CN113877530A - Carbon molecular sieve adsorbent for selectively separating methane and nitrogen and preparation method thereof - Google Patents

Carbon molecular sieve adsorbent for selectively separating methane and nitrogen and preparation method thereof Download PDF

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CN113877530A
CN113877530A CN202111294995.3A CN202111294995A CN113877530A CN 113877530 A CN113877530 A CN 113877530A CN 202111294995 A CN202111294995 A CN 202111294995A CN 113877530 A CN113877530 A CN 113877530A
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molecular sieve
methane
carbon molecular
nitrogen
sieve adsorbent
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黄晨
陈禹嘉
袁英
贺安平
李克兵
杨云
李旭
青晨
赵安民
张可羡
张向辉
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Southwest Research and Desigin Institute of Chemical Industry
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract

The invention specifically provides a carbon molecular sieve adsorbent for selectively separating methane and nitrogen and a preparation method thereof. The adsorbent shows excellent selective adsorption performance in a methane and nitrogen gas separation system, and has good application value.

Description

Carbon molecular sieve adsorbent for selectively separating methane and nitrogen and preparation method thereof
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to a carbon molecular sieve adsorbent for selectively separating methane and nitrogen and a preparation method thereof.
Background
Methane is widely distributed in nature, is an important raw material with wide application in industrial production, and is a gas with quite remarkable greenhouse effect. The concentration of methane in mineral resources such as natural gas, coal bed gas, shale gas, oil field gas and the like is generally low, and nitrogen with relatively high content is mixed, so that the methane component can be more effectively utilized only by separating and purifying the methane component from the nitrogen. Because the explosion limit of methane gas is 5-15%, coal mine safety regulations require that low-concentration coal bed gas with the methane concentration below 30% cannot be utilized, almost all coal mining directly discharges coal gas with the methane concentration below 30% into the atmosphere, more than 70% of coal bed gas in China belongs to low-concentration coal bed gas with the methane concentration below 30%, and the quantity of coal bed gas entering the atmosphere along with coal mining is about 200 billion cubic meters every year. Meanwhile, with the continuous popularization of the nitrogen-flooding oil extraction process, the content of nitrogen in the return exhaust gas is increased, and the content of nitrogen in partial areas reaches 10% -45%, so that the quality of natural gas is greatly reduced, and the product gas is difficult to sell. Therefore, the methane purification technology has very wide application prospect and market, can enrich methane resources to make full use of the methane resources, can prevent the methane resources from being discharged into the atmosphere to aggravate greenhouse effect, and has important significance of environmental protection.
The most critical and difficult part of methane purification is the separation of methane and nitrogen, the purpose can be achieved simply and efficiently by using a Carbon Molecular Sieve (CMS) material as an adsorbent and by using a Pressure Swing Adsorption (PSA) technology, and the Carbon Molecular sieve adsorbent has the advantages of low cost, simple and convenient equipment, simple process, excellent separation effect and the like, and the Carbon Molecular sieve adsorbent and the preparation thereof are the core of the technology.
The research on the separation of methane and nitrogen relates to the fields of MOF, molecular sieve membranes and the like, wherein part of the research reaches the stage of demonstration engineering. The molecular gate nitrogen methane separation technology is a relatively popular research direction, and the principle of the technology is that the technology contains mixed oxide of tetrahedral silicon and octahedral titanium, and oxygen atoms on the orifice position of an eight-membered ring can be modified to move the mixed oxide, so that the orifice diameter can be continuously regulated below a nanometer scale, and gas molecules with different sizes can be controlled to pass through the orifice. On the basis of this, several different types of molecular sieves, such as pure silica molecular sieves, are also becoming possible adsorbent materials. In 2021, 4 months, the complete technology for creating the zeolite molecular sieve methane and nitrogen separation adsorbent and enriching the low-concentration coal bed gas is identified by the scientific and technological achievements of the union of petroleum and chemical industries in China, and the technology is completed by units such as Taiyuan university, southwest institute of chemical engineering and design, Inc., and the like. The project aims at recycling coal bed gas with 16-50% of methane content, adopts a pressure swing adsorption separation technology, takes an adsorbent as a core, and preferably selects a zeolite molecular sieve adsorbent for separating high-selectivity methane and nitrogen. The adsorbent has the advantages that the pure silicon molecular sieve has developed pore channel structure, large adsorption capacity, the optimal separation coefficient of methane and nitrogen reaches about 5.7, the pore structure is regular, and the high temperature resistance and the water resistance are excellent. However, the adsorbent has some problems: the synthesis process of the molecular sieve is complex, and particularly, the synthesis process of the molecular sieve needs a plurality of crystal seed iterations when gas mass transfer is improved and the synthesis process of the microcrystal is related, so the synthesis period is long; in addition, the nano-calcium carbonate is used as a template agent, so that the preparation cost is high, and large-scale popularization and production are not easy.
The novel membrane separation denitrification technology of northwest oil field petroleum engineering research institute has been reported in 2020, and through research and development of novel synthetic membrane and membrane separation denitrification process overall design and collaborative optimization, the nitrogen desorption rate reaches 90%, and simultaneously, this adsorbent can preferentially adsorb nitrogen in the natural gas to the adsorption nitrogen ability is higher than methane 6 times, and methane/nitrogen separation effect is showing. Although the membrane technology can realize the high-efficiency separation of methane and nitrogen, the membrane preparation technology has the problems of high difficulty, low compressive strength and difficult large-scale use, and has a larger distance from the industrial target.
The mesoporous silicon material and the metal composite organic material adsorbent are used as popular materials for adsorption and separation research, have high separation coefficients, but are limited by the preparation difficulty, the use cost, the separation and adsorption working conditions and the like of the materials. The PSA method utilizes the carbon molecular sieve to separate and purify methane/nitrogen gas is an optimal mode except MOF materials, and the PSA carbon molecular sieve adsorbent material for large-scale coal bed gas, shale gas or methane purification is a key research object of engineering application research because the structural stability problem of the MOF materials has a longer distance from industrial application. The carbon molecular sieve adsorbent applied in the current industrial production has the problems of uneven pore structure and size, so that the separation effect is general, high-purity methane gas is difficult to separate from natural gas, coal bed gas, shale gas and oil field gas, and the preparation method needs to be improved to solve the problem and improve the separation and purification effect.
Disclosure of Invention
The invention aims to provide a carbon molecular sieve adsorbent for efficiently separating methane and nitrogen and a preparation method thereof. The invention effectively solves the problems of non-uniform pore channel structure, unsatisfactory selective separation effect and the like of the carbon molecular sieve existing in the process of industrially producing the carbon molecular sieve adsorbent.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a carbon molecular sieve adsorbent for selectively separating methane and nitrogen is prepared from phenolic resin and metal nitrate through mixing with adhesive, extruding to form strips, carbonizing, and depositing.
In a preferred embodiment of the present invention, the metal nitrate is any one of nickel nitrate, iron nitrate, cobalt nitrate, chromium nitrate, zinc nitrate, and lanthanum nitrate.
As a better embodiment in the application, in the adsorbent, the mass percent of the metal nitrate is 0.1-1 wt%, and the mass percent of the binder is 1-20 wt%; the balance of phenolic resin, and the sum of the total mass percentage is 100%.
In a preferred embodiment of the present invention, the binder is any one of coal tar, pitch, and resin.
As a preferred embodiment of the present application, a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen comprises the following specific steps:
(1) molding: fully stirring the crushed phenolic resin, 0.1-1 wt% of ethanol solution of metal nitrate and 1-20 wt% of binder together until the mixture is uniformly mixed, extruding the mixture by using a strip extruder to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions.
(2) Carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 500-1000 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 30-300 min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: taking a proper amount of the carbon molecular sieve precursor and placing the precursor in a high-temperature converterN within 100mL/min2In the air flow, the temperature is increased to 500-1000 ℃ at the temperature increase rate of 10 ℃/min, and then 100mL/min N is used2And continuously introducing a proper amount of carbon source into the gas flow, stopping introducing the carbon source after 20-120 min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent for selectively separating methane and nitrogen.
In a preferred embodiment of the present invention, the temperature of the carbonization treatment is 800 ℃ and the time is 240 min.
As a preferred embodiment of the present application, the temperature of the carbon deposition treatment is 750 ℃ and the time is 60 min.
In a preferred embodiment of the present invention, the carbon source is any one of benzene, methane, ethane and cyclohexane, and more preferably benzene.
As a better implementation mode in the application, the carbon molecular sieve adsorbent prepared by the method has the advantages that the methane component is efficiently separated and purified in a methane and nitrogen system, the adsorption and separation performance is more excellent, and the N content of the sample is measured by a static adsorption device within 3min2The adsorption capacity of the catalyst reaches 3.981mL/g, and the catalyst is used for CH4The adsorption capacity of (b) was 0.638 mL/g.
The carbon molecular sieve sample on the market at present is mainly deposited on a carbonized material, the deposition is mainly concentrated on the surface of the material, the uniformity of the deposition site is not controllable, and compared with the prior industrial technology, the invention has the following beneficial effects:
the carbon molecular sieve adsorbent prepared by the method has the advantages that the methane component is efficiently separated and purified in a methane and nitrogen gas system, and the adsorption and separation performance is more excellent. The metal nitrate component is introduced in the forming stage, and is decomposed into metal oxide and nitric oxide in the process of forming the carbon molecular sieve through carbonization treatment, wherein the generation and overflow of the nitric oxide can promote the carbon molecular sieve to form a richer pore channel structure, and meanwhile, the metal oxide can be uniformly dispersed on the inner wall of the pore channel, so that the carbon source is promoted to be cracked and deposited preferentially around the carbon source in the carbon deposition process, and the size and the structure of the pore channel are more favorably and accurately regulated and controlled to be more uniform.
The carbon molecular sieve adsorbent prepared by the second step has low cost, high activity, excellent capability of selectively adsorbing nitrogen and easy regeneration and reutilization.
And (III) the process for preparing the carbon molecular sieve adsorbent for separating methane from nitrogen is a process technology capable of quickly engineering conversion based on the actual situation of the current production of carbon molecular sieve products.
Drawings
Fig. 1 is a schematic flow chart of a carbon deposition apparatus in a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen according to the present invention.
FIG. 2 is a schematic diagram of a static adsorption test process according to an embodiment of the present invention.
FIG. 3 is a schematic view of a dynamic adsorption test process according to an embodiment of the present invention.
Detailed Description
A carbon molecular sieve adsorbent for selectively separating methane and nitrogen is prepared from phenolic resin and metal nitrate through mixing with adhesive, extruding to form strips, carbonizing, and depositing.
The preparation process of the adsorbent is as follows:
(1) molding: fully stirring the crushed phenolic resin, 0.1-1 wt% of ethanol solution of metal nitrate and 1-20 wt% of coal tar binder together until the mixture is uniformly mixed, extruding and molding by using a strip extruder to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions; wherein the metal nitrate is one of nickel nitrate, ferric nitrate, cobalt nitrate, chromium nitrate, zinc nitrate and lanthanum nitrate; the binder is one of coal tar, pitch and resin;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 500-1000 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 30-300 min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: carbon depositionThe flow of the device is shown in figure 1 (taking liquid phase sediment as an example), a proper amount of the carbon molecular sieve precursor is taken and placed in a high-temperature converter, and the temperature is controlled at 100mL/min N2In the air flow, the temperature is increased to 500-1000 ℃ at the temperature increase rate of 10 ℃/min, and then 100mL/min N is used2And continuously introducing a proper amount of carbon source into the gas flow, stopping introducing the carbon source after 20-120 min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent for selectively separating methane and nitrogen.
Preferably, the carbon source is one of benzene, methane, ethane, and cyclohexane.
The static adsorption test method related in the application comprises the following steps: under the conditions of certain pressure, temperature and test time, the volumes of helium, nitrogen and methane adsorbed by carbon molecular sieve adsorbents with the mass of 1g +/-0.1 g are respectively tested, the volumes are tested for multiple times, and the average value is taken for calculation to obtain the corresponding adsorption capacities of nitrogen and methane and the separation coefficient of the nitrogen and methane mixed gas, and the flow chart of the device is shown in figure 2.
Analyzing the test result data of the static adsorption instrument: under certain pressure and temperature conditions, the volumes of helium, nitrogen and methane absorbed by the sample in 3min are respectively tested, and the adsorption capacities of nitrogen and methane and N are calculated2/CH4The separation coefficient, the above data can be calculated by the following formula:
Figure BDA0003336317080000071
wherein C isi、CjThe adsorption capacities of the gas components i and j are respectively set as mL/g and ViIs the adsorption volume of gas component i in units of mL, VHeThe volume of adsorbed He is expressed in mL, the K value is the equilibrium coefficient at the test temperature, m is the mass of the test sample, and the units g and S are the separation coefficients.
The dynamic adsorption test method related in the application comprises the following steps: the test raw material gas mixture ratio is 70% methane and 30% nitrogen by volume fraction, the test sample mass is 14g +/-0.5 g, and the adsorption experiment is carried out at room temperature; and (3) flushing the system with helium, vacuumizing, introducing helium as balance gas into the system after the vacuum degree reaches-0.1 MPa to reach the test pressure of 0.8MPa, performing an adsorption experiment, and finally obtaining the volume fraction concentration of the enriched methane by an infrared detector.
The present invention will be described in further detail with reference to specific examples to better understand the technical solutions and objects of the present invention, but the present invention is not limited thereto.
Example 1:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen comprises the following steps:
(1) molding: weighing 2.48g of nickel nitrate hexahydrate in 30mL of absolute ethyl alcohol, and stirring to dissolve the nickel nitrate hexahydrate; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 60min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent loaded with 0.5 wt% of nickel metal element; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, numbered as sample 1.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Example 2:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen comprises the following steps:
(1) molding: weighing 1.24g of nickel nitrate hexahydrate in 30mL of absolute ethanol, and stirring to dissolve the nickel nitrate hexahydrate; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 60min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent loaded with 0.25 wt% of nickel metal element; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, and numbered as sample 2.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Example 3:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen comprises the following steps:
(1) molding: weighing 3.72g of nickel nitrate hexahydrate in 30mL of absolute ethyl alcohol, and stirring to dissolve the nickel nitrate hexahydrate; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 90min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent loaded with 0.75 wt% of nickel metal element; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, numbered as sample 3.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Example 4:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane/nitrogen comprises the following steps:
(1) molding: weighing 2.28g of zinc nitrate hexahydrate in 30mL of absolute ethanol, and stirring to dissolve the zinc nitrate hexahydrate; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene vapor into the gas flow, stopping introducing the benzene vapor after 60min, and naturally cooling to room temperature to obtain a carbon molecular sieve adsorbent loaded with 0.5 wt% of zinc metal element; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, numbered sample 4.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Example 5:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen comprises the following steps:
(1) molding: weighing 1.24g of nickel nitrate hexahydrate and 1.14g of zinc nitrate hexahydrate in 30mL of absolute ethanol, and stirring to dissolve the nickel nitrate hexahydrate and the zinc nitrate hexahydrate; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 60min, and naturally cooling to room temperature to obtain a carbon molecular sieve adsorbent loaded with 0.25 wt% of nickel metal elements and 0.25 wt% of zinc metal elements; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, numbered sample 5.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Example 6:
a method for preparing a carbon molecular sieve adsorbent for selectively separating methane/nitrogen comprises the following steps:
(1) molding: weighing 3.26g of an aqueous solution (50 wt%) of manganese nitrate into 30mL of absolute ethanol, and stirring to fully mix the solution; weighing 100g of phenolic resin, crushing to obtain powder, fully stirring the powder together with the prepared solution and 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using an extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing the particles under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene vapor into the gas flow, stopping introducing the benzene vapor after 60min, and naturally cooling to room temperature to obtain a carbon molecular sieve adsorbent loaded with 0.5 wt% of manganese metal element; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for use, numbered sample 6.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Regeneration experiments:
a test for regeneration of a carbon molecular sieve adsorbent for selective separation of methane and nitrogen comprising the steps of:
placing the carbon molecular sieve adsorbent sample subjected to the adsorption test in the embodiment 1 into a closed container, performing vacuum-pumping regeneration treatment for 10min by using a vacuum pump to completely desorb the gas adsorbed in the sample, then respectively measuring the volumes of helium, nitrogen and methane adsorbed in the sample within 3min under normal pressure by using a static adsorption device, and calculating to obtain the carbon molecular sieve adsorbent sampleAdsorption capacity of nitrogen and methane and N2/CH4A separation factor; the dynamic adsorption device is adopted to measure the volume fraction of 70 percent CH of the sample under the pressure condition of 0.8MPa4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was repeated 5 times (regeneration sample 1, regeneration sample 2, regeneration sample 3, regeneration sample 4, and regeneration sample 5 were obtained, respectively), and the results are shown in table 3.
Comparative example 1:
a preparation method of a carbon molecular sieve adsorbent material modified by metal oxide comprises the following steps:
(1) molding: weighing 100g of phenolic resin, crushing to obtain powder, fully stirring with 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using a strip extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) impregnation and loading: weighing 2.48g of nickel nitrate hexahydrate in 30mL of absolute ethyl alcohol, and stirring to dissolve the nickel nitrate hexahydrate; adding the solution into a formed and carbonized carbon molecular sieve, slowly stirring for 30min, standing in a 70 ℃ oven for 4h, completely drying, transferring into a high-temperature converter, and adding 100mL/min of N2In the air flow, raising the temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 240min, then naturally cooling to room temperature, and taking out for later use;
(4) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 60min, and naturally cooling to room temperature to obtain a carbon molecular sieve adsorbent loaded with 0.5 wt% of nickel metal oxide by an impregnation method; subjecting the obtained carbon toThe molecular sieve adsorbent was packaged in a sample bag for use, numbered comparative sample 1.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Comparative example 2:
a preparation method of a carbon molecular sieve adsorbent material modified by metal oxide comprises the following steps:
(1) molding: weighing 100g of phenolic resin, crushing to obtain powder, fully stirring with 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using a strip extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) impregnation and loading: weighing 3.72g of nickel nitrate hexahydrate in 30mL of absolute ethyl alcohol, and stirring to dissolve the nickel nitrate hexahydrate; adding the solution into a formed and carbonized carbon molecular sieve, slowly stirring for 30min, standing in a 70 ℃ oven for 4h, completely drying, transferring into a high-temperature converter, and adding 100mL/min of N2In the air flow, raising the temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 240min, then naturally cooling to room temperature, and taking out for later use;
(4) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene steam into the gas flow, stopping introducing the benzene steam after 60min, and naturally cooling to room temperature to obtain a carbon molecular sieve adsorbent loaded with 0.75 wt% of nickel metal oxide by an impregnation method; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for later use, numbered comparative sample 2.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Comparative example 3:
a preparation method of a carbon molecular sieve adsorbent material which is not modified by metal elements comprises the following steps:
(1) molding: weighing 100g of phenolic resin, crushing to obtain powder, fully stirring with 10g of coal tar (10 wt%) until the powder is uniformly mixed, extruding and molding by using a strip extruding machine to obtain particles with the length of about 20mm and the diameter of about 5mm, and drying and curing under natural conditions;
(2) carbonizing: placing the granules in a high temperature converter at 100mL/min N2In the air flow, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 240min, and then naturally cooling to room temperature to obtain a carbon molecular sieve precursor;
(3) carbon deposition: 50g of the carbon molecular sieve precursor is weighed and placed in a high-temperature converter under the condition of N of 100mL/min2In the gas stream, the temperature was raised to 750 ℃ at a ramp rate of 10 ℃/min, and then 100mL/min N was used2Continuously introducing a proper amount of benzene vapor into the gas flow, stopping introducing the benzene vapor after 60min, and naturally cooling to room temperature to obtain the carbon molecular sieve adsorbent which is not modified by metal; the resulting carbon molecular sieve adsorbent was packaged in a sample bag for later use, numbered comparative sample 3.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
Comparative example 4:
a proper amount of carbon molecular sieve samples produced in batches in the current market are taken and numbered as a comparative sample 4.
Respectively measuring the volume of helium, nitrogen and methane adsorbed by the sample in 3min under normal pressure by using a static adsorption device, and calculating to obtain the adsorption capacity of nitrogen and methane and N2/CH4The results of the separation coefficient are shown in table 1.
The sample is measured to have 70 percent of CH by volume fraction under the pressure condition of 0.8MPa by adopting a dynamic adsorption device4-30％N2The adsorption condition of the mixed gas is detected by taking an infrared analyzer as a detector to detect CH at an outlet in real time4The volume fraction of (2) is changed to obtain the optimal CH within about 1min4The purification effect was as shown in Table 2.
TABLE 1 examples and comparative examples carbon molecular sieve adsorbent vs CH4And N2Result of static adsorption measurement of
Figure BDA0003336317080000191
TABLE 2 examples and comparative examples carbon molecular sieve adsorbent on 70% CH4-30％N2Results of hybrid pneumatic dynamic adsorption measurements
Figure BDA0003336317080000192
Figure BDA0003336317080000201
Table 3 example 1 repeated regeneration of carbon molecular sieve adsorbent followed by CH4And N2Static adsorption assay and for 70% CH4-30％N2Results of hybrid pneumatic dynamic adsorption measurements
Figure BDA0003336317080000202
From tables 1 and 2, it can be found that adding a proper amount of metal nitrate component to the raw materials for synthesizing the carbon molecular sieve adsorbent can effectively increase the N of the prepared carbon molecular sieve adsorbent2And CH4The separation coefficient is increased, and methane gas with higher enrichment concentration is obtained, such as samples added with nickel nitrate or/and zinc nitrate in examples 1 to 5 show more excellent selective adsorption performance, wherein the effect of adding 0.5 wt% of nickel nitrate is most remarkable, but not all metal salt components have obvious separation improvement effect, such as the sample added with manganese nitrate in example 6 does not show the adsorption performance of the samples in examples 1 to 4; the results of the separation experiments using impregnation loaded with nitrates in comparative examples 1 and 2 were found to be significantly less effective than the samples of examples 1 to 4, and the examples and comparative examples using modified deposition as above were both superior to the blank experiment of comparative example 3 in which no active component was added and superior to the adsorptive separation effect of comparative example 4 in mass production of carbon molecular sieves.
As can be seen from table 3, the samples of example 1 were subjected to vacuum treatment to completely desorb the adsorbed gas, and then the static adsorption test and the dynamic adsorption test were performed again, and the above steps were repeated 5 times, so that the obtained samples all showed very good selective adsorption performance, and still had high adsorption performance after multiple tests. Since the mass-produced carbon molecular sieve is mainly used for nitrogen production, it can be found that the adsorption capacity for nitrogen is extremely low. Compared with other samples, the results show that the carbon molecular sieve adsorbent prepared by adding the metal nitrate into the raw material through the forming, carbonizing and carbon depositing treatment has a more uniform pore channel structure, and is more favorable for selectively adsorbing the formation of a nitrogen pore channel.
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. Numerous combinations will be known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A carbon molecular sieve adsorbent for selectively separating methane and nitrogen, characterized in that:
the adsorbent uses phenolic resin and metal nitrate as main raw materials, the two raw materials are uniformly mixed and then are uniformly mixed with a binder, and after extrusion molding, carbonization and carbon deposition treatment are carried out, so that the carbon molecular sieve adsorbent for selectively separating methane and nitrogen is finally obtained.
2. A carbon molecular sieve adsorbent for selectively separating methane and nitrogen according to claim 1, wherein: the metal nitrate is any one of nickel nitrate, ferric nitrate, cobalt nitrate, chromium nitrate, zinc nitrate and lanthanum nitrate.
3. A carbon molecular sieve adsorbent for selectively separating methane and nitrogen according to claim 1 or 2, wherein: the mass percentage of the metal nitrate is 0.1-1 wt%.
4. A carbon molecular sieve adsorbent for selectively separating methane and nitrogen according to claim 1, wherein: the binder is any one of coal tar, pitch and resin.
5. A method of preparing a carbon molecular sieve adsorbent for selectively separating methane and nitrogen as claimed in claim 1 or 4, wherein: the mass percentage of the binder is 1-20 wt%.
6. The method for preparing the carbon molecular sieve adsorbent for selectively separating methane and nitrogen according to claim 1, which comprises the following steps:
1) molding: fully stirring the phenolic resin, the metal nitrate and the binder together until the mixture is uniformly mixed, and extruding the mixture by using a strip extruder for strip forming;
2) carbonizing: in N2Carbonizing treatment is carried out in airflow;
3) carbon deposition: in N2Introducing carbon source into the gas flow to perform carbon deposition treatment.
7. The method of claim 6, wherein: the carbonization treatment in the step 2) is carried out at the temperature of 500-1000 ℃ for 30-300 min.
8. The method of claim 6, wherein: the temperature of the carbon deposition treatment in the step 3) is 500-1000 ℃, and the time is 20-120 min.
9. The method of claim 6, wherein: the carbon source in the step 3) is any one of benzene, methane, ethane and cyclohexane.
10. A carbon molecular sieve adsorbent prepared by the method of any one of claims 6 to 9, wherein: is prepared byThe carbon molecular sieve adsorbent is used for efficiently separating and purifying methane components in a methane and nitrogen gas system, shows more excellent adsorption and separation performance, and is used for measuring N in 3min by adopting a static adsorption device2The adsorption capacity of the catalyst reaches 3.981mL/g, and the catalyst is used for CH4The adsorption capacity of (b) was 0.638 mL/g.
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