CN110773129B - Binary-substituted benzene modified molecular sieve and preparation method and application thereof - Google Patents

Binary-substituted benzene modified molecular sieve and preparation method and application thereof Download PDF

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CN110773129B
CN110773129B CN201911088560.6A CN201911088560A CN110773129B CN 110773129 B CN110773129 B CN 110773129B CN 201911088560 A CN201911088560 A CN 201911088560A CN 110773129 B CN110773129 B CN 110773129B
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沈俊
罗仕忠
王荣
敬方梨
刘伟
黎志敏
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Sichuan University
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Abstract

The invention relates to a binary substituted benzene modified molecular sieve and a preparation method and application thereof, belonging to the technical field of adsorbents. The invention solves the technical problem of providing a preparation method of a binary substituted benzene modified molecular sieve. The method comprises the steps of impregnating a molecular sieve with a binary substituted benzene solution, carrying out solid-liquid separation, and drying the solid to obtain the binary substituted benzene modified molecular sieve. The binary substituted benzene modified molecular sieve is successfully prepared by carrying out impregnation modification on the molecular sieve, the preparation method is simple and controllable, the energy consumption is low, the cost is low, and the obtained modified molecular sieve can be used as N2/CH4、O2/CH4、(N2+O2)/CH4Isosystematic selective adsorbents, especially in the separation of N2/CH4When is CH4The adsorption capacity of the method is low, the separation ratio of nitrogen to methane is large, and the method can be applied to purifying methane in coal bed gas, oil field gas or biogas.

Description

Binary-substituted benzene modified molecular sieve and preparation method and application thereof
Technical Field
The invention relates to a binary substituted benzene modified molecular sieve and a preparation method and application thereof, belonging to the technical field of adsorbents.
Background
Methane (CH)4) Can be used as fuel, such as natural gas and coal bed gas, and is widely applied to civil use and industry; can also be used as chemical raw materials for producing acetylene, hydrogen, synthetic ammonia, carbon black, nitrochloromethane, carbon disulfide, methane chloride, dichloromethane, trichloromethane, carbon tetrachloride, hydrocyanic acid and the like; furthermore, methane is a greenhouse gas with a significant greenhouse effect, CH4Is CO2Molecular greenhouse effect is 21 times, ozone layer destruction capability is 7 times of that of carbon dioxide, and CH4The emission into the atmosphere causes, on the one hand, a serious waste of resources and, on the other hand, a greenhouse effect. Therefore, for CH in oil field gas (oil field gas), Coal Bed Methane (CBM) and Biogas (Biogas) resources4The utilization of the energy-saving and environment-friendly energy-saving agent has double meanings of energy conservation and environmental protection.
Oil field gas, coal bed gas and biogas usually contain nitrogen and oxygen with certain concentrations, so that the purity and the calorific value of methane are low and cannot reach the industrial standard, and meanwhile, the existence of oxygen increases the risk of explosion. Using this CH fraction for concentration4Less concentrated resources, need to be on N2、O2And CH4The mixed gas of (2) is separated. The technologies developed and researched at present mainly include a membrane separation technology, a low-temperature cryogenic separation technology, a pressure swing adsorption separation technology and the like. Among them, the Pressure Swing Adsorption (PSA) technology is a novel gas adsorption separation technology, has the advantages of simple equipment, flexible operation, simple and convenient maintenance, low operation energy consumption, low investment, good performance and the like, and is considered to be the most possible way to fully utilize CH4Gas separation technology of resources.
The core of PSA is the adsorbent, the performance of which determines whether or not it can achieve separation of the mixed gas and the separation effect. Theoretically, the main component of coal bed gas, natural gas, oil field gas and the like is CO2、CH4And N2Etc. CO2And CH4The physical properties of the molecules are very different and easy to separate, but N is2And CH4The critical temperature of the two is very low, the two are close in physical property and kinetic diameter, and are not easy to separate, so that CH4The core technology of gas separation lies in CH4And N2The separation is efficient.
Carbon Molecular Sieves (CMS) are a new adsorbent developed in the seventies of the 20 th century, are excellent nonpolar Carbon materials, have more pore diameters between 0.3nm and 1nm, and are mainly used for separating various mixed gases. At present, the adsorbent is the first pressure swing adsorption air separation nitrogen-rich adsorbent in engineering, but CH4And N2In the separation of (2), the separation efficiency of the conventional CMS is not high, and improvement thereof is required.
Patent CN101596445A discloses a preparation method of a carbon molecular sieve adsorbent, which takes a high molecular polymer as a raw material, and prepares the adsorbent for separating CH from low-concentration gas by pressure swing adsorption through the preparation processes of solidification, dry distillation, fine crushing, molding, carbonization and activation and carbon deposition pore regulation4Carbon molecular sieve of gas, the carbon molecular sieve being paired with CH4Has high adsorption capacity, large selective adsorption coefficient, good strength, low cost and no pollution, and the performance of the catalyst reaches or exceeds the level of a carbon molecular sieve of a Japanese sample. However, the adsorbent is mainly used for adsorbing CH4Also, desorption is required to achieve CH4The purpose of effective utilization.
Patent CN109179369A discloses a preparation method of a carbon molecular sieve for adsorbing and separating methane and nitrogen by using a phenolic resin matrix. According to the method, carbonization and deposition hole adjustment are integrated in the preparation process, energy loss is reduced, energy is saved, the influence of heat on the change of the aperture of the substrate in the carbonization cooling and deposition heating processes is reduced, the aperture is stable, the aperture of the obtained substrate is small, the deposition time is reduced, the nitrogen adsorption capacity is 6.5-7.5 ml/g, and the methane adsorption capacity is 7-10 ml/g of a deposited sample under the atmospheric pressure of 25 degrees/1. Although the molecular sieve prepared by the method can be used for kinetic separation of nitrogen and methane, the separation ratio is not high, and nitrogen and methane cannot be effectively separated.
Patent CN101935032A discloses a method for preparing carbon molecular sieve by using chemical activator KOH or physical activator CO2The method comprises the steps of carrying out secondary activation reaming on a conventional carbon molecular sieve for an activating agent, carrying out pressure swing adsorption operation by using the carbon molecular sieve subjected to secondary activation as an adsorbent, showing the preferential selectivity of nitrogen adsorption, and carrying out pressure swing adsorption separation of methane-nitrogen by using the adsorbent to realize the purpose of directly purifying methane. Although this method can separate and absorb nitrogen gas, the absorption of methane is also increased, and the methane yield is not high. In addition, CO is used2The activation reaming has the defects of high-temperature energy consumption, complex process and the like.
In summary, most of the existing methods for improving carbon molecular sieves are to increase N by deposition pore blocking or activation pore-expanding process2The adsorption quantity is increased while the CH is inevitably increased4So that the separation of nitrogen and methane is relatively low; in addition, when the adsorbent preferentially adsorbs methane, the methane can be enriched and utilized only by carrying out secondary desorption and recompression on the methane, and the separation energy consumption is higher.
Disclosure of Invention
In view of the above disadvantages, the present invention aims to effectively separate nitrogen from methane by modifying a molecular sieve to reduce the adsorption amount of the molecular sieve to methane.
The invention solves the first technical problem by providing a preparation method of a binary substituted benzene modified molecular sieve.
The preparation method of the binary substituted benzene modified molecular sieve comprises the following steps: soaking the molecular sieve by adopting a binary substituted benzene solution, performing solid-liquid separation, and drying the solid to obtain the binary substituted benzene modified molecular sieve, wherein the structural formula of the binary substituted benzene is shown in the specification
Figure BDA0002266179010000021
R1Is C1-C4 alkyl, halogen or nitro, R2is-SO3H. -COOH, -OH or-CH2OH。
Preferably, the binary fetchingR of substituted benzene1Is methyl or nitro; r2is-SO3H or-COOH.
Preferably, the molecular sieve is a carbon molecular sieve, an A-type molecular sieve, an X-type molecular sieve, a Y-type molecular sieve, a ZSM molecular sieve, an SAPO molecular sieve, a silicon-titanium molecular sieve or activated carbon; preferably, the molecular sieve is a carbon molecular sieve.
Preferably, the molecular sieve is a carbon molecular sieve.
Preferably, the dibasic substituted benzene is p-toluenesulfonic acid (TSA).
For sufficient impregnation, preferably, the impregnation is an equal volume impregnation or an excess impregnation.
Preferably, the concentration of the binary substituted benzene solution is 0.001-20 wt%. More preferably, the concentration of the binary substituted benzene solution is 0.01-10 wt%; more preferably, the concentration of the binary substituted benzene solution is 0.01-1 wt%.
Specifically, the present invention preferably employs the following operations: uniformly mixing and soaking the molecular sieve and the binary substituted benzene solution, filtering and separating, and drying the filtered molecular sieve at 60-200 ℃ to obtain the binary substituted benzene modified molecular sieve.
The invention solves the second technical problem by providing a binary substituted benzene modified molecular sieve.
The binary substituted benzene modified molecular sieve is prepared by the preparation method of the binary substituted benzene modified molecular sieve. The modified molecular sieve is used for separating N2/CH4Compared with unmodified methane, the methane adsorption capacity is sharply reduced, so that the methane can be effectively separated and purified, the separation ratio is high, and the yield of the methane is high.
The invention also provides the binary substituted benzene modified molecular sieve as N2/CH4、O2/CH4Or (N)2+O2)/CH4Use of a selective adsorbent for a system.
The molecular sieve of the invention can be used as a selective adsorbent by adjusting the aperture through process parameters. For separating N2/CH4Can selectively adsorb N2(ii) a And for separating O2/CH4When adsorbing O selectively2(ii) a For separation (N)2+O2)/CH4While selectively adsorbing N2And O2Thereby achieving the purpose of separating the mixed gas.
The invention also provides application of the binary substituted benzene modified molecular sieve in purifying methane in coal bed gas, oil field gas or biogas. Because the modified molecular sieve hardly adsorbs methane, the modified molecular sieve can be used as an adsorbent for purifying methane from coal bed gas, oil field gas or biogas, thereby achieving the purposes of energy conservation and environmental protection.
Compared with the prior art, the invention has the following beneficial effects:
the binary substituted benzene modified molecular sieve is successfully prepared by carrying out impregnation modification on the molecular sieve, the preparation method is simple and controllable, the energy consumption is low, the cost is low, and the obtained binary substituted benzene modified molecular sieve can be used as N2/CH4、O2/CH4Or (N)2+O2)/CH4In particular in the separation of N2/CH4When is CH4The adsorption capacity of the method is extremely low, the separation ratio of nitrogen to methane is large, and the method can also be applied to methane purification in coal bed gas, oil field gas or biogas.
Drawings
FIG. 1 shows BET characterization patterns of carbon molecular sieves used as raw materials in examples 1 to 5 of the present invention and samples in example 1.
FIG. 2 is a schematic view of a static adsorption experimental apparatus in test example 1 of the present invention; in the figure: 1-a PLC module; 2-a pressure sensor; 3-a reference cell; 4-an adsorption tank; 5-constant temperature water bath; 6-a vacuum pump; 7-CH4A gas cylinder; 8-N2A gas cylinder; 9-He gas cylinder.
FIG. 3 is a graph showing adsorption isotherms of the raw material carbon molecular sieves used in examples 1 to 5 of the present invention.
FIG. 4 is the adsorption isotherm of the modified carbon molecular sieve obtained in example 1 of the present invention.
FIG. 5 is the adsorption isotherm of the modified carbon molecular sieve obtained in example 2 of the present invention.
FIG. 6 is the adsorption isotherm of the modified carbon molecular sieve obtained in example 3 of the present invention.
FIG. 7 is the adsorption isotherm of the modified carbon molecular sieve obtained in example 4 of the present invention.
FIG. 8 is the adsorption isotherm of the modified carbon molecular sieve obtained in example 5 of the present invention.
Detailed Description
The preparation method of the binary substituted benzene modified molecular sieve comprises the following steps: soaking the molecular sieve by adopting a binary substituted benzene solution, performing solid-liquid separation, and drying the solid to obtain the binary substituted benzene modified molecular sieve, wherein the structural formula of the binary substituted benzene is shown in the specification
Figure BDA0002266179010000041
R1Is C1-C4 alkyl, halogen or nitro, R2is-SO3H. -COOH, -OH or-CH2OH。
The research finds that R in the binary substituted benzene2The radicals can react with hydroxyl groups in the molecular sieve to adjust the pore diameter of the molecular sieve, so as to achieve the effect of partially adjusting the pores, and generate the effect of shape selection when the molecular sieve separates gas, particularly the effect of separating N2/CH4When is CH4Has a molecular dynamic diameter of 0.38nm, N2Has a molecular dynamics diameter of 0.364nm, and can selectively adsorb N2To CH4The adsorption capacity is low, and the purpose of separating the mixed gas is achieved. And R is1The group has electron-withdrawing effect and can promote better N adsorption2。
R in the invention1And R2All are substituent groups on a benzene ring, and no special requirement is imposed on the substituted position, namely R1And R2The positional relationship of (A) may be para, meta or ortho.
Preferably, R of said disubstituted benzene1Is methyl or nitro; r2is-SO3H or-COOH.
Molecular sieves commonly used in the art are suitable for use in the present invention, and preferably, the molecular sieve is Carbon Molecular Sieve (CMS), a type a molecular sieve (e.g., 4A molecular sieve, 5A molecular sieve), an X type molecular sieve, a Y type molecular sieve, a ZSM molecular sieve (e.g., ZSM-5 molecular sieve), a SAPO molecular sieve (e.g., SAPO-34 molecular sieve, SAPO-11 molecular sieve), a silicon titanium molecular sieve, activated carbon, or the like.
Preferably, the molecular sieve is a carbon molecular sieve. Research shows that the pore size distribution of the carbon molecular sieve mainly has two intervals: 0.3-0.4nm and 0.42-0.7nm, the pores of 0.3-0.4nm can be reduced after the pore is adjusted by the method, the pore distribution of 0.42-0.7nm is changed, the pore diameter tends to shrink, thereby further separating N2/CH4。
Preferably, the dibasic substituted benzene is p-toluenesulfonic acid (TSA).
For sufficient impregnation, preferably, the impregnation is an equal volume impregnation or an excess impregnation.
The solvent of the binary substituted benzene solution can be water, and can also be various organic solvents such as ethanol, acetone, benzene, toluene, chlorobenzene, cyclohexane, ethyl acetate, glycerol, propylene oxide, dimethyl sulfoxide and the like, and only needs to be capable of dissolving the binary substituted benzene. In order to save cost, the binary substituted benzene solution is preferably a binary substituted benzene aqueous solution.
Preferably, the concentration of the binary substituted benzene solution is 0.001-20 wt%. More preferably, the concentration of the binary substituted benzene solution is 0.01-10 wt%; more preferably, the concentration of the binary substituted benzene solution is 0.01-1 wt%.
Specifically, the present invention preferably employs the following operations: stirring, mixing and soaking the molecular sieve and a binary substituted benzene solution, filtering and separating, and drying the filtered molecular sieve at 60-200 ℃ to obtain the binary substituted benzene modified molecular sieve.
Wherein, the binary substituted benzene solution can be prepared by the following method: at normal temperature, a certain amount of binary substituted benzene is mixed with deionized water, and then the mixture is stirred to completely dissolve the binary substituted benzene, so that a binary substituted benzene solution is obtained.
The binary substituted benzene modified molecular sieve is prepared by the preparation method of the binary substituted benzene modified molecular sieve. The modified molecular sieve is classifiedFrom N2/CH4Compared with unmodified methane, the methane adsorption capacity is sharply reduced, so that the methane can be effectively separated and purified, the separation ratio is high, and the yield of the methane is high.
The invention also provides the binary substituted benzene modified molecular sieve as N2/CH4、O2/CH4Or (N)2+O2)/CH4And the like.
In the present invention, "/" is "and", for example, N2/CH4Is a mixed gas system of nitrogen and methane, O2/CH4Is a mixed gas system of oxygen and methane, (N)2+O2)/CH4Is a mixed gas system of nitrogen, oxygen and methane.
CH4Has a molecular dynamic diameter of 0.38nm, N2Has a molecular kinetic diameter of 0.364nm, O2Has a molecular kinetic diameter of 0.346 nm. The molecular sieve of the invention can be used as a selective adsorbent by adjusting the aperture through process parameters. For separating N2/CH4Can selectively adsorb N2(ii) a And for separating O2/CH4When adsorbing O selectively2(ii) a For separation (N)2+O2)/CH4While selectively adsorbing N2And O2Thereby achieving the purpose of separating the mixed gas.
The invention also provides application of the binary substituted benzene modified molecular sieve in purifying methane in coal bed gas, oil field gas or biogas. Because the modified molecular sieve hardly adsorbs methane, the modified molecular sieve can be used as an adsorbent for purifying methane from coal bed gas, oil field gas or biogas, thereby achieving the purposes of energy conservation and environmental protection.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
The TSA modified carbon molecular sieve is prepared by the following method:
1) preparing a TSA aqueous solution with a certain concentration: mixing a certain amount of TSA with deionized water at normal temperature, and then stirring the mixture to completely dissolve the TSA in the water, wherein the solution is clear and transparent, and a TSA aqueous solution with the concentration of 0.5 wt% is obtained;
2) and fully mixing and stirring the ground carbon molecular sieve (40-60 meshes) and the TSA aqueous solution, then carrying out suction filtration separation on the modified carbon molecular sieve solid impregnated with the TSA, and drying the filtered solid at 150 ℃ overnight to obtain the final TSA modified carbon molecular sieve sample.
The BET method is adopted to determine the specific surface area of the raw material carbon molecular sieve and the modified carbon molecular sieve sample, and the map of the specific surface area is shown in figure 1.
As can be seen from FIG. 1, the pore size distribution of the carbon molecular sieve was significantly changed by the TSA modification of the present invention.
Examples 2 to 5
By adopting the method of example 1, only changing the concentration of the TSA aqueous solution to obtain a series of TSA aqueous solution modified carbon molecular sieves with different loading amounts, and the specific changed parameters are shown in Table 1.
TABLE 1
Example numbering Concentration of aqueous TSA solution (%)
Example 1 0.5
Example 2 0.01
Example 3 0.05
Example 4 0.1
Example 5 1
Test example 1
And (3) measuring the adsorption capacity of the raw material carbon molecular sieve and the modified samples obtained in the embodiments 1-5 on nitrogen and methane by using a static adsorption method. The specific measurement method is as follows:
as shown in fig. 2, the static adsorption apparatus is composed of a PLC module 1, a pressure sensor 2, a reference tank 3, an adsorption tank 4, a constant temperature water bath 5, a vacuum pump 6, an electromagnetic valve, a needle stop valve, a thermocouple, an electromagnetic relay, and the like. Utilize constant temperature water bath 5 to keep the adsorption process constancy of temperature, utilize reference cell 3 to calculate the free volume, realize gaseous adsorption process through the switching of adsorption cell 4, reference cell 3, solenoid valve, aciculiform stop valve, realize the record of pressure and the transmission of signal of telecommunication through pressure sensor 2, realize gaseous automatic adsorption process through the coordinated control of PLC module 1, electromagnetic relay, solenoid valve. And (4) obtaining the adsorption capacity of the adsorbate gas on the adsorbent by iteration of the RK state equation according to the equilibrium pressure data after the adsorption process under different initial pressures. And (5) vacuumizing by using a vacuum pump to regenerate the adsorbent.
The static adsorption device comprises the following operation steps:
weighing a certain amount of sample, placing into an adsorption tank 4, adjusting a constant temperature water bath 5 to an experimental temperature, starting an experiment after the temperature of the water bath is stable, and ensuring He gas steel cylinders 9 and N before the experiment2Gas cylinder 8, CH4The main valve of the gas steel cylinder 7 is in an open state, and the pressure reducing valve is opened to a pressure slightly higher than the highest pressure required by the experiment:
1. instrument leak detection
And opening a valve for controlling the He gas steel cylinder, observing whether the pressure changes, slowly opening the valve for controlling the adsorption tank if the pressure does not change, observing whether the pressure continuously drops, and if the pressure is stable to a certain pressure after the pressure drops, ensuring that the instrument is normal and the air tightness is good.
2. Test procedure
And opening the programmed PLC program, and automatically carrying out the instrument according to preset steps. That is, after the apparatus is evacuated, the valves are opened and closed in a matched manner, and He gas dead volume test and N are sequentially performed2Adsorption test, CH4And (5) testing gas adsorption. Respectively controlling He gas steel cylinder and N2Gas cylinder, CH4The gas steel cylinder is opened and closed, so that the gas pressure of the system is increased; the adsorption tank and the vacuum pump are controlled to be opened and closed, and the adsorption process and the desorption process are respectively realized. And the PLC module records the initial pressure and the balance pressure data after each boosting.
3. Data computation
After the experimental data are obtained through the PLC control program, the RK state equation is sequentially used for iterative calculation to obtain the free volume of the adsorption system and the ethane-ethylene gas adsorption capacity, and the calculation process is as follows:
from the RK state equation:
Figure BDA0002266179010000071
the above formula is modified to an iterative formula:
Figure BDA0002266179010000072
wherein a and b are respectively RK state equation constants as follows:
Figure BDA0002266179010000073
Figure BDA0002266179010000074
the ideal state equation is then used to provide an initial value V0：
Figure BDA0002266179010000075
Will be an initial value V0And (3) substituting the formula (2) for iteration to obtain the adsorption quantity of nitrogen and methane.
The isothermal adsorption curves of the raw material carbon molecular sieve and the modified samples obtained in examples 1 to 5 for nitrogen and methane are shown in FIGS. 3 to 8.
As is evident from FIGS. 3 to 8, the carbon molecular sieve obtained by modification by the modification method of the present invention retains the original molecular sieve N2In the same time of adsorption amount, CH4The adsorption capacity is sharply reduced, the nitrogen-methane separation ratio is high, and the method can be applied to the separation of nitrogen-methane.

Claims (8)

1. For selective adsorption of N2/CH4In the system N2The preparation method of the binary substituted benzene modified molecular sieve is characterized by comprising the following steps:
after a molecular sieve is impregnated by adopting a binary substituted benzene solution, carrying out solid-liquid separation, and drying solids to obtain a binary substituted benzene modified molecular sieve, wherein the binary substituted benzene is p-toluenesulfonic acid; the molecular sieve is a carbon molecular sieve; the concentration of the binary substituted benzene solution is 0.001-20 wt%.
2. The process of claim 1 for the selective adsorption of N2/CH4In the system N2The preparation method of the binary substituted benzene modified molecular sieve is characterized by comprising the following steps: the impregnation is equal volume impregnation or excess impregnation.
3. The process of claim 1 for the selective adsorption of N2/CH4In the system N2The preparation method of the binary substituted benzene modified molecular sieve is characterized by comprising the following steps: the concentration of the binary substituted benzene solution is 0.01-10 wt%.
4. The process of claim 3 for the selective adsorption of N2/CH4In the system N2The preparation method of the binary substituted benzene modified molecular sieve is characterized by comprising the following steps: the above-mentionedThe concentration of the binary substituted benzene solution is 0.01-1 wt%.
5. The process according to any one of claims 1 to 4 for the selective adsorption of N2/CH4In the system N2The preparation method of the binary substituted benzene modified molecular sieve is characterized by comprising the following steps: uniformly mixing and soaking the molecular sieve and the binary substituted benzene solution, filtering and separating, and drying the filtered molecular sieve at 60-200 ℃ to obtain the binary substituted benzene modified molecular sieve.
6. The binary substituted benzene modified molecular sieve is characterized in that: use of a catalyst according to any one of claims 1 to 5 for the selective adsorption of N2/CH4In the system N2The binary substituted benzene modified molecular sieve is prepared by the preparation method.
7. The dibasic substituted benzene modified molecular sieve of claim 6 as N2/CH4Selective adsorption of N to the System2The use of (1).
8. The use of the dibasic substituted benzene modified molecular sieve of claim 6 in the purification of methane from coal bed gas, oil field gas or biogas.
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