Preparation method of natural gas
By reacting furfural slag with Rayney catalyst under mild conditions, the efficient conversion of furfural slag into natural gas is achieved, and the problem of difficulty in effectively using furfural slag in the prior art is solved, and an efficient and environmentally friendly natural gas preparation process is achieved.
Patent Information
- Application Number
- CN202311279863.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-28
- Publication Date
- 2025-03-28
AI Technical Summary
The prior art is difficult to effectively use furfural slag to convert all its carbon-carbon bonds into natural gas, and the recycling of catalysts is difficult to achieve.
By mixing furfural slag, Rainy-type catalyst and water, reacting under a hydrogen atmosphere, and using the recycling technology of Rainy-type catalyst, the complete carbon-carbon bond fracture of the furfural slag is converted into natural gas under mild conditions.
The efficient conversion of furfural slag into natural gas is achieved, and the carbon yield of natural gas can be as high as 90.2%, and the catalyst can be recycled, reducing the cost of the preparation process and the process is green and pollution-free.
Smart Images
Figure BDA0004478342760000031
Abstract
Description
Technical Field
[0001] The present application relates to a method for preparing natural gas, and belongs to the field of natural gas production. Background Art
[0002] Biomass is an important renewable energy source with the characteristics of wide distribution and abundant reserves. The annual biomass produced by photosynthesis on the earth is as high as 170-200 billion tons, which makes biomass an indispensable part of nature. The preparation of natural gas from biomass is of great significance for the resource utilization of biomass and the clean production route of natural gas. Furfural, also known as furan formaldehyde, is an important organic chemical raw material, widely used in the pharmaceutical, daily chemical and food industries. The production of furfural in my country began in 1943. Furfural production resources are abundant. Over the past few decades, we have developed into a large industrial furfural production country with considerable level and scale. The current method of industrial production of furfural can only be generated by hydrolysis of agricultural and sideline products. Generally, it is produced from the waste materials of agricultural and sideline products such as corn cobs, corn stalks, wheat straw, rice straw, rice husks, cottonseed husks, peanut shells and sugarcane bagasse. The residual solid after extracting furfural is furfural residue. Furfural residue is a renewable biomass resource worth using.
[0003] Natural gas is one of the basic energy sources in the world. It is mainly composed of CH4 (70-90%) and a small amount of C2-C4 hydrocarbons. It can be used for power generation, heating, ammonia production and hydrogen production. Therefore, it is of great significance to effectively catalyze the complete cracking of CC bonds in furfural residue into natural gas.
[0004] In view of the current situation in my country where furfural residue is mainly used to compost organic fertilizer and produce organic-inorganic compound fertilizer, a catalyst is used to break all carbon-carbon bonds of furfural residue to convert it into natural gas with methane as the main gas component. The natural gas produced in this process meets the transportation requirements of urban natural gas pipelines and has important economic value. Summary of the invention
[0005] The present invention develops a method for producing natural gas using furfural residue as raw material, realizing a revolutionary technology for preparing natural gas under mild conditions from waste furfural residue, providing important guarantee for the sustainable development of my country's environment and economy, and opening up a new path for natural gas production.
[0006] According to one aspect of the present application, a method for preparing natural gas is provided, comprising the following steps:
[0007] Mixing raw materials containing furfural residue, catalyst and water, reacting in a closed container under a hydrogen atmosphere to obtain a product containing natural gas;
[0008] The furfural residue is the residual solid after furfural is extracted from agricultural and sideline products;
[0009] The catalyst is a Raney-type catalyst.
[0010] The separation and reuse of the catalyst is to obtain the catalyst after the reaction by centrifugation, and further recycle it for reuse.
[0011] The hydrogen can also be separated and recycled.
[0012] The agricultural and sideline products are selected from at least one of corn cobs, corn stalks, wheat straw, rice straw, rice husks, cottonseed husks, peanut husks and sugarcane bagasse.
[0013] The Raney-type catalyst is selected from at least one of Raney Ni, Raney Ni-Al, Raney Ni-Mo, Raney Ni-Sn, Raney Ni-Fe or Raney Ni-Cu.
[0014] The mass of the catalyst is 20 to 70 wt% of the mass of the furfural residue;
[0015] Optionally, the mass of the catalyst is 50-70wt% of the mass of the furfural residue.
[0016] Optionally, the mass of the catalyst is any value of 50wt%, 60wt%, 70wt% of the mass of the furfural residue, or a range value between any two values.
[0017] The pressure of the hydrogen is 0.1-7 MPa;
[0018] Optionally, the pressure of the hydrogen is 1 to 4 MPa;
[0019] Optionally, the pressure of the hydrogen is 2-4 MPa.
[0020] Optionally, the pressure of the hydrogen is any value among 2MPa, 3MPa, 4MPa, or a range between any two values.
[0021] The reaction temperature is 250-350°C;
[0022] Optionally, the reaction temperature is 280-350°C;
[0023] Optionally, the reaction temperature is 300-350°C.
[0024] Optionally, the reaction temperature is any value of 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, or any range therebetween.
[0025] The reaction time is 0.05 to 24 hours;
[0026] Optionally, the reaction time is 0.05 to 10 h;
[0027] Optionally, the reaction time is 0.5 to 10 hours.
[0028] Optionally, the reaction time is any value among 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a range between any two of them.
[0029] The beneficial effects of this application include:
[0030] 1) The method of the present application directly catalytically converts furfural residue under mild conditions to prepare natural gas, realizes the upgrading cycle of furfural residue, can almost completely break carbon-carbon bonds in a short time, and the carbon yield of natural gas can be as high as 90.2%. The prepared natural gas can be used for urban natural gas pipeline transportation and has great economic value. This process not only solves the environmental problems caused by the large accumulation of furfural residue, but also can produce natural gas, and the produced natural gas meets the transportation requirements of natural gas urban pipelines, provides important guarantees for the sustainable development of my country's environment and economy, and opens up a new path for natural gas production.
[0031] 2) The catalyst used in the present invention can be centrifugally separated and further recycled, thereby reducing the cost of the preparation process.
[0032] 3) The method of the present invention has simple operation steps, is green and pollution-free, and is an environmentally friendly process. DETAILED DESCRIPTION
[0033] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0034] The Raney-type catalysts in the embodiments of the present application: Raney Ni, Raney Ni-Mo, Raney Ni-Al, Raney Ni-Sn, Raney Ni-Fe and Raney Ni-Cu are obtained by activating their alloy powders. Take an appropriate amount of alloy powder and add 20wt% sodium hydroxide solution in an oil bath for 1 hour. After the reaction is completed, wash with water until neutral to obtain the corresponding Raney-type catalyst, which is used in the catalytic reaction.
[0035] The carbon yield in the examples of the present application is calculated as follows:
[0036]
[0037] Example 1
[0038] Weigh 0.5g of Raney Ni-Al catalyst and add it to a 50mL reactor, and add 1.0g of raw corncob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 3MPa of H2. Heat it to 300℃ with electric heating under 800rpm magnetic stirring and react for 60min. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0039] The natural gas yield was 90.2%, and the gas composition was: CH4 (99.1%), C2-C4 (0.1%), and CO2 (0.8%).
[0040] Example 2
[0041] Weigh 0.6g of Raney Ni catalyst and add it to a 50mL reactor, and add 1.2g of raw material corn cob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 2MPa of H2. Heat it to 330℃ with electric heating under 800rpm magnetic stirring and react for 120min. After the reaction is completed, stop stirring, cool the reactor to room temperature in an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0042] The natural gas yield was 88.4%, and the gas composition was: CH4 (99.3%), C2-C4 (0.4%), and CO2 (0.3%).
[0043] Example 3
[0044] Weigh 0.7g of Raney Ni-Mo catalyst and add it to a 50mL reactor, and add 1.5g of raw corn cob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 4MPa of H2. Heat it to 310℃ with electric heating under 800rpm magnetic stirring and react for 180min. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0045] The natural gas yield was 86.4%, and the gas composition was: CH4 (98.7%), C2-C4 (1.0%), and CO2 (0.3%).
[0046] Example 4
[0047] Weigh 0.5g of Raney Ni-Fe catalyst and add it to a 50mL reactor, and add 1.0g of raw corn cob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 4MPa of H2. Heat it to 320℃ with electric heating under 800rpm magnetic stirring and react for 300min. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0048] The natural gas yield was 87.4%, and the gas composition was: CH4 (99.0%), C2-C4 (0.4%), and CO2 (0.6%).
[0049] Example 5
[0050] Weigh 0.5g of Raney Ni-Sn catalyst and add it to a 50mL reactor, and add 1.0g of raw corncob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 4MPa of H2. Heat it to 300℃ with electric heating under 800rpm magnetic stirring and react for 30min. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0051] The natural gas yield was 83.4%, and the gas composition was: CH4 (99.2%), C2-C4 (0.4%), and CO2 (0.4%).
[0052] Example 6
[0053] Weigh 0.6g of Raney Ni-Cu catalyst and add it to a 50mL reactor, and add 1.2g of raw corncob furfural residue at the same time. Seal the reactor, fill it with N2 3 to 5 times, exhaust the air in the reactor, fill it with H2 3 to 5 times, exhaust the N2 in the reactor, and finally fill it with 4MPa of H2. Heat it to 310℃ with electric heating under 800rpm magnetic stirring and react for 300min. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction generated gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0054] The natural gas yield was 80.4%, and the gas composition was: CH4 (99.2%), C2-C4 (0.4%), and CO2 (0.4%).
[0055] Example 7
[0056] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with rice straw furfural residue. The gas product obtained was natural gas with a yield of 90.2% and a gas composition of CH4 (99.0%), C2~C4 (0.4%), and CO2 (0.6%).
[0057] Example 8
[0058] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with rice husk furfural residue. The gas product obtained was natural gas with a yield of 87.1% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0059] Example 9
[0060] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with peanut shell furfural residue. The gas product obtained was natural gas with a yield of 83.4%, and the gas composition was: CH4 (99.0%), C2~C4 (0.1%), CO2 (0.9%).
[0061] Example 10
[0062] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with sugarcane furfural residue. The gas product obtained was natural gas with a yield of 86.2% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0063] Embodiment 11
[0064] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with wheat straw furfural residue. The gas product obtained was natural gas with a yield of 83.5%, and the gas composition was: CH4 (99.0%), C2~C4 (0.1%), CO2 (0.9%).
[0065] Example 12
[0066] The preparation process described in Example 1 was repeated, except that the raw material corn cob furfural residue was replaced with corn straw furfural residue. The gas product obtained was natural gas with a yield of 86.3% and a gas composition of: CH4 (99.2%), C2~C4 (0.2%), and CO2 (0.6%).
[0067] Embodiment 13
[0068] The preparation process described in Example 2 was repeated, except that the raw material corn cob furfural residue was replaced with cottonseed hull furfural residue. The gas product obtained was natural gas with a yield of 87.1% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0069] Embodiment 14
[0070] The preparation process described in Example 2 was repeated, except that the raw material corn cob furfural residue was replaced with rice husk furfural residue. The gas product obtained was natural gas with a yield of 84.2% and a gas composition of CH4 (98.2%), C2-C4 (1.2%), and CO2 (0.6%).
[0071] Embodiment 15
[0072] The preparation process described in Example 2 was repeated, except that the raw material corn cob furfural residue was replaced with rice straw furfural residue. The gas product obtained was natural gas with a yield of 83.3% and a gas composition of CH4 (99.2%), C2~C4 (0.2%), and CO2 (0.6%).
[0073] Example 16
[0074] The preparation process described in Example 2 was repeated, except that the raw material corn cob furfural residue was replaced with cottonseed hull furfural residue. The obtained gas product had a natural gas yield of 85.4% and a gas composition of CH4 (99.5%), C2-C4 (0.2%), and CO2 (0.3%).
[0075] Embodiment 17
[0076] The preparation process described in Example 2 was repeated, except that the reaction time was changed to 100 min. The gas product obtained was natural gas with a yield of 84.1% and a gas composition of CH4 (99.4%), C2-C4 (0.1%), and CO2 (0.5%).
[0077] Embodiment 18
[0078] The preparation process described in Example 2 was repeated, except that the reaction time was changed to 90 min. The gas product obtained was natural gas with a yield of 86.2% and a gas composition of CH4 (99.3%), C2-C4 (0.2%), and CO2 (0.5%).
[0079] Embodiment 19
[0080] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 80 min. The gas product obtained was natural gas with a yield of 87.1% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0081] Embodiment 20
[0082] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 70 min. The gas product obtained was natural gas with a yield of 87.2% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0083] Embodiment 21
[0084] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 60 min. The gas product obtained was natural gas with a yield of 87.5%, and the gas composition was: CH4 (99.2%), C2-C4 (0.2%), CO2 (0.6%).
[0085] Embodiment 22
[0086] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 50 min. The gas product obtained was natural gas with a yield of 87.2% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0087] Embodiment 23
[0088] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 30 min. The gas product obtained was natural gas with a yield of 84.1% and a gas composition of: CH4 (99.4%), C2-C4 (0.1%), and CO2 (0.5%).
[0089] Embodiment 24
[0090] The preparation process described in Example 3 was repeated, except that the reaction time was changed to 10 min. The gas product obtained was natural gas with a yield of 86.3%, and the gas composition was: CH4 (99.3%), C2-C4 (0.2%), CO2 (0.5%).
[0091] Embodiment 25
[0092] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 250°C. The gas product obtained was natural gas with a yield of 88.2% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0093] Embodiment 26
[0094] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 260°C. The gas product obtained was natural gas with a yield of 79.1% and a gas composition of CH4 (97.3%), C2-C4 (1.1%), and CO2 (1.6%).
[0095] Embodiment 27
[0096] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 270°C. The gas product obtained was natural gas with a yield of 78.2% and a gas composition of CH4 (97.2%), C2-C4 (0.4%), and CO2 (2.4%).
[0097] Embodiment 28
[0098] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 280°C. The gas product obtained was natural gas with a yield of 84.1% and a gas composition of CH4 (99.2%), C2-C4 (0.2%), and CO2 (0.6%).
[0099] Embodiment 29
[0100] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 290°C. The gas product obtained was natural gas with a yield of 84.2% and a gas composition of CH4 (99.4%), C2-C4 (0.1%), and CO2 (0.5%).
[0101] Embodiment 30
[0102] The preparation process described in Example 4 was repeated, except that the reaction temperature was changed to 300°C. The gas product obtained was natural gas with a yield of 86.3%, and the gas composition was: CH4 (99.3%), C2~C4 (0.2%), CO2 (0.5%).
[0103] Embodiment 31
[0104] The preparation process described in Example 5 was repeated, except that the reaction temperature was changed to 310°C. The gas product obtained was natural gas with a yield of 85.3%, and the gas composition was: CH4 (99.2%), C2~C4 (0.2%), CO2 (0.6%).
[0105] Embodiment 32
[0106] The preparation process described in Example 5 was repeated, except that the hydrogen pressure was changed to 3.5 MPa. The gas product obtained was natural gas with a yield of 86.2%, and the gas composition was: CH4 (99.6%), C2~C4 (0.1%), CO2 (0.3%).
[0107] Embodiment 33
[0108] The preparation process described in Example 5 was repeated, except that the hydrogen pressure was changed to 3.0 MPa. The gas product obtained was natural gas with a yield of 82.6%, and the gas composition was: CH4 (99.1%), C2~C4 (0.3%), CO2 (0.6%).
[0109] Embodiment 34
[0110] The preparation process described in Example 5 was repeated, except that the hydrogen pressure was changed to 2.5 MPa. The gas product obtained was natural gas with a yield of 86.4%, and the gas composition was: CH4 (99.2%), C2~C4 (0.2%), CO2 (0.6%).
[0111] Embodiment 35
[0112] The preparation process described in Example 5 was repeated, except that the hydrogen pressure was changed to 2.0 MPa. The gas product obtained was natural gas with a yield of 84.2%, and the gas composition was: CH4 (99.4%), C2~C4 (0.1%), CO2 (0.5%).
[0113] Embodiment 36
[0114] The preparation process described in Example 5 was repeated, except that the hydrogen pressure was changed to 1.5 MPa. The gas product obtained was natural gas with a yield of 86.2%, and the gas composition was: CH4 (99.3%), C2~C4 (0.2%), CO2 (0.5%).
[0115] Embodiment 37
[0116] The preparation process described in Example 6 was repeated, except that the hydrogen pressure was changed to 1.0 MPa. The gas product obtained was natural gas with a yield of 84.4%, and the gas composition was: CH4 (97.2%), C2~C4 (1.2%), CO2 (1.6%).
[0117] Embodiment 38
[0118] The preparation process described in Example 6 was repeated, except that the hydrogen pressure was changed to 0.5 MPa. The gas product obtained was natural gas with a yield of 78.2%, and the gas composition was: CH4 (99.2%), C2~C4 (0.2%), CO2 (0.6%).
[0119] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing natural gas, characterized in that: The following steps are involved: Mixing raw materials containing furfural residue, catalyst and water, reacting in a closed container under a hydrogen atmosphere to obtain a product containing natural gas; The furfural residue is the residual solid after furfural is extracted from agricultural and sideline products; The catalyst is a Raney-type catalyst.
2. The method according to claim 1, characterized in that The agricultural and sideline products are selected from at least one of corn cobs, corn stalks, wheat straw, rice straw, rice husks, cottonseed husks, peanut husks and sugarcane bagasse.
3. The method according to claim 1, characterized in that The Raney-type catalyst is selected from at least one of Raney Ni, Raney Ni-Al, Raney Ni-Mo, Raney Ni-Sn, Raney Ni-Fe or Raney Ni-Cu.
4. The method according to claim 1, characterized in that: The mass of the catalyst is 20-70 wt % of the mass of the furfural residue.
5. The method according to claim 1, characterized in that The mass of the catalyst is 50-70wt% of the mass of the furfural residue.
6. The method according to claim 1, characterized in that The pressure of the hydrogen is 0.1-7 MPa; Preferably, the pressure of the hydrogen is 1 to 4 MPa; Preferably, the pressure of the hydrogen is 2-4 MPa.
7. The method according to claim 1, characterized in that The reaction temperature is 250-350°C; Preferably, the reaction temperature is 280-350°C; Preferably, the reaction temperature is 300-350°C.
8. The method according to claim 1, characterized in that The reaction time is 0.05 to 24 hours; Preferably, the reaction time is 0.05 to 10 h; Preferably, the reaction time is 0.5 to 10 h.