阅读说明：本技术 有机固废气化一体化高效制氢和制甲烷工艺 (Organic solid waste gasification integrated efficient hydrogen and methane production process ) 是由 樊文俊 宋云彩 冯杰 荆洁颖 李文英 于 2021-09-27 设计创作，主要内容包括：本发明属于煤化工和有机固废处理技术领域,且公开了有机固废气化一体化高效制氢和制甲烷工艺,包括气化炉、净化塔、甲烷化、制氢反应器与PSA分离设备,通过往气化炉内部注入煤、有机固废原料与气化剂水、氧,经过三者混合共气化步骤,制备得到合成气,内部产生的灰渣定期处理即可。本发明通过设置一整套的处理流程,利用有机固废一体化同时制备高纯氢、高纯甲烷和CO2的富集,可以将低品位的含碳原料转化为高纯度的产品,同时此工艺过程可以同时利用到有机固废气化的水,补充进入制氢反应器,提高了工艺过程中H元素的利用率。(The invention belongs to the technical field of coal chemical industry and organic solid waste treatment, and discloses an organic solid waste gasification integrated efficient hydrogen production and methane production process. The invention sets a whole set of treatment flow, utilizes the integration of organic solid wastes to simultaneously prepare the enrichment of high-purity hydrogen, high-purity methane and CO2, can convert low-grade carbon-containing raw materials into high-purity products, and simultaneously can simultaneously utilize water gasified by the organic solid wastes to supplement and enter the hydrogen production reactor in the technical process, thereby improving the utilization rate of H elements in the technical process.)

1. The organic solid waste gasification integrated efficient hydrogen production and methane production process comprises a gasification furnace, a purification tower, methanation, a hydrogen production reactor and PSA separation equipment, and is characterized in that the organic solid waste gasification integrated efficient hydrogen production and methane production process comprises the following specific operation steps:

(1) injecting coal, organic solid waste raw materials, gasifying agent water and oxygen into a gasification furnace, mixing the coal, the organic solid waste raw materials, the gasifying agent water and the oxygen, and gasifying the mixture to prepare synthetic gas, wherein ash generated in the gasification furnace is periodically treated;

(2) introducing the synthesis gas obtained in the step (1) into a purification tower, and removing and separating ash, tar, water and sulfur-containing compounds in the synthesis gas to obtain clean synthesis gas;

(3) introducing the clean synthesis gas obtained in the step (2) into a methanation reactor, and then carrying out methanation reaction in the methanation reactor to prepare methane;

(4) separating the methane obtained in the step (3) to separate out a part of high-quality methane and a part of methane mixed gas;

(5) introducing the methane mixed gas obtained in the step (4) into a hydrogen production reactor, and adding corresponding materials in the process to perform a methane steam reforming reaction to prepare hydrogen;

(6) and (4) treating the hydrogen obtained in the step (5) by PSA (pressure swing adsorption) separation equipment to obtain high-quality hydrogen, wherein a part of the hydrogen flows back to the working section of the methanation reactor to supplement the required hydrogen.

2. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: the corresponding materials in the step (5) specifically refer to metal nickel as a catalyst, calcium oxide as an absorbent and water body for supplement.

3. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: in the step (1), adjusting the oxygen equivalent of a gasifying agent, the water inflow and the furnace temperature of a gasification furnace so as to achieve the minimum tar generation in the gasification furnace; in the step (2), the biomass semi-coke is used as a catalyst at the outlet of the gasification furnace to catalyze the cracking of tar.

4. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: in the step (2), the temperature of the synthesis gas is reduced to 80-100 ℃, and ash residue and a small amount of tar are removed by sedimentation.

5. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: in the step (3), a fluidized bed reactor is adopted, and the reaction temperature is 220-480 ℃.

6. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: in the step (5), the hydrogen production reactor uses a Ni/CaO composite catalyst to carry out reaction at the reaction temperature of 550 ℃ and 650 ℃ and under the pressure of 0.1 MP.

7. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 6, characterized in that: loading Ni on SiO₂The shell is made of nano-scale CaO as a core material.

8. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: the purity of the high-quality methane in the step (4) is more than or equal to 90 percent.

9. The organic solid waste gasification integrated efficient hydrogen and methane production process according to claim 1, characterized in that: hydrogen production reactor outlet gas H₂＞96％，CO＜500ppm，CO₂＜3％。

Technical Field

The invention belongs to the technical field of coal chemical industry and organic solid waste treatment, and particularly relates to an organic solid waste gasification integrated efficient hydrogen production and methane production process.

Background

With the rapid development of economy and the improvement of life quality, the generated domestic garbage and solid waste are increased day by day, and the solid waste still contains higher energy, so that the environmental pressure can be relieved and the utilization rate of elements and energy can be improved by fully utilizing the solid waste; in addition, the co-gasification of the coal and the organic solid waste does not increase the operation difficulty, and due to the interaction of the coal and the solid waste, the utilization rate of elements and energy can be improved, and the emission of pollutants is reduced.

In addition, hydrogen production is a process with very high water consumption, solid waste garbage has relatively high water content compared with coal, water in the solid waste garbage can be used for supplementing water for a subsequent hydrogen production working section, the water consumption of the process can be reduced, the national water saving strategy is met, at present, industrial hydrogen sources mainly come from a coal hydrogen production process, and how to efficiently prepare hydrogen by using coal is an important technical problem.

In order to solve the problems, the patent provides an organic solid waste gasification integrated efficient hydrogen and methane production process.

Disclosure of Invention

The invention aims to solve the problems, provides an organic solid waste gasification integrated high-efficiency hydrogen and methane production process, and has the advantages that organic solid waste thermal conversion synthesis gas is used as a raw material, a specially designed jacket reactor is used for realizing integration of synthesis gas methanation and hydrogen production processes, and the purpose of simultaneously preparing high-purity hydrogen and high-purity methane from organic solid waste is realized; in addition, by coupling two reactions, the invention can simultaneously obtain high-purity hydrogen, methane and carbon dioxide, and can utilize water in solid waste to supplement the hydrogen source of the system.

In order to achieve the purpose, the invention provides the following technical scheme: the organic solid waste gasification integrated efficient hydrogen and methane production process comprises a gasification furnace, a purification tower, methanation, a hydrogen production reactor and PSA separation equipment, and comprises the following specific operation steps:

(1) injecting coal, organic solid waste raw materials, gasifying agent water and oxygen into a gasification furnace, mixing the coal, the organic solid waste raw materials, the gasifying agent water and the oxygen, and gasifying the mixture to prepare synthetic gas, wherein ash generated in the gasification furnace is periodically treated;

(2) introducing the synthesis gas obtained in the step (1) into a purification tower, and removing and separating ash, tar, water and sulfur-containing compounds in the synthesis gas to obtain clean synthesis gas;

(3) introducing the clean synthesis gas obtained in the step (2) into a methanation reactor, and then carrying out methanation reaction in the methanation reactor to prepare methane;

(4) separating the methane obtained in the step (3) to separate out a part of high-quality methane and a part of methane mixed gas;

(5) introducing the methane mixed gas obtained in the step (4) into a hydrogen production reactor, and adding corresponding materials in the process to perform a methane steam reforming reaction to prepare hydrogen;

(6) and (4) treating the hydrogen obtained in the step (5) by PSA (pressure swing adsorption) separation equipment to obtain high-quality hydrogen, wherein a part of the hydrogen flows back to the working section of the methanation reactor to supplement the required hydrogen.

As a preferred technical scheme of the invention, the corresponding material in the step (5) specifically refers to metal nickel as a catalyst, calcium oxide as an absorbent and water body for supplement.

As a preferred technical scheme of the invention, in the step (1), the oxygen equivalent of a gasifying agent, the water inflow and the furnace temperature of the gasification furnace are adjusted so as to achieve the minimum tar generation in the gasification furnace; in the step (2), the biomass semi-coke is used as a catalyst at the outlet of the gasification furnace to catalyze the cracking of tar.

As a preferred technical scheme of the invention, in the step (2), the temperature of the synthesis gas is reduced to 80-100 ℃, ash and a small amount of tar are removed by sedimentation, and sulfur-containing compounds in the synthesis gas are removed by a methanol absorption tower.

As a preferable technical scheme of the invention, a fluidized bed reactor is adopted in the step (3), the reaction temperature is 220-.

As a preferred technical scheme of the invention, in the hydrogen production reactor in the step (5), the Ni/CaO composite catalyst is used for reaction at the reaction temperature of 550-650 ℃ and the pressure of 0.1MP, the composite catalyst can be regenerated at the reaction temperature of 600-700 ℃ and the pressure of 0.1MP in the catalyst regeneration tower, and the high-concentration CO byproduct is generated₂。

As a preferable technical scheme of the invention, Ni is loaded on SiO₂The Ni/SiO is prepared by taking nano-scale CaO as a core material as a shell₂A core-shell structure coated with CaO.

As a preferred technical scheme of the invention, the purity of the high-quality methane in the step (4) is more than or equal to 90 percent

As a preferred technical scheme of the invention, the outlet gas H of the hydrogen production reactor₂＞96％，CO＜500ppm，CO₂＜3％。

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

according to the invention, a whole set of treatment process is set, the organic solid waste raw material, gasifying agent water and oxygen are injected into the gasification furnace in advance for processing, then the generated crude synthesis gas CO and H2 pass through the purification tower, the methanation reactor, the hydrogen production reactor and the PSA separation device, and finally high-purity methane and hydrogen are effectively prepared, and the organic solid waste is utilized to integrate and simultaneously prepare high-purity hydrogen, high-purity methane and enrichment of CO2, so that low-grade carbon-containing raw materials can be converted into high-purity products, and meanwhile, the water gasified by the organic solid waste can be utilized in the process and supplemented into the hydrogen production reactor, so that the utilization rate of H elements in the process is improved.

Drawings

FIG. 1 is a schematic view of the overall process of the present invention.

In the figure: 1. organic solid waste raw materials; 2. gasifying agent water and oxygen; 3. roughly preparing synthesis gas CO and H2; 4. purified syngas CO and H2; 5. CH4 and H2O; 7. high quality methane and methane mixed gas; 8. low purity hydrogen; 11. high-purity reverse hydrogen supply.

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.

As shown in figure 1, the invention provides an organic solid waste gasification integrated efficient hydrogen and methane production process, which comprises a gasification furnace, a purification tower, methanation, a hydrogen production reactor and PSA separation equipment, and is characterized in that the organic solid waste gasification integrated efficient hydrogen and methane production process comprises the following specific operation steps:

(1) injecting coal, organic solid waste raw materials, gasifying agent water and oxygen into a gasification furnace, mixing the coal, the organic solid waste raw materials, the gasifying agent water and the oxygen, and gasifying the mixture to prepare synthetic gas, wherein ash generated in the gasification furnace is periodically treated;

(2) introducing the synthesis gas obtained in the step (1) into a purification tower, and removing and separating ash, tar, water and sulfur-containing compounds in the synthesis gas to obtain clean synthesis gas;

(3) introducing the clean synthesis gas obtained in the step (2) into a methanation reactor, and then carrying out methanation reaction in the methanation reactor to prepare methane;

(4) separating the methane obtained in the step (3) to separate out a part of high-quality methane and a part of methane mixed gas;

(5) introducing the methane mixed gas obtained in the step (4) into a hydrogen production reactor, and adding corresponding materials in the process to perform a methane steam reforming reaction to prepare hydrogen;

(6) and (4) treating the hydrogen obtained in the step (5) by PSA (pressure swing adsorption) separation equipment to obtain high-quality hydrogen, wherein a part of the hydrogen flows back to the working section of the methanation reactor to supplement the required hydrogen.

Wherein, the corresponding material in the step (5) specifically refers to metal nickel as a catalyst, calcium oxide as an absorbent and water body for supplement.

In the step (1), adjusting the oxygen equivalent of a gasifying agent, the water inflow and the furnace temperature of the gasification furnace so as to minimize the generation of tar in the gasification furnace; in the step (2), the biomass semi-coke is used as a catalyst at the outlet of the gasification furnace to catalyze the cracking of tar.

Wherein, in the step (2), the temperature of the synthesis gas is reduced to 80-100 ℃, ash and a small amount of tar are removed by sedimentation, and sulfur-containing compounds in the synthesis gas are removed by a methanol absorption tower.

Wherein, in the step (3), a fluidized bed reactor is adopted, the reaction temperature is 220-.

Wherein, in the step (5), the hydrogen production reactor uses Ni/CaO composite catalyst to react at the reaction temperature of 550-650 ℃ and the pressure of 0.1MP, the composite catalyst can be regenerated at the reaction temperature of 600-700 ℃ and the pressure of 0.1MP in the catalyst regeneration tower, and high-concentration CO byproduct is produced₂。

Wherein Ni is supported on SiO₂The Ni/SiO is prepared by taking nano-scale CaO as a core material as a shell₂A core-shell structure coated with CaO.

Wherein, the purity of the high-quality methane in the step (4) is more than or equal to 90 percent

Wherein, the outlet gas H of the hydrogen production reactor₂＞96％，CO＜500ppm，CO₂＜3％。

Example one

Mixing 3340.8kg of solid waste with 5011.2kg of coal, and then carrying out co-gasification, wherein water in a gasification agent is 1830.48kg, oxygen is 2784kg, and the gasification temperature is 1074 ℃;

introducing the synthesis gas obtained by gasification in the gasification furnace into a purification tower to remove H in the synthesis gas₂S, COS, etc.; cooling the gas at the outlet of the purification tower to 40 ℃ through a cooler, introducing the gas into a flash tower to remove moisture in the gas, and obtaining the productThe purified gas is CO₂/CO/H₂The mixed gas of (3);

mixing the mixed gas with a reflux H₂Mixing and introducing the mixture into a methanation reactor, reacting at 303 ℃ under the condition of 28.4bar, wherein the catalyst in the reactor is a high-activity methanation catalyst, and obtaining methane gas with the purity of 95%;

dehydrating and purifying the methane gas obtained by the reaction, separating 52.5% of methane as a product, and allowing water removed from the rest gas by a drying and methanation section and additional water to enter a hydrogen production section;

the hydrogen production section adopts adsorption and reinforcement integrated hydrogen production, and Ni/CaO composite catalyst is used for reaction at the reaction temperature of 550-650 ℃ and the pressure of 0.1 MP;

the composite catalyst can be regenerated in a catalyst regeneration tower at the temperature of 600-700 ℃ and the temperature of 0.1MP, and the process can generate high-purity hydrogen with the purity of 99.99 percent and byproduct high-purity CO with the purity of 90-95 percent₂。

The data show that the process is superior to the traditional coal-to-methane technology in the aspects of energy consumption, coal consumption, water consumption and the like, and has great industrialization potential.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.