阅读说明：本技术 一种氢气甲烷混合燃料、co2吸附剂及其制备方法 (Hydrogen and methane mixed fuel and CO2Adsorbent and preparation method thereof ) 是由 董宝霞 邰运龙 滕云雷 于 2020-05-18 设计创作，主要内容包括：本发明公开了一种氢气甲烷混合燃料、CO<Sub>2</Sub>吸附剂及其制备方法,氢气甲烷混合燃料、CO<Sub>2</Sub>吸附剂是利用金属氢化物还原贝壳或蛋壳制得的,蛋壳或贝壳与金属氢化物的摩尔比为1:1～4,该氢气甲烷混合燃料中氢气和甲烷的摩尔比为1:1～8,CO<Sub>2</Sub>吸附剂为氧化钙@炭材料,氧化钙和炭的摩尔比为1～4:1,并提供氢气甲烷混合燃料、CO<Sub>2</Sub>吸附剂的制备方法,本发明的氢气甲烷混合燃料、CO<Sub>2</Sub>吸附剂,有利于缓解能源危机、温室效应、全球变暖等问题,同时使得蛋壳和贝壳变废为宝,减少因处理贝壳或蛋壳带来的环境污染问题。(The invention discloses a hydrogen and methane mixed fuel and CO 2 Adsorbent and preparation method thereof, hydrogen and methane mixed fuel and CO 2 The adsorbent is prepared by reducing shells or eggshells by using metal hydride, the molar ratio of the eggshells or the shells to the metal hydride is 1: 1-4, the molar ratio of hydrogen to methane in the hydrogen-methane mixed fuel is 1: 1-8, and CO is 2 The adsorbent is a calcium oxide @ carbon material, the molar ratio of calcium oxide to carbon is 1-4: 1, and hydrogen and methane mixed fuel and CO are provided 2 Method for preparing adsorbent, hydrogen and methane mixture of the inventionFuel, CO 2 The adsorbent is beneficial to relieving the problems of energy crisis, greenhouse effect, global warming and the like, simultaneously, the eggshells and the shells are changed into valuable, and the problem of environmental pollution caused by processing the shells or the eggshells is reduced.)

1. Hydrogen and methane mixed fuel and CO₂An adsorbent characterized by: the hydrogen and methane mixed fuel and CO₂The adsorbent is prepared by reducing shells or eggshells by using metal hydrides, the molar ratio of the eggshells or the shells to the metal hydrides is 1: 1-4, the molar ratio of hydrogen to methane in the hydrogen-methane mixed fuel is 1: 1-8, and the CO is₂The adsorbent is a calcium oxide @ carbon material, and the molar ratio of calcium oxide to carbon is 1-4: 1.

2. The hydrogen-methane hybrid fuel, CO, of claim 1₂An adsorbent characterized by: the metal hydride is one or more of calcium hydride, magnesium hydride or lithium hydride.

3. Hydrogen and methane mixed fuel and CO as defined in claim 1₂The preparation method of the adsorbent is characterized by comprising the following steps:

(1) separating eggshell or shell with membrane, washing, drying, pulverizing to obtain granular eggshell or shell;

(2) pretreating the granular eggshell or shell, and then grinding;

(3) and mixing and grinding the ground granular eggshells or shells and metal hydride to prepare the hydrogen-methane mixed fuel and the calcium oxide @ carbon material.

4. Hydrogen and methane mixed fuel, CO, according to claim 3₂The preparation method of the adsorbent is characterized by comprising the following steps: in the step (1), the diameter of the granular eggshell or shell is 0.1-5 mm.

5. Hydrogen and methane mixed fuel, CO, according to claim 3₂The preparation method of the adsorbent is characterized by comprising the following steps: in the step (2), the diameter of the pretreated granular eggshell or shell is 0.1-2 um.

6. Hydrogen and methane mixed fuel, CO, according to claim 3₂The preparation method of the adsorbent is characterized by comprising the following steps: in the steps (2) and (3), the grinding is ball milling, the diameter of ball milling steel balls is 6-10 mm, and the weight of the ball milling steel balls is 24-30 g.

7. The hydrogen-methane hybrid fuel, CO, of claim 6₂The preparation method of the adsorbent is characterized by comprising the following steps: the rotation speed of the ball milling is 350-550 rpm/min, and the ball milling time is 12-48 h.

8. The hydrogen-methane hybrid fuel, CO, of claim 6₂The preparation method of the adsorbent is characterized by comprising the following steps: the weight ratio of the ball-milling steel balls to the eggshells or shells is 80: 1-100: 1.

9. Hydrogen and methane mixed fuel, CO, according to claim 3₂The preparation method of the adsorbent is characterized by comprising the following steps: in the step (3), the metal hydride is granular, and the diameter of the metal hydride is 0.1-5 mm.

10. The hydrogen-methane mixed fuel and CO of claim 3₂The preparation method of the adsorbent is characterized by comprising the following steps: step (3) is carried out in an argon atmosphere, H of which₂O/O₂The level was below 0.1 ppm.

Technical Field

The invention relates to a mixed fuel, an adsorbent and a preparation method thereof, in particular to a hydrogen-methane mixed fuel and CO₂An adsorbent and a preparation method thereof, belonging to the field ofIn the technical fields of clean energy and sustainable development.

Background

The shell morphology varies widely, but basically consists of 94% of CaCO by weight₃Crystals and an organic matrix constituting about 6% by weight of the shell. According to statistics, 300-700 g of waste shells are generated when 1kg of shellfish is processed. After tens of millions of tons of shellfish are processed, the number of waste shells is huge. In the traditional treatment method, shells are randomly stacked or uniformly incinerated as solid waste. Although this method can treat a large amount of waste shells, it has a great disadvantage. Is not beneficial to environmental protection and is waste in sustainable recycling economy.

In an era of increasingly common environmental problems, it has become necessary to effectively utilize resources to meet global energy demands, the egg industry has rapidly developed with the development of economy and the improvement of the standard of living of people, and the global egg production has reached 6.5 × 10 per year at present⁷Ton, which accounts for 185% of the egg production in 1990, producing about 800 million tons of eggshells per year. This material is sometimes used as a fertilizer, soil amendment or animal feed additive, but most are typically discharged and disposed of in landfills that produce off-flavors and facilitate microbial growth. Egg shell and egg shell (94% CaCO)₃) Is a calcium-rich material that is commonly used as a waste product in the food industry. If the waste water can be recycled, the problems caused by environmental pollution can be avoided, and economic benefits can be generated.

The inorganic mineral carbonate as the main component of the eggshell can be rapidly supplemented through the carbonization process, and is possible to be a renewable resource for producing fuel and chemicals. Fossil fuels such as coal and gasoline have a long natural history and are not renewable. The inorganic carbonate is abundant in the earth and is a cheap natural carbon source. Therefore, the direct conversion of these carbonates to methane is of great importance. At present, the conversion process of methane mainly utilizes metal or metal oxide as a catalyst to CO₂And H₂Heating is carried out. Other processes include electrochemical and photoreduction. The conversion of methane using metals or metal oxides as catalysts has very high safety requirements in hydrogen gas streams, and the methane is catalyzedThe process is not easy to control and is sometimes accompanied by the formation of by-products. The limitation of the storage condition of the active metal substance and the reactivity of the metal oxide is also a problem to be solved.

Disclosure of Invention

The purpose of the invention is as follows: the first purpose of the invention is to provide a hydrogen-methane mixed fuel and CO which are energy-saving, environment-friendly, high in adsorption efficiency and capable of relieving global warming₂Adsorbent, the second purpose of the invention is to provide the hydrogen-methane mixed fuel and CO₂A preparation method of the adsorbent.

The technical scheme is as follows: the hydrogen and methane mixed fuel and CO of the invention₂The adsorbent is prepared by reducing shells or eggshells by using metal hydrides, the molar ratio of the eggshells or the shells to the metal hydrides is 1: 1-4, the molar ratio of hydrogen to methane in the hydrogen-methane mixed fuel is 1: 1-8, and CO is₂The adsorbent is a calcium oxide @ carbon material, and the molar ratio of calcium oxide to carbon is 1-4: 1.

The hydrogen and methane mixed fuel and CO of the invention₂The preparation method of the adsorbent comprises the following steps:

(1) separating eggshell or shell with membrane, washing, drying, pulverizing to obtain granular eggshell or shell;

(2) pretreating granular eggshells or shells, and then grinding;

(3) and mixing and grinding the ground granular eggshells or shells and metal hydride to prepare the hydrogen-methane mixed fuel and the calcium oxide @ carbon material.

Has the advantages that: compared with the prior art, the invention can obtain the following beneficial effects: the waste eggshell shells are adopted as production raw materials, so that the energy is saved, the environment is protected, the waste is changed into valuable, and the sustainable development is facilitated; the metal hydride is used as a reducing agent to provide a hydrogen source, 100% of combustible gas is prepared, the main components are methane and hydrogen, and no other byproduct gas is generated; the solid sample after the reaction was subjected to CO in an atmosphere of carbon dioxide₂Adsorption, reduction of greenhouse effect and important significance for relieving global warming; compared with the method for preparing combustible gas in hydrogen atmosphere, the method is more stable and stableThe operation is convenient; the hydrogen and methane mixed gas is beneficial to improving the problem that the combustion rate of natural gas is slow, shortening the combustion lag period and improving the resource utilization rate and economic benefit; CO 2₂The adsorbent realizes the cyclic utilization process, improves the economic benefit and is used for the traditional CO₂The temperature change and pressure change adsorption greatly reduces the energy consumption.

Drawings

FIGS. 1(a) - (f) are comparative graphs of gas product detection according to the present invention, FIGS. 1(a) and 1(d) are comparative graphs of GC, respectively, of shell and eggshell, FIGS. 1(b) and 1(e) are infrared comparative graphs of gas, respectively, of shell and eggshell, and FIGS. 1(c) and 1(f) are comparative graphs of methane yield and methane gas content of shell and eggshell, respectively;

FIGS. 2(a) - (d) are comparative graphs of solid product detection according to the present invention, FIGS. 2(a) and 2(b) are infrared comparative graphs of solid products of shells and eggshells, respectively, and FIGS. 2(c) and 2(d) are XRD comparative graphs of solid products of shells and eggshells, respectively;

FIGS. 3(a) - (b) are BET and pore size distribution diagrams of the shell solid product of the present invention;

FIGS. 4(a) - (b) are Raman detection images of shell and eggshell solid products of the present invention;

FIG. 5 is a graph showing comparison of carbon dioxide adsorption of solid products obtained by subjecting shells and eggshells of the present invention to 48 hours at a rotation speed of 450rpm and 550rpm at a molar ratio of 1:2, respectively;

fig. 6 is a XRD comparison pattern of the shells, eggshells and calcium hydride of the present invention.

Detailed Description