Background
Among the traditional fossil energy sources, natural gas is considered to be expected to be the preferred energy source for replacing coal and petroleum due to the advantages of abundant reserves, high calorific value, no pollution and the like. Compared with the conventional liquid fuel, the main disadvantage of natural gas is that the volumetric energy density is lower, which is only 0.11% of that of gasoline, so how to realize high-capacity storage of natural gas and improve the volumetric energy density of natural gas become the key to limit the wide-range application of natural gas, especially for the large-scale popularization of the rapidly developed Natural Gas Vehicles (NGV) in recent years.
At present, natural gas storage technologies mainly comprise four types: compressed Natural Gas (CNG), Liquefied Natural Gas (LNG), natural gas hydrates (NHG), and Adsorbed Natural Gas (ANG) storage technologies. Compared with other technologies, the CNG technology is mature and has been commercially applied to natural gas automobiles, the volume energy density is 9.2 MJ/L and is about 29 percent of that of gasoline, but the CNG storage pressure is as high as 20MPa, the requirement on equipment materials is very high, and the cost is also high. The LNG technology is to store natural gas in a liquid form under the pressure of 112K and 0.1MPa, the energy density can reach 22.2MJ/L which is about 72 percent of that of gasoline, but the LNG technology has high cost and complex design of a storage tank, and has safety risks of leakage and the like. NGH technology, which stores natural gas and water as clathrate hydrates, is currently immature. The ANG technology is characterized in that a porous adsorbent is filled in a storage tank, and natural gas is adsorbed and stored at normal temperature and medium and low pressure (3-4 MPa) by utilizing the huge specific surface area and rich pore channel structure of the adsorbent. Because of the low operation pressure, the high energy storage density, the relatively low cost and the more convenient and safer use of the ANG technology, the ANG technology is expected to replace CNG and LNG technologies to realize large-scale application, and the most important thing is to prepare the adsorbent with high methane adsorption capacity.
Among a plurality of adsorbent materials, the activated carbon has strong adsorption capacity due to the characteristics of large specific surface area, rich pore channel structures and the like, and can be used as an adsorbent for adsorbing and storing methane. The activated carbon used as a methane adsorbent is required to have a large specific surface area, the activated carbon with an ultrahigh specific surface area is generally prepared by a KOH chemical activation method, the prepared activated carbon contains a plurality of micropores with the pore diameter less than 0.8nm, the pore diameter of the part of micropores is too small, methane is difficult to adsorb, and the part of micropores are wasted; meanwhile, the activated carbon suitable for adsorbing and storing methane also has a certain mesopore as a gas channel, so that the development and preparation of the activated carbon with high surface area and reasonable pore structure distribution have very important significance in improving the methane adsorption quantity.
Patent CN1091073C discloses a preparation method of activated carbon for adsorbing and storing methane, and the prepared activated carbon has a surface area of 1916-2700 m2The adsorption amount of the formed activated carbon to methane at 3.5MPa was 170 v/v.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the activated carbon and the preparation method and the application thereof, and the activated carbon with reasonable pore structure distribution and high specific surface area is prepared by comprehensively regulating and controlling a process route and reaction conditions, so that high-capacity adsorption of methane is realized.
The first aspect of the invention provides activated carbon, wherein the accessibility A of the activated carbon is 1.4-2.2; wherein the accessibility A is a parameter for representing the performance of adsorbing and storing methane by the activated carbon, and the accessibility A is calculated by the following formula:
wherein
Is the micropore volume of the activated carbon measured by the t-plot method,
is total pore volume (cm) of activated carbon
3/g),
Is the cumulative total pore volume (cm) of micropores smaller than 2nm calculated by DFT method
3/g),
The cumulative pore volume (cm) of 0.8-2.0 nm pores calculated by DFT method
3(g), S is the specific surface area (m) of the activated carbon
2/g)。
The second aspect of the present invention provides a method for preparing activated carbon, which comprises the following steps:
(1) uniformly mixing petroleum coke, an activating agent and a transition metal compound, and then carrying out an activation reaction;
(2) and (2) washing and drying the activated product obtained in the step (1) to obtain the activated carbon.
In the preparation method of the activated carbon, the petroleum coke in the step (1) is solid coke generated by cracking and coking vacuum residue by a coking device.
In the preparation method of the activated carbon, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate and potassium bicarbonate, and potassium hydroxide is preferred.
In the preparation method of the activated carbon, the transition metal compound in the step (1) is one or more of transition metal salt, transition metal oxide and transition metal hydroxide, and the transition metal can be one or more of Fe, Co, Ni, Cu, Cr, Mo and Pt; the transition metal compound may be one or more of iron nitrate, iron sulfate, iron chloride, iron phosphate, iron acetate, iron sesquioxide, iron hydroxide, nickel nitrate, nickel sulfate, nickel chloride, nickel phosphate, nickel acetate, nickel oxide, nickel hydroxide, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt phosphate, cobalt acetate, cobalt oxide, cobalt hydroxide, copper nitrate, copper sulfate, copper chloride, copper phosphate, copper acetate, copper oxide, copper hydroxide, chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, chromium oxide, chromium hydroxide, molybdenum nitrate, molybdenum sulfate, molybdenum chloride, molybdenum phosphate, molybdenum acetate, molybdenum oxide, molybdenum hydroxide, platinum nitrate, platinum sulfate, platinum chloride, platinum phosphate, platinum acetate, platinum oxide, and platinum hydroxide, and more preferably one or more of iron sesquioxide, nickel nitrate, and cobalt nitrate.
In the preparation method of the activated carbon, the mass ratio of the petroleum coke, the activating agent and the transition metal compound in the step (1) is 1: 0.5-10: 0.001-0.5, and preferably 1: 1-8: 0.01-0.2.
In the above method for preparing activated carbon, the specific process of the activation reaction in step (1) is: heating the uniformly mixed petroleum coke, activating agent and transition metal compound to a temperature A in an atmosphere A, preserving heat for a certain time A, then adjusting the temperature to a temperature B, stopping introducing the atmosphere A, introducing the atmosphere B, preserving heat for a certain time B under the condition of the temperature B, and cooling to obtain an activated product.
When the atmosphere A is a mixed gas of a carbon-containing gas and a carrier gas, the atmosphere B is nitrogen and/or an inert gas; wherein, the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1: 0.1-20, preferably 1: 0.2-10. The inert gas is one or more of helium, argon and neon. The temperature A is 400-850 ℃, and preferably 500-800 ℃; the heat preservation time A is 5-200 min, preferably 20-120 min; the temperature B is 600-1100 ℃, preferably 700-950 ℃, and the heat preservation time B is 5-500 min, preferably 15-300 min.
When the atmosphere A is nitrogen and/or inert gas, the atmosphere B is a mixed gas of carbon-containing gas and carrier gas, wherein the inert gas is one or more of helium, argon and neon. The carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon. The volume ratio of the carbon-containing gas to the carrier gas is 1: 0.1-20, preferably 1: 0.2-10. The temperature A is 600-1100 ℃, preferably 700-950 ℃, and the heat preservation time A is 5-500 min, preferably 15-300 min. The temperature B is 400-850 ℃, and preferably 500-800 ℃; the heat preservation time B is 5-200 min, preferably 20-120 min.
In the preparation method of the activated carbon, the washing in the step (2) is performed by acid washing and then water washing; preferably, water washing is further performed before acid washing, wherein water washing refers to washing with water until the pH value of the filtrate is neutral. The acid washing is carried out by using inorganic acid solution, wherein the inorganic acid can be one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and hydrochloric acid is preferred. The concentration of the acid solution is 5-50 wt%, preferably 10-40 wt%. The pickling time is 5-600 min, preferably 30-400 min. The pickling temperature is 20-100 ℃, and preferably 40-80 ℃.
In the above method for preparing activated carbon, the drying process in step (2) may be normal pressure drying or vacuum drying; the drying temperature is 50-250 ℃, and preferably 60-150 ℃; the drying time is 2-16 h, preferably 5-12 h.
The third aspect of the invention provides activated carbon prepared by the method, wherein the accessibility A of the activated carbon is 1.4-2.2, and is calculated by the following formula:
(ii) a Wherein
Is the micropore volume of the activated carbon measured by the t-plot method,
is total pore volume (cm) of activated carbon
3/g),
Is the cumulative total pore volume (cm) of micropores smaller than 2nm calculated by DFT method
3/g),
The cumulative pore volume (cm) of 0.8-2.0 nm pores calculated by DFT method
3(g), S is the specific surface area (m) of the activated carbon
2/g)。
The invention also provides a method for preparing the activated carbon.
Compared with the prior art, the active carbon and the preparation method thereof have the following advantages:
1. the preparation method of the activated carbon has the advantages of reasonable pore distribution of the activated carbon, proper specific surface area, good methane storage effect, simple preparation method and the like, and not only has micropores capable of absorbing a large amount of methane, but also has mesopores capable of accelerating mass transfer.
2. The preparation method of the activated carbon for adsorbing and storing methane comprises the steps of introducing a transition metal compound in the petroleum coke activation process, forming a diffusion path formed by leading the transition metal compound into a petroleum coke bulk phase by using an activating agent, and leading the transition metal compound to enter a petroleum coke-based activated carbon pore channel along with the activating agent in a molten state to form a high-dispersion structure; meanwhile, carbon-containing gas is subjected to vapor deposition under the catalytic action of transition metal to grow a carbon nano structure on the surface of the active carbon pore channel. Thus, on the basis that the alkali-activated petroleum coke mainly forms tiny micropores, hole expansion is further realized, and a channel for adsorbing and storing methane is provided; meanwhile, the carbon nano structure has high graphitization degree, has high aromatic atoms, can contain pi electrons with high density, has stronger methane adsorption performance, and can prepare the activated carbon with reasonable hole distribution, proper specific surface area and high methane adsorption capacity.
3. In the preparation method of the activated carbon for adsorbing and storing methane, petroleum coke is used as a raw material for preparing the activated carbon, so that a novel utilization method for the petroleum coke is provided, and the resource utilization of the petroleum coke is realized.
Detailed Description
The technical content and technical effects of the present invention will be further described with reference to the following specific examples, but the present invention is not limited thereto.
In the examples and comparative examples of the present invention, the pore structure of activated carbon was characterized and tested by ASAP 2460 physical adsorption apparatus of Micromeritics, USA, and by N
2The physical adsorption method is used for measuring the specific surface area, the pore volume and the pore size distribution of the activated carbon. Analysis conditions were as follows: before testing, the samples were first treated under vacuum at 300 ℃ to>4h, the test was carried out at liquid nitrogen temperature (77.35K). An adsorption-desorption isotherm is obtained by measurement according to a static method, the specific surface area S of the activated carbon is calculated according to a BET (Brunauer-Emmett-Teller) equation,<cumulative pore volume of 2nm micropores
And cumulative pore volume of 0.8 to 2.0nm pores
Calculated by DFT method, total pore volume
The total pore volume is desorbed by single point of the pores, and the pore volume of the micropores
Calculated by the t-plot method. The adsorption capacity of the activated carbon to methane is measured by adopting an ASAP2050 high-pressure physical adsorption instrument of Micromeritics company in America, and the test conditions are as follows: 25 ℃, 3.5MPa, and the unit of adsorption capacity is mL/(g, STP), wherein STP is the standard condition, i.e. 1 standard atmosphere and 0 ℃.
Example 1
Uniformly mixing petroleum coke ground to 20-300 meshes, potassium hydroxide and nickel nitrate according to the mass ratio of 1:3:0.05, activating for 60min at 900 ℃ in nitrogen atmosphere, cooling to 600 ℃ in nitrogen atmosphere, stopping introducing nitrogen, introducing methane/nitrogen mixed gas (the volume ratio of methane to nitrogen is 2: 10), preserving the temperature for 60min at 600 ℃, cooling to room temperature, and passing the activated product through waterFiltering and washing until the pH value of the filtrate is neutral, then adding 10wt% of dilute hydrochloric acid into a filter cake, washing for 180min at 60 ℃, continuously washing the product after filtering and separating with water until the pH value of the filtrate is neutral, and drying the solid product for 5h at 120 ℃ to obtain the active carbon AC-1. The accessibility degree A of AC-1 is 2.0, and the specific surface area is 1937m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 236ml/(g, STP).
Example 2
Uniformly mixing petroleum coke, potassium hydroxide and cobalt nitrate which are ground to have the granularity of 20-300 meshes according to the mass ratio of 1:4:0.1, introducing acetylene/nitrogen mixed gas (the volume ratio of acetylene to nitrogen is 1: 5), keeping the temperature at 700 ℃ for 30min, stopping introducing the acetylene/nitrogen mixed gas, introducing nitrogen instead, continuously heating to 850 ℃, and keeping the temperature for 30 min. Cooling to room temperature, filtering and washing the activated product with water until the pH value of the filtrate is neutral, then adding 20wt% of dilute sulfuric acid into the filter cake, washing at 50 ℃ for 240min, continuously washing the product after filtering and separation with water until the pH value of the filtrate is neutral, and drying the solid product at 100 ℃ for 12h to obtain the active carbon AC-2. The accessibility A of AC-2 was 1.9, the specific surface area 1843m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 215mL/(g, STP).
Example 3
Uniformly mixing petroleum coke, potassium hydroxide and ferric oxide which are ground to have the granularity of 20-300 meshes according to the mass ratio of 1:7:0.2, activating for 60min at 950 ℃ in a nitrogen atmosphere, cooling to 800 ℃ in the nitrogen atmosphere, stopping introducing nitrogen, introducing a methane/nitrogen mixed gas (the volume ratio of methane to nitrogen is 1: 8), preserving the temperature for 30min at 800 ℃, cooling to room temperature, adding 10wt% of dilute sulfuric acid into an activated product, washing for 180min at 70 ℃, filtering and separating, continuously washing the product with water until the pH value of the filtrate is neutral, and drying the solid product for 5h at 150 ℃ to obtain the activated carbon AC-3. The accessibility degree A of AC-3 is 1.7, the specific surface area is 1521m2/g, the adsorption capacity of the adsorbent to methane at 25 ℃ under 3.5MPa is 201mL/(g, STP).
Example 4
Uniformly mixing petroleum coke ground to 20-300 meshes, potassium hydroxide and copper nitrate according to the mass ratio of 1:3:0.15, activating at 900 ℃ for 30min in nitrogen atmosphere, and cooling to the temperature ofAnd (2) stopping introducing nitrogen at 650 ℃, introducing an ethylene/nitrogen mixed gas (the volume ratio of ethylene to nitrogen is 1: 6) instead, preserving the heat at 650 ℃ for 60min, cooling to room temperature, adding 10wt% of dilute hydrochloric acid into the activated product, washing at 40 ℃ for 200min, filtering, separating, continuously washing the product with water until the pH value of the filtrate is neutral, and drying the solid product at 120 ℃ for 12h to obtain the activated carbon AC-4. The accessibility A of AC-4 is 1.8, the specific surface area is 1764m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 195mL/(g, STP).
Example 5
Uniformly mixing petroleum coke, potassium hydroxide and chromium nitrate which are ground to have the granularity of 20-300 meshes according to the mass ratio of 1:4:0.1, introducing acetylene/nitrogen mixed gas (the volume ratio of acetylene to nitrogen is 1: 5), keeping the temperature at 600 ℃ for 40min, stopping introducing the acetylene/nitrogen mixed gas, introducing nitrogen instead, continuously heating to 850 ℃, and keeping the temperature for 30 min. Cooling to room temperature, filtering and washing the activated product with water until the pH value of the filtrate is neutral, then adding 20wt% of dilute hydrochloric acid into the filter cake, washing for 250min at 60 ℃, continuously washing the product after filtering and separation with water until the pH value of the filtrate is neutral, and drying the solid product for 10h at 150 ℃ to obtain the active carbon AC-5. The accessibility degree A of AC-5 is 1.8, the specific surface area is 1895m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 203mL/(g, STP). Comparative example 1
Uniformly mixing petroleum coke ground to the particle size of 20-300 meshes and potassium hydroxide according to the mass ratio of 1:3, activating for 60min at 900 ℃ in a nitrogen atmosphere, cooling to 600 ℃ in the nitrogen atmosphere, stopping introducing nitrogen, introducing a methane/nitrogen mixed gas (the volume ratio of methane to nitrogen is 2: 10), preserving the temperature for 60min at 600 ℃, cooling to room temperature, filtering and washing an activated product with water until the pH value of the filtrate is neutral, adding 10wt% of dilute hydrochloric acid into a filter cake, washing for 180min at 60 ℃, continuously washing the filtered and separated product with water until the pH value of the filtrate is neutral, and drying a solid product for 5h at 120 ℃ to obtain the activated carbon AC-4. The accessibility A of AC-4 is 1.1, the specific surface area is 723m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 73mL/(g, STP). .
Comparative example 2
Grinding petroleum coke, potassium hydroxide and nickel nitrate to the granularity of 20-300 meshesUniformly mixing the components in a weight ratio of 1:3:0.05, activating the mixture for 60min at 900 ℃ in a nitrogen atmosphere, cooling the mixture to 600 ℃ in the nitrogen atmosphere, preserving the heat for 60min at 600 ℃, cooling the mixture to room temperature, filtering and washing an activated product with water until the pH value of the filtrate is neutral, then adding 10wt% of dilute hydrochloric acid into a filter cake, washing the filter cake for 180min at 60 ℃, continuously washing the filtered and separated product with water until the pH value of the filtrate is neutral, and drying the solid product for 5h at 120 ℃ to obtain the active carbon AC-5. The accessibility A of AC-5 is 2.3, the specific surface area is 2845m2/g, 3.5MPa, and the adsorption capacity of methane at 25 ℃ is 150mL/(g, STP).