gas preparation and purification coupling process, and is characterized in that: the one-step low-temperature liquid-phase reforming gas preparation and purification coupling process comprises the following steps: alcohol-based fuel is continuously fed into a liquid-phase reforming hydrogen production reactor according to a set flow, liquid-phase reforming hydrogen production, water gas shift and methanation reaction are carried out at the temperature of 190 ℃ and under the saturation pressure, the pressure of the reactor is increased due to the generated H2 and CH4 gases, the pressure of the reactor is regulated and controlled to be stabilized within the range of 4.0-7.0MPa by controlling an exhaust back pressure valve of a gas-liquid separator, the working state of the reactor is maintained to be a liquid-phase reforming hydrogen production state, the self-pressurization effect is caused in the liquid-phase reforming hydrogen production process, and the formed high-pressure (4.0-7.0 MPa) fuel gas is fed into a boiler to be.

2. The process of claim 1 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: and the alcohol-based fuel is continuously pumped into the liquid-phase reforming hydrogen production reactor by a plunger pump according to a set flow pipeline.

3. The process of claim 1 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: the axial flow overflow-lift type reactor is designed by adopting a flow mass transfer coupling strengthening strategy of fixed filling of a catalytic material and fluid axial flow back mixing overflow, gas, liquid and solid multiphase mixing and interphase mass transfer in the reactor are strengthened through the fluid mechanics and buoyancy lift action of a porous medium, and the reactor design with compact structure and high-strength gas production are optimized.

4. The process of claim 3 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: the reactor is added with a molybdenum carbide material synthesized by a CVD method with molybdenum salt as a precursor in the process of liquid-phase reforming hydrogen production, and a molybdenum carbide-based liquid-phase reforming hydrogen production catalyst prepared by loading metal active components is loaded, the evolution of the stable annular and cage-shaped cluster structure of methanol-water molecules to a chain structure is modulated through the limited domain and wall surface electronic effect of the low-dimensional molybdenum carbide-based catalyst regular nano mass transfer channel, and then the water molecules and methanol molecules in the nanometer pore channel of the limited domain are activated through the synergy of the molybdenum carbide carrier and the monatomic metal, so that the H2 and CH4 fuel gas can be efficiently prepared through ultralow-temperature liquid-phase reforming.

5. The process of claim 4 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: the hydrogen catalyst is prepared by regulating and controlling a catalyst crystalline phase, a micro-nano pore channel structure and an active center by regulating molybdenum salt, a template, CVD and heat treatment parameters.

6. The process of claim 1 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: the reactor mixes boiler hot water and alcohol-based fuel for low-temperature liquid-phase reforming gas production, and the boiler hot water and the alcohol-based fuel are mixed and enter the reactor for low-temperature liquid-phase reforming gas production after exchanging heat with boiler flue gas waste heat.

7. The process of claim 1 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: the bottom of the reactor is provided with a heater, and the heater provides fuel gas for preparing H2 and CH4 from alcohol-based fuel at the reaction temperature of 190-250 ℃.

8. The process of claim 1 for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, wherein: high pressure (4.0-7.0 Mpa) fuel gas is adsorbed and purified by a filler type fuel gas purifying tower and then is sent into a boiler to be combusted to generate steam.

Technical Field

The invention relates to the technical field of gas making process methods, in particular to a process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel.

Background

The alcohol-based fuel boiler is a novel environment-friendly boiler and is mechanical equipment which takes methanol as main fuel to heat water into hot water or steam. The methanol fuel standard for boilers and the local standard for substituting natural gas by methanol, namely 'general technical requirement for methanol fuel for boilers' and 'technical condition for methanol fuel storage and supply facilities' have been promulgated in various regions such as Shanxi in China.

Methanol boiler users in northwest and other areas of China reach millions of families, and alcohol-based fuel for combustion is generally prepared by blending 70% of methanol and other components. In order to improve the economy of the alcohol-based fuel for boiler combustion, the alcohol-based fuel of the boiler users at present is generally prepared by mixing methanol and inferior and cheap oil so as to reduce the cost of the alcohol-based fuel. However, the cheap alcohol-based fuel used for the boiler to burn for a long time inevitably generates acidic corrosive species in the burning process, so that the heating surface of the boiler is seriously corroded, and even the whole boiler is scrapped, and a large amount of research works in a methanol and biological oil liquid phase reforming hydrogen production laboratory are reported internationally, but the used catalyst is a noble metal catalyst, and the high catalyst cost is a key for hindering the industrial application of the catalyst.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, which solves the problems that the traditional alcohol-based fuel is usually mixed by methanol and inferior and cheap oil materials so as to reduce the cost of the alcohol-based fuel, the heating surface of a boiler is corroded in the using process, even the whole boiler is scrapped, and the cost of a catalyst used in the hydrogen production process is overhigh.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel adopts a one-step low-temperature liquid-phase reforming gas preparation and purification coupling process, and the one-step low-temperature liquid-phase reforming gas preparation and purification coupling process comprises the following steps: alcohol-based fuel is continuously fed into a liquid-phase reforming hydrogen production reactor according to a set flow, liquid-phase reforming hydrogen production, water gas shift and methanation reaction are carried out at the temperature of 190 ℃ and under the saturation pressure, the pressure of the reactor is increased due to the generated H2 and CH4 gases, the pressure of the reactor is regulated and controlled to be stabilized within the range of 4.0-7.0MPa by controlling an exhaust back pressure valve of a gas-liquid separator, the working state of the reactor is maintained to be a liquid-phase reforming hydrogen production state, the self-pressurization effect is caused in the liquid-phase reforming hydrogen production process, and the formed high-pressure (4.0-7.0 MPa) fuel gas is fed into a boiler to be.

As a preferable technical scheme of the invention, the alcohol-based fuel is continuously pumped into the liquid phase reforming hydrogen production reactor by a plunger pump according to a set flow pipeline.

As a preferred technical scheme of the invention, a flow mass transfer coupling strengthening strategy of fixed filling of catalytic materials and axial flow back mixing and overflow of fluid is adopted, an axial flow overflow type reactor is designed, gas, liquid and solid multi-phase mixing and interphase mass transfer in the reactor are strengthened through the fluid mechanics and buoyancy effect of porous medium, and the reactor design with compact structure and high-strength gas production are optimized.

As a preferable technical scheme of the invention, in the process of liquid-phase reforming hydrogen production, the reactor is added with a molybdenum salt serving as a precursor to synthesize a molybdenum carbide material by a CVD method, and the molybdenum carbide-based liquid-phase reforming hydrogen production catalyst prepared by loading metal active components modulates the evolution of the methanol-water molecule stable annular and cage-shaped cluster structures to chain structures by the confinement and wall surface electronic effect of the low-dimensional molybdenum carbide-based catalyst regular nano mass transfer channel, and further activates water molecules and methanol molecules in the confinement in a nano pore channel by the cooperation of a molybdenum carbide carrier and a monatomic metal, so that the H2 and CH4 fuel gas can be efficiently prepared by ultralow-temperature liquid-phase reforming.

As a preferred technical scheme of the invention, the hydrogen catalyst is prepared by regulating and controlling a catalyst crystalline phase, a micro-nano pore channel structure and an active center by regulating and controlling molybdenum salt, a template, CVD and heat treatment parameters.

According to a preferable technical scheme of the invention, the reactor is used for preparing gas by mixing boiler hot water and alcohol-based fuel and using the mixture for low-temperature liquid-phase reforming, and the boiler hot water and the alcohol-based fuel are mixed and enter the reactor for preparing gas by low-temperature liquid-phase reforming after exchanging heat with the waste heat of boiler flue gas.

As a preferable technical scheme of the invention, the bottom of the reactor is provided with a heater, and the fuel gas reaction temperature of the heater for preparing H2 and CH4 by alcohol-based fuel is 190-250 ℃.

As a preferred technical scheme of the invention, high-pressure (4.0-7.0 Mpa) fuel gas is adsorbed and purified by a filler type fuel gas purification tower and then is sent into a boiler to be combusted to generate steam.

(III) advantageous effects

Compared with the prior art, the invention provides a process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of alcohol-based fuel, which has the following beneficial effects:

the process for preparing H2 and CH4 fuel gas by low-temperature liquid-phase reforming of the alcohol-based fuel not only solves the problem of corrosion of the heating surface of a boiler, promotes the large-scale application of the reforming technology and equipment, obviously reduces the emission of combustion pollutants of the boiler, improves the atmospheric environment, but also combines the waste heat of the flue gas of the boiler with the chemical energy of methanol, improves the steam production capacity of the boiler, breaks through the problem of the stability of the hydrothermal service of a non-noble metal catalyst for preparing the gas by low-temperature liquid-phase reforming, greatly reduces the cost of the catalyst, and ensures that the low-temperature liquid-phase reforming gas preparation technology has obvious economic and social.

Drawings

FIG. 1 is a schematic view of the low temperature liquid phase reforming of H2 and CH4 fuel gas according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.