CN113061073A - Method for preparing methane fuel by using hydrogen storage metal to induce carbonate hydrogenation - Google Patents
Method for preparing methane fuel by using hydrogen storage metal to induce carbonate hydrogenation Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 9
- 238000003860 storage Methods 0.000 title claims abstract description 9
- 239000000446 fuel Substances 0.000 title claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- 239000011575 calcium Substances 0.000 claims abstract description 59
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 53
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims description 33
- 229910000831 Steel Inorganic materials 0.000 claims description 23
- 239000010959 steel Substances 0.000 claims description 23
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 abstract description 75
- 229910052987 metal hydride Inorganic materials 0.000 abstract description 6
- 150000004681 metal hydrides Chemical class 0.000 abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 12
- 150000001342 alkaline earth metals Chemical class 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000004451 qualitative analysis Methods 0.000 description 10
- 238000004445 quantitative analysis Methods 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
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Abstract
利用储氢金属诱导碳酸盐加氢制备甲烷燃料的方法，属于清洁能源和可持续发展技术领域，无氧条件下，将颗粒状储氢金属钙、碳酸钙和钢珠装入球磨罐中，再向球磨罐通入氢气进行常温反应，制得甲烷，或者无氧条件下，将颗粒状储氢金属钙与碳酸钙装入加热装置，再向加热装置通入氢气进行加热反应，制得甲烷。以上两种方法都以金属和氢气为原料，反应过程中生成了金属氢化物，金属氢化物可还原金属碳酸盐，得到氢气甲烷混合气体无其他副产物气体产生。本发明产率高、选择性好、成本低廉。
The method for preparing methane fuel by using hydrogen storage metal to induce carbonate hydrogenation belongs to the technical field of clean energy and sustainable development. Pour hydrogen into the ball mill to carry out the reaction at room temperature to obtain methane, or under anoxic conditions, put granular hydrogen-storing metal calcium and calcium carbonate into the heating device, and then pass hydrogen into the heating device for heating reaction to obtain methane. Both of the above two methods use metal and hydrogen as raw materials. During the reaction, metal hydrides are generated, and the metal hydrides can reduce metal carbonates to obtain a mixed gas of hydrogen and methane without the production of other by-product gases. The invention has high yield, good selectivity and low cost.
Description
Technical Field
The invention belongs to the technical field of clean energy and sustainable development, and particularly relates to a methane production technology.
Background
The problems of environmental pollution, energy source dilemma, global warming and the like become key challenges for people in modern society. Carbon dioxide is a greenhouse gas (GHG) mainly caused by the large consumption of fossil fuels, and its emission amount reaches a historical level several years ago. Thus, reducing carbon dioxide in the atmosphere remains a significant challenge. Research has found that metal oxides as solid adsorbents can effectively capture carbon dioxide,carbon dioxide is converted to carbonate. It is anticipated that in the future, large amounts of carbonate will be produced to capture carbon dioxide. In addition, the inorganic mineral carbonate acts as CO2Are present in large amounts in nature, and thus the conversion of carbonates into useful chemical products is of interest to the scientific community. Methane is widely used, and has the advantage of high combustion value as hydrocarbon with the highest hydrogen-carbon ratio, so the demand of methane is increasing continuously. In recent years, the method for converting metal carbonate into hydrocarbons by high-temperature catalytic hydrogenation has received more and more attention due to its simplicity and convenience. But it is considered that the methane yield and selectivity of the process is low. At present, the reaction of metal carbonate and metal hydride is reported, a new way for hydrogenating the metal carbonate is developed, but the price of the metal hydride is relatively expensive, so that the cost for producing methane is high, and the popularization and the application are not facilitated.
Disclosure of Invention
The invention aims to provide a method for preparing methane fuel by using hydrogen storage metal to induce carbonate hydrogenation with high yield and low cost.
The invention is realized by the following two methods:
the method comprises the following steps: under the anaerobic condition, granular hydrogen storage metal calcium, calcium carbonate and steel balls are loaded into a ball milling tank, and then hydrogen is introduced into the ball milling tank to carry out normal temperature reaction, so as to prepare methane.
The second method comprises the following steps: under the anaerobic condition, granular hydrogen storage metal calcium and calcium carbonate are loaded into a heating device, and then hydrogen is introduced into the heating device for heating reaction to prepare methane.
The present invention preferably uses calcium metal with calcium carbonate, which is the highest methane yield compared to other carbonates.
Compared with the prior art, the two methods have the advantages that metal and hydrogen are used as raw materials, metal hydride is generated in the reaction process, the metal hydride can reduce metal carbonate, and the obtained hydrogen and methane mixed gas has no other byproduct gas; compared with in CO2The method is more effective, more convenient and lower in cost; compared with the direct synthesis of methane fuel in carbonate and hydrogenThe invention has the advantages of higher yield, better selectivity and lower cost.
Most of the methods for preparing methane in the prior art are carried out in the presence of a high-temperature catalyst, but the method for preparing methane by using the calcium metal induced carbonate hydrogenation method at room temperature adopts a mechanical ball milling method, the highest yield of the produced methane at room temperature can reach 60%, and the selectivity can reach 100%. The invention also adopts heating condition to prepare methane by calcium metal induced carbonate hydrogenation, the highest yield of the produced methane can reach 91 percent, and the selectivity can reach 100 percent.
Further, in the first method, the hydrogen pressure is selected to be 5-16 bar, and methane is generated only when the hydrogen pressure is 5 bar.
Further, in the first method, the rotation speed of ball milling at room temperature is 450-600 rpm, and the energy for generating methane can be provided only when the rotation speed reaches 450 rpm.
Further, in the second method, the hydrogen pressure is selected to be 2-16 bar, and methane is generated only when the hydrogen pressure is 2 bar during heating.
Further, in the second method, the heating temperature is 400-500 ℃, and 400 ℃ is found to be the threshold temperature.
Furthermore, the two methods need small metal particles in order to increase the contact surface between solid reactions and ensure that the reactions are more complete, and the particle size of the granular metal calcium is 0.01-1 mm.
Further, since the elemental metals and metal carbonates are relatively reactive and oxidation occurs upon direct exposure to air, the above two methods operate in a glove box filled with argon atmosphere and the argon atmosphere is H2O/O2The level was below 0.1 ppm.
In addition, in the two methods, the feeding molar ratio of the metal calcium to the calcium carbonate is 2-4: 1, which is proved by repeated experimental researches: the metallic calcium content directly affects the methane yield, and as the molar ratio of metallic calcium increases, the methane yield increases.
Drawings
FIG. 1 is a GC comparison of the gaseous products of example 1.
FIG. 2 is an infrared contrast plot of the gaseous product of example 1.
Figure 3 is a GC comparison of the gaseous products of example 2.
FIG. 4 is an infrared contrast plot of the gaseous product of example 2.
Figure 5 is a GC comparison of the gaseous products of example 3.
FIG. 6 is an infrared contrast plot of the gaseous product of example 3.
Figure 7 is a GC comparison of the gaseous products of example 4.
FIG. 8 is an infrared contrast plot of the gaseous product of example 4.
FIG. 9 is a GC comparison of the gaseous products of example 5.
FIG. 10 is an infrared contrast plot of the gaseous product of example 5.
FIG. 11 is a GC comparison of the gaseous products of example 6.
FIG. 12 is an infrared contrast plot of the gaseous product of example 6.
Figure 13 is a GC comparison of the gaseous products of example 7.
FIG. 14 is an infrared contrast plot of the gaseous product of example 7.
FIG. 15 is a GC comparison of the gaseous products of example 8.
FIG. 16 is an infrared contrast plot of the gaseous product of example 8.
FIG. 17 is a GC comparison of the gaseous products of example 9.
FIG. 18 is an infrared contrast plot of the gaseous product of example 9.
FIG. 19 is a GC comparison of the gaseous products of example 10.
FIG. 20 is an infrared contrast plot of the gaseous product of example 10.
Detailed Description
Example 1
At room temperature, hydrogen storage metal calcium and magnesium are used for inducing calcium carbonate to be hydrogenated to prepare methane, and the method comprises the following steps:
(1) the calcium metal is ground to obtain a granular calcium metal having a particle size of about 0.01 to 1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm) at room temperatureRespectively weighing 450 mg of total mass of alkaline earth metal calcium and magnesium and calcium carbonate according to the molar ratio of 3:1, putting the calcium and magnesium and calcium carbonate into different ball milling tanks, respectively adding 20 ball milling steel balls into the two ball milling tanks, wherein the total mass is 18 g, the diameter of each ball milling steel ball is 3.14 mm, the weight ratio of each ball milling steel ball to a sample is 30:1, and introducing high-purity H2 (16 bar), mechanical ball milling reaction was carried out at 550 rpm for 24 hours, and the obtained gas was qualitatively and quantitatively analyzed by a gas chromatograph and a gas infrared detector.
The gas sample obtained above was detected and the gas chromatograms were compared, and the results are shown in fig. 1 and 2. It should be noted that: "3 Mg-CaCO" in FIG. 13"denotes a reaction system consisting of Mg and CaCO3Composition and Mg with CaCO3The feeding molar ratio of (A) to (B) is 3:1, and the like.
A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present.
The methane yield of the implementation method under the condition that the molar ratio of the metal calcium to the calcium carbonate is 3:1 is 35.14%, and the methane yield obtained under the condition that the molar ratio of the magnesium to the calcium carbonate is 3:1 is very low and is not enough to calculate. The comparison shows that the calcium and calcium carbonate system has superior methanation performance compared with the magnesium and calcium carbonate system.
Example 2
At room temperature, alkaline earth metal calcium is used for inducing calcium carbonate to be hydrogenated to prepare methane, and the steps are as follows:
(1) the calcium metal is ground to obtain a granular calcium metal having a particle size of about 0.01 to 1 mm.
(2) In an argon atmosphere (H)2O/O2Level is 0.08 ppm), respectively weighing 450 mg of total mass of alkaline earth metal calcium and calcium carbonate according to the mol ratio of 2: 1, 3:1 and 4: 1 at room temperature, putting the weighed materials into different ball milling tanks, adding 20 ball milling steel balls, wherein the total mass is 18 g, the diameter of each ball milling steel ball is 3.14 mm, the weight ratio of each ball milling steel ball to a sample is 30:1, introducing high-purity H2(16 bar), machine operating at 550 rpm for 24 hoursPerforming mechanical ball milling reaction, and performing qualitative and quantitative analysis on the obtained gas through a gas chromatograph and a gas infrared detector.
The gas sample obtained above was detected and the gas chromatograms were compared, and the results are shown in fig. 3 and 4. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. It can be seen from the figure that as the molar ratio of metal Ca increases, the methane peak area and the peak intensity in the gas chromatogram increase.
The methane yields of metal calcium and calcium carbonate obtained by the implementation method in the molar ratios of 2: 1, 3:1 and 4: 1 are respectively 26.43%, 35.14% and 37.23%, and it can be seen that the higher the calcium ratio is, the more excellent the methane yield effect is.
Example 3
At room temperature, alkaline earth metal calcium is used for inducing calcium carbonate to be hydrogenated to prepare methane, and the steps are as follows:
(1) the calcium metal is ground to obtain a granular size, and the particle size of the granular calcium metal is about 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), weighing 450 mg of total mass of metallic calcium and calcium carbonate according to the molar ratio of 3:1 at room temperature, putting the weighed materials into a ball milling tank, adding 20 ball milling steel balls, wherein the total mass is 18 g, the diameter of each ball milling steel ball is 3.14 mm, the weight ratio of each ball milling steel ball to a sample is 30:1, respectively introducing high-purity hydrogen of 5 bar, 10 bar and 16 bar, performing mechanical ball milling reaction for 24 hours at 550 rpm, and performing qualitative and quantitative analysis on the obtained gas through a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 5 and 6. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. It can be seen from the figure that hydrogen is associated withThe increase in gas pressure, the methane peak area and the peak intensity in the gas chromatograph increased.
The yields of methane obtained by the method at 5 bar, 10 bar and 16 bar hydrogen pressure were 27.88%, 29.18% and 35.14%, respectively, and it can be seen that the higher the hydrogen pressure, the more excellent the methane yield.
Example 4
At room temperature, alkaline earth metal calcium is used for inducing calcium carbonate to be hydrogenated to prepare methane, and the steps are as follows:
(1) the calcium metal is ground to obtain a granular size, and the particle size of the granular calcium metal is about 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), weighing 450 mg of total mass of metallic calcium and calcium carbonate according to the molar ratio of 3:1 at room temperature, putting the weighed materials into a ball milling tank, adding 20 ball milling steel balls, wherein the total mass is 18 g, the diameter of each ball milling steel ball is 3.14 mm, the weight ratio of each ball milling steel ball to a sample is 30:1, respectively introducing high-purity hydrogen gas of 16 bar, performing mechanical ball milling reaction for 2, 6, 12, 24 and 48 hours at 550 rpm, and performing qualitative and quantitative analysis on the obtained gas by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 7 and 8. In FIG. 7, a very clear peak appeared around 10 min, which was detected as CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. From the graph, it can be seen that the reaction time was 2h, the area of methane peak in the GC-to-gas infrared graph was almost zero, and after the reaction time was 6h, the methane signal became clear, but the yield was low. The methane peak area and peak intensity in the gas chromatograph increased with increasing reaction time.
The methane yield obtained by the method is low at 2h and 6h, and the methane yield is 10%, 35.14% and 45.77% at 12 h, 24 h and 48 h respectively, and the longer the reaction time is, the better the methane yield is.
Example 5
At room temperature, alkaline earth metal calcium is used for inducing calcium carbonate to be hydrogenated to prepare methane, and the steps are as follows:
(1) the calcium metal is ground to obtain a granular size, and the particle size of the granular calcium metal is about 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), weighing 450 mg of total mass of metal calcium and calcium carbonate according to the molar ratio of 3:1 at room temperature, putting the weighed materials into a ball milling tank, adding 20 ball milling steel balls, wherein the total mass is 18 g, the diameter of each ball milling steel ball is 3.14 mm, the weight ratio of each ball milling steel ball to a sample is 30:1, introducing high-purity hydrogen gas of 16 bar, performing mechanical ball milling reaction for 24 hours at 450 rpm, 550 rpm, 580 rpm and 600 rpm respectively, and performing qualitative and quantitative analysis on the obtained gas through a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 9 and 10. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. From the graph, it can be found that the methane peak area and the peak intensity in the gas chromatogram increase with the increase of the hydrogen pressure.
The methane yield obtained by the implementation method under the rotating speeds of 450, 550, 580 and 600 rpm is respectively trace, 35.14, 60.41 and 56.00 percent, and the effect of the methane yield is more excellent when the rotating speed is higher under the same conditions.
Example 6
The method for preparing methane by using alkaline earth metal calcium to induce calcium carbonate to be hydrogenated under the heating condition comprises the following steps:
(1) the calcium metal is ground to obtain granular calcium metal with a particle size of 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level is 0.08 ppm), the total mass of alkaline earth metal calcium and calcium carbonate is weighed according to the mol ratio of 2: 1, 3:1 and 4: 1 respectively at room temperature, and CaCO is firstly added3Placing into a steel heating pipe, and spreading Ca powder on CaCO3Filling high purityH2(16 bar), heating reaction is carried out for 48 hours at 500 ℃, and qualitative and quantitative analysis is carried out on the obtained gas by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 11 and 12. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. It can be seen from the figure that as the molar ratio of metal Ca increases, the methane peak area and the peak intensity in the gas chromatogram increase.
The methane yields of metal calcium and calcium carbonate obtained by the implementation method in the molar ratios of 2: 1, 3:1 and 4: 1 are respectively 31.4%, 62% and 91.36%, and it can be seen that the higher the metal calcium ratio is, the more excellent the methane yield effect is.
Example 7
The method for preparing methane by using alkaline earth metal calcium to induce calcium carbonate to be hydrogenated under the heating condition comprises the following steps:
(1) the calcium metal is ground to obtain granular calcium metal with a particle size of 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level is 0.08 ppm), the total mass of the alkaline earth metal calcium and the calcium carbonate is weighed to be 150 mg according to the mol ratio of 4: 1 at room temperature, and CaCO is firstly added3Placing into a steel heating pipe, and spreading Ca powder on CaCO3Filling high-purity H into the upper part2(16 bar), heating reaction is carried out for 48 hours at 350, 450, 480, 500 and 525 ℃, and the obtained gas is subjected to qualitative and quantitative analysis by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 13 and 14. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present. FromIt can be seen that the area of the methane peak and the peak intensity in the gas chromatogram increase with increasing heating temperature.
The yields of methane obtained after 48 hours of reaction at 350 ℃, 450 ℃, 480 ℃, 500 ℃ and 525 ℃ in this embodiment were 0%, 29.7%, 33.9%, 91.36% and 87.6%, respectively, and it can be seen that the yield of methane can be improved by appropriately increasing the temperature.
Example 8
The method for preparing methane by using alkali metal and alkaline earth induced metal carbonate hydrogenation under the heating condition comprises the following steps:
(1) the metal is treated to obtain granular calcium with a particle size of 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), weighing 150 mg of metal and corresponding metal carbonate according to the molar ratio of 4: 1 at room temperature, placing the carbonate into a steel heating pipe, laying the metal above the metal carbonate, and filling high-purity H2(16 bar), heating reaction is carried out for 48 hours at 500 ℃, and the obtained gas is subjected to qualitative and quantitative analysis by a gas chromatograph and a gas infrared detector.
Under otherwise identical conditions, no metal is added, only Li is added2CO3Or CaCO3Putting into steel heating pipe, and charging high purity H2(16 bar), heating reaction is carried out for 48 hours at 500 ℃, and the obtained gas is subjected to qualitative and quantitative analysis by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 15 and 16. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present.
Li2CO3、Li-Li2CO3、Na-Na2CO3、Mg-MgCO3、CaCO3And Ca-CaCO3The system is at 500 deg.CThe yield of the methane obtained after 48 hours of reaction is respectively 0%, 50.02%, 13.76%, 12.68%, 29.5% and 91.36%, the addition of the metal effectively improves the methanation performance of the system, and the Ca and CaCO3The system has the highest methane yield, and the second is Li-Li2CO3And (4) preparing the system.
Description of the drawings: the above "Li2CO3"means that no metal is added and the reaction system has only Li2CO3And H2(ii) a The above "Li-Li2CO3"indicates that metallic Li is added and the reaction system contains Li and Li2CO3And H2(ii) a The other is similar.
Example 9
The method for preparing methane by using alkaline earth metal calcium to induce calcium carbonate to be hydrogenated under the heating condition comprises the following steps:
(1) the metal is treated to obtain granular calcium with a particle size of 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), weighing the metal and the corresponding metal carbonate according to the molar ratio of 4: 1 at room temperature to obtain a total mass of 150 mg, firstly putting the carbonate into a steel heating pipe, then spreading the metal above the metal carbonate, and filling pure H with different pressures2Heating reaction is carried out for 48 hours at 500 ℃, and qualitative and quantitative analysis is carried out on the obtained gas by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 17 and 18. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present.
The yields of methane obtained after 48 h reactions at 2 bar, 8 bar, 10 bar, 12 bar, 14 bar and 16 bar of this embodiment were 7.98%, 25.8%, 26.9%, 52.47%, 90.23% and 91.36%, respectively, and it can be seen that increasing the hydrogen pressure appropriately increases the yield of methane.
Example 10
The method for preparing methane by using alkaline earth metal calcium to induce calcium carbonate to be hydrogenated under the heating condition comprises the following steps:
(1) the metal is treated to obtain granular calcium with a particle size of 0.1 mm.
(2) In an argon atmosphere (H)2O/O2Level 0.08 ppm), the metal and the corresponding metal carbonate are weighed according to the molar ratio of 4: 1 at room temperature to obtain the total mass of 150 mg, the carbonate is firstly put into a steel heating pipe, then the metal is flatly laid above the metal carbonate, and 16 bar of pure H is filled2Heating reaction is carried out at 500 ℃ for different time, and qualitative and quantitative analysis is carried out on the obtained gas by a gas chromatograph and a gas infrared detector.
The gas samples obtained above were detected and the gas chromatograms were compared, and the results are shown in fig. 19 and 20. A very obvious peak appears around 10 min, and the peak is detected to be CH4Peak(s). Found at 3000 cm in the gas infrared image-1、1300 cm-1The obvious hydrocarbon stretching vibration peak is nearby, and CH is further proved4Is present.
The methane yields obtained in this example system after 2, 6, 12, 24 and 48 h reactions at 500 ℃ were 0%, 30.16%, 28.6%, 38.37% and 91.36%, respectively, and it can be seen that the methane yield can be improved by appropriately extending the heating time.
Claims (9)
1. The method for preparing the methane fuel by using the hydrogen storage metal to induce the hydrogenation of the carbonate is characterized by comprising the following steps: under the anaerobic condition, granular metal calcium, calcium carbonate and steel balls are loaded into a ball milling tank, and then hydrogen is introduced into the ball milling tank to carry out normal-temperature reaction, so as to prepare methane.
2. The method of claim 1, wherein: the hydrogen pressure is 5-16 bar.
3. The method of claim 1, further comprising: the rotating speed of the ball milling is 450-600 rpm.
4. The method for preparing the methane fuel by using the hydrogen storage metal to induce the hydrogenation of the carbonate is characterized by comprising the following steps: under the anaerobic condition, granular metal calcium and calcium carbonate are loaded into a heating device, and then hydrogen is introduced into the heating device for heating reaction to prepare methane.
5. The method of claim 4, wherein: the hydrogen pressure is 2-16 bar.
6. The method of claim 4, further comprising: the temperature condition of the heating reaction is 400-500 ℃.
7. The method according to claim 1 or 4, characterized in that: the particle size of the metal Ca is 0.01-1 mm.
8. The method of claim 1 or 4, wherein: h of the argon atmosphere2O/O2The level was below 0.1 ppm.
9. The method of claim 1 or 4, wherein: the feeding molar ratio of the metal calcium to the calcium carbonate is 2-4: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113582798A (en) * | 2021-09-09 | 2021-11-02 | 北京化工大学 | A kind of inorganic carbonate hydrogenation decomposition method using hydrogen storage solvent as hydrogen source |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080156909A1 (en) * | 2005-03-09 | 2008-07-03 | Studiengesellschaft Kohle Mbh | Method For Synthesizing Compounds |
| CN105339336A (en) * | 2013-02-24 | 2016-02-17 | 二氧化碳材料公司 | Conversion of CO2 to fuels and chemicals |
| CN105517951A (en) * | 2013-09-25 | 2016-04-20 | 太平洋水泥株式会社 | Method for producing metal hydride |
-
2021
- 2021-04-19 CN CN202110419263.6A patent/CN113061073A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080156909A1 (en) * | 2005-03-09 | 2008-07-03 | Studiengesellschaft Kohle Mbh | Method For Synthesizing Compounds |
| CN105339336A (en) * | 2013-02-24 | 2016-02-17 | 二氧化碳材料公司 | Conversion of CO2 to fuels and chemicals |
| CN105517951A (en) * | 2013-09-25 | 2016-04-20 | 太平洋水泥株式会社 | Method for producing metal hydride |
Non-Patent Citations (3)
| Title |
|---|
| GUOCUI MAO ET AL.: "alkaline earth metal-induced hydrogenation of the CaO-Captured CO2 to metane at room temperature" * |
| SONG ZHANG ET AL.: "Storage and in-situ preparation of H2-mixed CH4 fuel by thermochemical reduction of inorganic carbonates with activated metal hydrides" * |
| 王璐: "利用金属氢化物和金属碳酸盐通过机械化学法制备清洁燃料的研究" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582798A (en) * | 2021-09-09 | 2021-11-02 | 北京化工大学 | A kind of inorganic carbonate hydrogenation decomposition method using hydrogen storage solvent as hydrogen source |
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