CN115109616B - Method for producing natural gas - Google Patents
Method for producing natural gas Download PDFInfo
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- CN115109616B CN115109616B CN202110303544.5A CN202110303544A CN115109616B CN 115109616 B CN115109616 B CN 115109616B CN 202110303544 A CN202110303544 A CN 202110303544A CN 115109616 B CN115109616 B CN 115109616B
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- forestry waste
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 324
- 239000003345 natural gas Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000002023 wood Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000010902 straw Substances 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002028 Biomass Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 235000010099 Fagus sylvatica Nutrition 0.000 claims description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 9
- 241000018646 Pinus brutia Species 0.000 claims description 9
- 235000011613 Pinus brutia Nutrition 0.000 claims description 9
- 241000219000 Populus Species 0.000 claims description 8
- 241000209140 Triticum Species 0.000 claims description 8
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 7
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 5
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 5
- 229910018054 Ni-Cu Inorganic materials 0.000 claims description 4
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 4
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 4
- 229910018481 Ni—Cu Inorganic materials 0.000 claims description 4
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 240000000731 Fagus sylvatica Species 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 45
- 229910052799 carbon Inorganic materials 0.000 abstract description 45
- 239000000428 dust Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 9
- 241001070947 Fagus Species 0.000 description 59
- 238000002360 preparation method Methods 0.000 description 37
- 238000003756 stirring Methods 0.000 description 10
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004451 qualitative analysis Methods 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000010907 stover Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018140 Al-Sn Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 229910018564 Al—Sn Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/04—Cyclic processes, e.g. alternate blast and run
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application discloses a method for producing natural gas, which at least comprises the following steps: (1) crushing agricultural and forestry waste; (2) Mixing crushed agricultural and forestry waste with water and a catalyst, and reacting in a closed pressure container with a reducing atmosphere; the catalyst is a Raney type catalyst. Wherein the carbon yield of the natural gas can reach 95 percent. The invention provides a method for producing natural gas by utilizing agricultural and forestry waste such as wood dust, straw and the like, which has the advantages of environment-friendly process, simple and convenient process, easy operation and high treatment efficiency, and obtains high-purity biomass natural gas.
Description
Technical Field
The application relates to a method for producing natural gas, which belongs to the field of natural gas production.
Background
Along with the continuous reduction of fossil resources and the increasing severity of environmental pollution, natural gas is a high-quality and efficient clean and green energy source, and can provide corresponding fuel for industrial production and resident life and is increasingly paid attention to. Biomass is the most important component of renewable resources in nature and plays an important role in modern energy structures. Aiming at the current situation of energy shortage in China, china is taken as an agricultural large country, a large amount of agricultural wastes such as straws and the like are produced each year, but the utilization rate is extremely low, and the direct burning phenomenon is often limited. The development of the technology for preparing the natural gas by taking the agricultural and forestry wastes such as the wood chips, the straws and the like as raw materials can not only relieve the problem of shortage of natural gas supply, but also effectively solve the three agricultural problems of high-efficiency utilization of the agricultural wastes.
At present, researches on natural gas preparation by biomass conversion are reported, and mainly include a fermentation method, a pyrolysis gasification method and a subcritical or supercritical water gasification method. The fermentation method needs to pretreat the biomass raw material, improves the contact area between cellulose and screening bacterial groups, and the methane content in the generated biogas is about 50-75%. The method has the advantages of wide sources of raw materials, mild reaction conditions, longer reaction period, low efficiency and CO in the fermentation process 2 The discharge amount of the gas is large (25-50%). The pyrolysis gasification method is to directly gasify biomass at a high temperature of 600-1000 ℃ to obtain CO and CO 2 、H 2 And CH (CH) 4 Mixed gas of CH 4 Below 10% and also produces significant amounts of tar and coke during the process. The subcritical or supercritical water gasification method is another method for preparing natural gas by biomass conversion, and is used for preparing CH by directly catalyzing primary biomass conversion at 300-600 DEG C 4 But CO in the gas product obtained 2 Content of (C) and CH 4 Is equivalent or higher in content. In summary, the gas mixture obtained by the currently reported natural gas preparation method cannot meet the transportation requirement of the urban natural gas pipeline, and the solid residues remained after the reaction need to be separated, so that the corresponding energy consumption and the production cost are further increased.
Aiming at the prior process of preparing natural gas by catalytic conversion of biomass with high reaction temperature or CH in gas products 4 Low content, etc., there is a need to develop a highly efficient reaction system to reduce the reaction temperature of natural gas produced by biomass conversion and to increase CH in the gaseous products 4 The content of the natural gas pipeline can meet the conveying requirement of the urban natural gas pipeline, and has important significance.
Disclosure of Invention
Based on the background, the application provides a method for preparing natural gas under mild conditions by using wood dust, straw and other agricultural and forestry wastes.
In order to achieve the above object, the method comprises at least the following steps:
(1) Crushing agricultural and forestry waste;
(2) Mixing the crushed agricultural and forestry waste with water and a catalyst, and reacting in a closed pressure container with a reducing atmosphere.
Specifically, in the step (2), crushed agricultural and forestry waste is directly added into a reaction kettle, then reaction solvent water and a catalyst are sequentially added, and reducing gas is filled into the reaction device; after the reaction is finished, separating out the reducing gas which does not participate in the reaction, recycling, wherein the residual gas is natural gas and can directly enter a natural gas pipeline for conveying.
Optionally, the catalyst is a Raney catalyst.
Optionally, the method further comprises the steps of separation and reuse of the catalyst, separation and reuse of the reducing gas.
Optionally, the separation and reuse of the catalyst is to directly attract the reacted catalyst by using a magnet, and further recycle the catalyst.
Optionally, the Raney catalyst is one of Raney Ni, raney Ni-Al, raney Ni-Mo, raney Ni-Sn, raney Ni-Fe or Raney Ni-Cu. Optionally, in the step (1), the crushing is to process the agricultural and forestry waste into particles with the particle diameter smaller than 1 cm. Preferably, the size of the particles is 4-200 mesh. Optionally, in the step (1), the agricultural and forestry waste is wood chips and/or straw.
Optionally, the wood chips are selected from at least one of beech, pine, birch or poplar.
Optionally, the straw is selected from at least one of corn straw, wheat straw or rice straw.
Optionally, in the step (2), the volume of the water is 10-65% of the total volume of the pressure vessel.
Preferably, the volume of the water is 20-50% of the total volume of the pressure vessel.
Further preferably, the volume of water is 30-45% of the total volume of the pressure vessel.
Optionally, the addition amount of the crushed agricultural and forestry waste is 1-25% of the mass of the water.
Preferably, the addition amount of the crushed agricultural and forestry waste is 1-15% of the mass of the water.
Further preferably, the addition amount of the crushed agricultural and forestry waste is 2-10% of the mass of the water.
Optionally, the addition amount of the catalyst is 5-60% of the mass of the crushed agricultural and forestry waste.
Preferably, the addition amount of the catalyst is 20-60% of the mass of the crushed agricultural and forestry waste.
Optionally, in the step (2), the reducing atmosphere is a hydrogen atmosphere.
Optionally, the pressure of the hydrogen is 0.1-8 MPa.
Preferably, the pressure of the hydrogen is 1-6 MPa.
Further preferably, the pressure of the hydrogen is 3-6 MPa.
Optionally, in the step (2), the reaction temperature is 150-350 DEG C o C。
Preferably, the temperature of the reaction is 200~350 o C。
Further preferably, the reaction temperature is 250 to 350 o C。
Optionally, in the step (2), the reaction time is 1-24 h.
Preferably, the reaction time is 2-15 h.
Further preferably, the reaction time is 2-10 hours.
In this application, the size of the particles is expressed in terms of the maximum length of the particles, the number of openings per inch of screen being the number of openings in the screen, and is also used to express the size of the particles that can pass through the screen.
The method is adopted to directly catalyze and convert wood dust, straw and other agricultural and forestry wastes under mild conditions to prepare natural gas, wherein the carbon yield of the natural gas can reach 95%, and the prepared natural gas meets the conveying requirement of a natural gas urban pipeline, can directly enter the natural gas pipeline for conveying, and provides high-quality, high-efficiency, clean and green energy for industrial production and resident life.
The invention provides a method for producing natural gas by utilizing agricultural and forestry waste such as wood dust, straw and the like, which has the advantages of environment-friendly process, simple and convenient process, easy operation and high treatment efficiency, and obtains high-purity biomass natural gas. The invention designs and develops a high-efficiency catalytic reaction system, which can destroy the toughness structure of biomass at a lower temperature and directly prepare natural gas by catalyzing biomass conversion. The technology realizes the reform technology of preparing natural gas by the primary biomass under mild conditions so as to meet the conveying requirement of urban natural gas pipelines.
The beneficial effects that this application can produce include:
1) The invention realizes the preparation of natural gas by directly converting agricultural and forestry wastes such as wood chips, straws and the like under the condition of lower reaction temperature and pressure, and has mild reaction conditions, thus having lower requirements on reaction equipment and larger industrialization potential.
2) The catalyst used in the invention can be directly separated and further recycled, thus reducing the cost of the process.
3) The method has the advantages of simple operation steps, easy operation, low energy consumption and environment-friendly process.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Raney type catalyst in the examples of the present application: wherein Raney Ni and Raney Ni-Mo are directly purchased from chemical industry Co Ltd for large communication, the model of Raney Ni is RTH-2110, the content of Ni and Al elements is 95.7 percent and 4.3 percent respectively, the model of Raney Ni-Mo is RTH-3110, and the content of Ni, al and Mo elements is 93.6 percent, 2.1 percent and 4.3 percent respectively. In addition, raney Ni-Al, raney Ni-Sn, raney Ni-Fe and Raney Ni-Cu are Ni-Al, ni-Al-Sn, ni-Al-Fe and Ni-Al-Cu alloy powders purchased from chemical industry Co Ltd for large communication, and then dealumination activation treatment is carried out in NaOH solution to obtain corresponding Raney-type catalysts for catalytic reaction.
The carbon yields in the examples of the present application were calculated as follows:
。
example 1
Pulverizing beech, then weighing 0.5g of pulverized beech wood dust with the particle size of 4-200 meshes, adding the pulverized beech wood dust into a 50mL reaction kettle, sequentially adding 15mL of water as a reaction solvent and 0.3g of Raney Ni as a catalyst, and stirring by magnetic force to fully mix the materials. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 3.0 MPa, and closing the gas inlet and outlet. Heating to 340 by adopting an electric heating mode under 1000rpm magnetic stirring o C and held at this temperature for 600min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The qualitative and quantitative analysis of the gas products shows that the catalytic beech wood chips can be directly converted to prepare natural gas, wherein the content of methane is 93%. And the carbon yield of the natural gas product was 95%.
Example 2
Pulverizing beech, then weighing 1.0g of pulverized beech wood dust with the particle size of 4-200 meshes, adding the pulverized beech wood dust into a 50mL reaction kettle, sequentially adding 20mL of water as a reaction solvent and 0.4g of Raney Ni-Al as a catalyst, and stirring by magnetic force to fully mix the materials. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 4.0 MPa, and closing the gas inlet and outlet. Heating to 300 deg.C by electric heating under 1000rpm magnetic stirring o C and held at this temperature for 300min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The natural gas can be prepared by directly converting catalytic beech wood chips through qualitative and quantitative analysis of gas products, wherein the content of methane is 92%. And the carbon yield of the natural gas product was 95%.
Example 3
Pulverizing beech, then weighing 1.5g of pulverized beech wood dust with the particle size of 4-200 meshes, adding the pulverized beech wood dust into a 50mL reaction kettle, sequentially adding 15mL of water as a reaction solvent and 0.5g of Raney Ni-Mo as a catalyst, and stirring by magnetic force to fully mix the materials. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 5.0 MPa, and closing the gas inlet and outlet. Heating to 310 by electric heating under 1000rpm magnetic stirring o C and held at this temperature for 400min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The natural gas can be prepared by directly converting catalytic beech wood chips through qualitative and quantitative analysis of gas products, wherein the content of methane is 90%. And the carbon yield of the natural gas product was 93%.
Example 4
Pulverizing beech, weighing 0.8g, pulverizingAdding beech wood chips with the particle size of 4-200 meshes into a 50mL reaction kettle, sequentially adding 20mL of water as a reaction solvent and 0.4g of Raney Ni-Sn as a catalyst, and carrying out magnetic stirring to fully mix the materials. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 4.0 MPa, and closing the gas inlet and outlet. Heating to 330 by electric heating under 1000rpm magnetic stirring o C and held at this temperature for 420min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The natural gas can be prepared by directly converting catalytic beech wood chips through qualitative and quantitative analysis of gas products, wherein the content of methane is 80%. And the carbon yield of the natural gas product was 78%.
Example 5
Pulverizing beech, then weighing 0.6g of pulverized beech wood dust with the particle size of 4-200 meshes, adding the pulverized beech wood dust into a 50mL reaction kettle, sequentially adding 15mL of water as a reaction solvent and 0.3g of Raney Ni-Fe as a catalyst, and stirring by magnetic force to fully mix the materials. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 3.5 MPa, and closing the gas inlet and outlet. Heating to 340 by adopting an electric heating mode under 1000rpm magnetic stirring o C and held at this temperature for 500min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The natural gas can be prepared by directly converting catalytic beech wood chips through qualitative and quantitative analysis of gas products, wherein the content of methane is 86%. And the carbon yield of the natural gas product was 85%.
Example 6
Pulverizing beech, then weighing 1.2g pulverized beech wood dust with particle size of 4-200 meshes, adding into a 50mL reaction kettle, sequentially adding 20mL water as reaction solvent and 0.5g Raney Ni-Cu as catalyst, and magnetically stirringSo that they are thoroughly mixed. And (3) sealing the reaction kettle, replacing the gas in the reaction kettle with hydrogen for 5 times, then filling the hydrogen in the reaction kettle to 5.0 MPa, and closing the gas inlet and outlet. Heating to 320 deg.f by electric heating under 1000rpm magnetic stirring o C and held at this temperature for 600min. After the reaction, stirring was stopped, the reaction vessel was cooled to room temperature with ice water, and the gas product after the reaction was collected with an air bag and analyzed. The magnet is used for directly attracting and separating the reacted catalyst, and the catalyst is further recycled.
The natural gas can be prepared by directly converting catalytic beech wood chips through qualitative and quantitative analysis of gas products, wherein the content of methane is 85%. And the carbon yield of the natural gas product was 88%.
Example 7
The preparation procedure described in example 1 was repeated, except that the beech wood chips were changed to pine, the gas product obtained was natural gas, the methane content was 87%, and the carbon yield of the natural gas product was 91%.
Example 8
The preparation described in example 2 was repeated except that the beech wood chips were changed to pine, the gas product obtained was natural gas, in which the methane content was 86%, and the carbon yield of the natural gas product was 90%.
Example 9
The preparation described in example 3 was repeated, except that the beech wood chips were changed to pine, the gas product obtained was natural gas, in which the methane content was 85%, and the carbon yield of the natural gas product was 88%.
Example 10
The procedure described in example 4 was repeated except that the beech wood chips were changed to pine, the gas product obtained was natural gas, in which the methane content was 75%, and the carbon yield of the natural gas product was 76%.
Example 11
The preparation described in example 5 was repeated, except that the beech wood chips were changed to pine, the gas product obtained was natural gas, the methane content was 82%, and the carbon yield of the natural gas product was 84%.
Example 12
The procedure described in example 6 was repeated except that the beech wood chips were changed to pine, the gas product obtained was natural gas, the methane content was 83%, and the carbon yield of the natural gas product was 87%.
Example 13
The preparation procedure described in example 1 was repeated, except that the beech wood chips were changed to birch, the gas product obtained was natural gas, the methane content was 93%, and the carbon yield of the natural gas product was 93%.
Example 14
The preparation procedure described in example 2 was repeated, except that the beech wood chips were changed to birch, the gas product obtained was natural gas, the methane content was 93%, and the carbon yield of the natural gas product was 94%.
Example 15
The preparation procedure described in example 3 was repeated, except that the beech wood chips were changed to birch, the gas product obtained was natural gas, the methane content was 90%, and the carbon yield of the natural gas product was 92%.
Example 16
The preparation described in example 4 was repeated, except that the beech wood chips were changed to birch, the gas product obtained was natural gas, the methane content was 78%, and the carbon yield of the natural gas product was 76%.
Example 17
The preparation described in example 5 was repeated except that the beech wood chips were changed to pine, the gas product obtained was natural gas, in which the methane content was 85%, and the carbon yield of the natural gas product was 84%.
Example 18
The preparation procedure described in example 6 was repeated, except that the beech wood chips were changed to birch, the gas product obtained was natural gas, in which the methane content was 85%, and the carbon yield of the natural gas product was 87%.
Example 19
The preparation described in example 1 was repeated except that beech wood chips were changed to poplar, the gas product obtained was natural gas, in which the methane content was 92%, and the carbon yield of the natural gas product was 94%.
Example 20
The preparation procedure described in example 2 was repeated, except that beech wood chips were changed to poplar, the gas product obtained was natural gas, the methane content was 93%, and the carbon yield of the natural gas product was 95%.
Example 21
The preparation described in example 3 was repeated, except that beech wood chips were changed to poplar, the gas product obtained was natural gas, in which the methane content was 92%, and the carbon yield of the natural gas product was 94%.
Example 22
The preparation described in example 4 was repeated, except that beech wood chips were changed to poplar, the gas product obtained was natural gas, in which the methane content was 81%, and the carbon yield of the natural gas product was 80%.
Example 23
The preparation described in example 5 was repeated except that beech wood chips were changed to poplar, the gas product obtained was natural gas, in which the methane content was 88%, and the carbon yield of the natural gas product was 85%.
Example 24
The preparation described in example 6 was repeated except that beech wood chips were changed to poplar, the gas product obtained was natural gas, in which the methane content was 87%, and the carbon yield of the natural gas product was 90%.
Example 25
The preparation process described in example 1 was repeated except that beech wood chips were changed to corn stover, the gas product obtained was natural gas with a methane content of 84% and a carbon yield of 86% for the natural gas product.
Example 26
The preparation procedure described in example 2 was repeated, except that beech wood chips were changed to corn stover, the gas product obtained was natural gas, the methane content was 83%, and the carbon yield of the natural gas product was 85%.
Example 27
The preparation procedure described in example 3 was repeated, except that the beech wood chips were changed to corn stover, the gas product obtained was natural gas, the methane content was 81%, and the carbon yield of the natural gas product was 83%.
Example 28
The preparation described in example 4 was repeated except that beech wood chips were changed to corn stover, the gas product obtained was natural gas, wherein the methane content was 78% and the carbon yield of the natural gas product was 76%.
Example 29
The preparation process described in example 5 was repeated, except that beech wood chips were changed to corn stover, the gas product obtained was natural gas, wherein the methane content was 81%, and the carbon yield of the natural gas product was 80%.
Example 30
The preparation process described in example 6 was repeated, except that beech wood chips were changed to corn stover, the gas product obtained was natural gas, the methane content was 83%, and the carbon yield of the natural gas product was 81%.
Example 31
The preparation procedure described in example 1 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, in which the methane content was 79%, and the carbon yield of the natural gas product was 82%.
Example 32
The preparation process described in example 2 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, in which the methane content was 78%, and the carbon yield of the natural gas product was 80%.
Example 33
The preparation described in example 3 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, in which the methane content was 76%, and the carbon yield of the natural gas product was 78%.
Example 34
The preparation process described in example 4 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, the methane content was 73%, and the carbon yield of the natural gas product was 70%.
Example 35
The preparation process described in example 5 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, in which the methane content was 74%, and the carbon yield of the natural gas product was 76%.
Example 36
The preparation process described in example 6 was repeated, except that beech wood chips were changed to wheat straw, the gas product obtained was natural gas, in which the methane content was 76%, and the carbon yield of the natural gas product was 77%.
Example 37
The preparation procedure described in example 1 was repeated, except that beech wood chips were changed to straw, the gas product obtained was natural gas, the methane content was 78%, and the carbon yield of the natural gas product was 81%.
Example 38
The preparation procedure described in example 2 was repeated, except that beech wood chips were changed to straw, the gas product obtained was natural gas, the methane content was 77%, and the carbon yield of the natural gas product was 79%.
Example 39
The preparation described in example 3 was repeated except that beech wood chips were changed to straw, the gas product obtained was natural gas, in which the methane content was 75%, and the carbon yield of the natural gas product was 75%.
Example 40
The preparation described in example 4 was repeated except that beech wood chips were changed to straw, the gas product obtained was natural gas, the methane content was 73%, and the carbon yield of the natural gas product was 69%.
Example 41
The preparation described in example 5 was repeated except that beech wood chips were changed to straw, the gas product obtained was natural gas, in which the methane content was 74%, and the carbon yield of the natural gas product was 75%.
Example 42
The preparation described in example 6 was repeated except that beech wood chips were changed to straw, the gas product obtained was natural gas, in which the methane content was 76%, and the carbon yield of the natural gas product was 78%.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (7)
1. A method of producing natural gas, the method comprising at least the steps of:
(1) Crushing agricultural and forestry waste;
(2) Mixing crushed agricultural and forestry waste with water and a catalyst, and reacting in a closed pressure container with a reducing atmosphere;
the catalyst is a Raney type catalyst;
catalytic biomass conversion directly prepares natural gas;
the method also comprises the steps of separating and reutilizing the catalyst and separating and reutilizing the reducing gas;
the Raney catalyst is one of Raney Ni, raney Ni-Al, raney Ni-Mo, raney Ni-Sn, raney Ni-Fe or Raney Ni-Cu;
the addition amount of the catalyst is 20-60% of the mass of the crushed agricultural and forestry waste;
the reducing atmosphere is hydrogen atmosphere;
the pressure of the hydrogen is 3-6 MPa;
the reaction temperature is 250-350 DEG C o C；
The reaction time is 2-10 h.
2. The method according to claim 1, wherein in the step (1), the pulverization is performed by treating the agricultural and forestry waste to have a particle size of 4 to 200 mesh.
3. The method according to claim 1, wherein in step (1), the agricultural and forestry waste is wood chips and/or straw;
the wood chips are at least one selected from beech, pine, birch and poplar;
the straw is at least one selected from corn straw, wheat straw or rice straw.
4. The method of claim 1, wherein in step (2), the volume of water is 20-50% of the total volume of the pressure vessel.
5. The method of claim 4, wherein in step (2), the volume of water is 30-45% of the total volume of the pressure vessel.
6. The method according to claim 1, wherein in the step (2), the crushed agricultural and forestry waste is added in an amount of 1 to 15% by mass of the water.
7. The method according to claim 6, wherein in the step (2), the crushed agricultural and forestry waste is added in an amount of 2 to 10% by mass of the water.
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| CN101278033A (en) * | 2005-10-04 | 2008-10-01 | 保罗·谢勒学院 | Process for generating methane and/or methane hydrate from biomass |
| WO2013011207A1 (en) * | 2011-07-19 | 2013-01-24 | IFP Energies Nouvelles | Flexible method of transforming lignocellulosic biomass into hydrocarbons in the presence of an acid |
| CN102942971A (en) * | 2012-09-19 | 2013-02-27 | 太原理工大学 | Application of raney nickel as slurry reactor to synthesize methane catalyst |
| CN106753549A (en) * | 2016-12-20 | 2017-05-31 | 中国科学院广州能源研究所 | A kind of method that lignin depolymerization lightweight phenolic product hydrotreating prepares HC fuel |
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|---|---|---|---|---|
| CN101278033A (en) * | 2005-10-04 | 2008-10-01 | 保罗·谢勒学院 | Process for generating methane and/or methane hydrate from biomass |
| WO2013011207A1 (en) * | 2011-07-19 | 2013-01-24 | IFP Energies Nouvelles | Flexible method of transforming lignocellulosic biomass into hydrocarbons in the presence of an acid |
| CN102942971A (en) * | 2012-09-19 | 2013-02-27 | 太原理工大学 | Application of raney nickel as slurry reactor to synthesize methane catalyst |
| CN106753549A (en) * | 2016-12-20 | 2017-05-31 | 中国科学院广州能源研究所 | A kind of method that lignin depolymerization lightweight phenolic product hydrotreating prepares HC fuel |
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