CN110801710B - Gas trapping agent and preparation method and application thereof - Google Patents

Gas trapping agent and preparation method and application thereof Download PDF

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CN110801710B
CN110801710B CN201911088181.7A CN201911088181A CN110801710B CN 110801710 B CN110801710 B CN 110801710B CN 201911088181 A CN201911088181 A CN 201911088181A CN 110801710 B CN110801710 B CN 110801710B
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gas
trapping agent
adsorbent
solvent
gas trapping
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CN110801710A (en
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陈光进
杨明科
孙长宇
韩瑀
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/14—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 absorption
    • B01D53/1487—Removing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/046—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by adsorption, i.e. with the use of solids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel

Abstract

The invention provides a gas trapping agent and a preparation method and application thereof. The gas trapping agent comprises a main solvent, an adsorbent and a cosolvent; wherein the main solvent is 1, 3-dimethyl propylene urea; the adsorbent is a zeolite imidazole ester framework material; the cosolvent is cyclohexane and/or cyclohexane derivatives. The gas trapping agent has the advantages of low viscosity, high mass transfer speed, high desorption speed, difficult foaming and high regeneration performance of slurry, and can be used for separating gases such as refinery dry gas, natural gas, coke oven gas, flue gas, coal bed gas and the like.

Description

Gas trapping agent and preparation method and application thereof
Technical Field
The invention relates to a gas trapping agent, and belongs to the technical field of gas separation.
Background
An efficient gas purification method developed in recent years is to separate mixed gas by an absorption-adsorption coupling method. The method is to disperse porous materials with larger specific surface area and pore volume and good chemical and thermal stability in a solvent to form suspension slurry for gas separation. On one hand, the method combines the advantages of an absorption separation method and an adsorption separation method, takes the advantages of the absorption separation method and the adsorption separation method, strengthens the trapping and separating effect of the MOF material, and doubles the result with half the effort; on the other hand, the slurry method is adopted, so that the fluidity of the MOF material is increased, the dispersibility of the MOF material is improved, the power is saved, the slurry of the MOF material is uniformly mixed under the stirring action, the capturing effect is better, and the industrial continuous operation is possible.
In the previous studies, ethylene glycol, water or a mixed solution of the two is the most commonly used solvent, but the solvent system has certain disadvantages. On one hand, the system has high viscosity and low gas-liquid mass transfer rate, and is not beneficial to further improving the single-component gas trapping amount and the mixed gas separation effect; in another aspect, for C2And C2+When the absorption capacity is large, the solvent has strong interaction and is not easy to desorb components, the traditional solvent can be completely desorbed only by ensuring enough vacuumizing time under the high vacuum condition (-0.1MPa) after being saturated, the load of a vacuum pump is increased, and the maintenance cost and the energy consumption of equipment are improved. In addition, in practical industrial separation experiments, if the desorption requirement is met in a limited time, the desorption temperature needs to be increased or a gas purging unit needs to be added to fully desorb the rich liquid. The difficulty of desorption of the slurry system will directly affect the efficiency and cost of gas separation in industry.
Therefore, providing a slurry composition formula with easy desorption and low viscosity becomes one of the problems to be solved in the field.
Disclosure of Invention
In order to solve the above-mentioned problems, an object of the present invention is to provide a highly efficient gas trapping agent which is easily desorbed and has a low viscosity.
In order to achieve the above technical object, the present invention provides a gas trapping agent comprising a main solvent, an adsorbent and a co-solvent;
wherein the main solvent is 1, 3-dimethyl propylene urea
The adsorbent is zeolite imidazole ester framework material
The cosolvent is cyclohexane and/or cyclohexane derivatives.
The main solvent and the adsorbent adopted by the gas trapping agent have selective adsorption (absorption) performance on different gas components, and the separation effect of the mixed gas can be improved through double selection of the main solvent and the adsorbent.
In one embodiment of the present invention, the content of the co-solvent is 1% to 25%, the content of the adsorbent is 10% to 45%, and the balance is the main solvent, based on 100% of the total mass of the gas trapping agent.
Specifically, the content of the co-solvent may be 2 wt%, 5 wt%, 10 wt%, 15 wt%, 16 wt%, 20 wt%, 23 wt%, or the like.
Specifically, the content of the adsorbent may be 15 wt%, 20 wt%, 30 wt%, 35 wt%, 40 wt%, 43 wt%, or the like.
The gas trapping agent takes 1, 3-dimethyl propylene urea (DMPU) as a main solvent, the DMPU has low toxicity and strong stability, is not easy to hydrolyze, and does not generate acidic substances to damage the structure of the adsorbent under the water-containing condition.
The gas trapping agent takes DMPU as a main solvent, has better compatibility with an adsorbent, has high mass transfer efficiency and fast mass transfer time, and is not easy to foam and block a pipeline in the regeneration process of the trapping agent.
In one embodiment of the present invention, the slurry system is recycled four times for CO using DMPU as a solvent without the addition of a CO-solvent2The amount of adsorption of (A) is not changed, and the regeneration performance is excellent.
The cosolvent in the gas trapping agent is used as another solvent, the adopted cosolvent has low boiling point and low viscosity, and molecules cannot enter an adsorption pore channel of the imidazole ester framework material, so that the adsorption quantity of the imidazole ester framework material is influenced.
In one embodiment of the present invention, the cyclohexane derivative used may be methylcycloethane and/or ethylcyclohexane.
The gas trapping agent further reduces the viscosity of slurry and improves the desorption speed by adding the cosolvent on the basis of the main solvent DMPU. On one hand, the cosolvent has lower viscosity, the viscosity of the whole system is reduced, and the gas-liquid mass transfer efficiency is improved; on the other hand, the cosolvent is a low-boiling-point organic matter, and in the vacuum-pumping desorption process, the cosolvent extracts dissolved gas due to boiling or rapid volatilization, so that the purpose of improving the desorption efficiency is achieved.
In addition, during vacuum desorption, the equilibrium vacuum of the system is relatively low due to boiling of the co-solvent. In a specific embodiment of the invention, in the process of vacuum-pumping desorption, the ultimate vacuum degree of a slurry system without adding the cosolvent is-0.1 MPa, and the ultimate vacuum degree of a slurry system with adding the cosolvent is-0.09 MPa. The vacuum degree (-0.09MPa) can effectively reduce the load of the vacuum pump, thereby reducing the energy consumption and the maintenance cost.
Part of the cosolvent lost due to boiling in the gas trapping agent can be returned to the trapping agent by adding a condensing reflux device, and the desorbed enriched gas continues to pass through a condenser in a gas phase due to a low condensation point so as to separate the additive from the dissolved gas in a gas-liquid manner.
In the gas trapping agent of the present invention, the adsorbent is used for selectively adsorbing the gas to be trapped.
In one embodiment of the present invention, the zeolitic imidazolate framework material is a ZIF-8 zeolitic imidazolate framework material or a ZIF-67 zeolitic imidazolate framework material.
Specifically, the zeolite imidazolate framework material is a ZIF-8 zeolite imidazolate framework material.
In one embodiment of the invention, the gas trapping agent used has a solid content (adsorbent) (the remaining part after drying under specified conditions is in mass percent of the total) of 10% to 40%.
The preparation method of the gas trapping agent comprises the following steps:
and uniformly mixing the main solvent and the cosolvent, then adding the adsorbent, mixing and stirring to obtain the gas trapping agent.
The gas trapping agent is used for separating target gases in refinery dry gas, natural gas, coke oven gas, flue gas and coal bed gas. For example, C can be trapped2And C2+Alkane or alkene of the component, filtering out useless or harmful N2、CO2Etc. if necessary, the beneficial components can be further separated and purified; or can capture CO2、N2Etc. recovering the H passing therethrough2And (4) and the like.
When the gas trapping agent is used for separating flue gas, the gas-liquid ratio can be 150-200: 1.
when the gas trapping agent gas is used for separating natural gas, the gas-liquid ratio can be 100-150: 1.
when the gas trapping agent is used for separating refinery gas and coke oven gas, the gas-liquid ratio can be 50-100: 1.
when the gas trapping agent is used for separating coal bed gas, the gas-liquid ratio can be 30-60: 1.
the gas-liquid ratio in the invention refers to the ratio of the volume of the mixed gas to the volume of the gas trapping agent under the standard condition.
After the gas collector of the invention absorbs gas and is saturated, the gas can be desorbed by reducing pressure, thereby realizing the regeneration of slurry, and the recovered slurry can be reused to absorb gas again.
The gas trapping agent has the advantages of low viscosity, high mass transfer speed, high desorption speed, difficult foaming and high regeneration performance of slurry.
Drawings
FIG. 1 is a graph comparing the solubility curves of methane measured in example 1.
FIG. 2 is a graph comparing the methane adsorption kinetics curves measured in example 3.
Fig. 3 is a graph of ethane solubility of fresh and regenerated slurries at different desorption conditions as measured in example 4.
Fig. 4 is a graph of ethane solubility of fresh and regenerated slurries at different desorption conditions as measured in comparative example 2.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
In this example, a methane adsorption solubility test at 20 ℃ was carried out using a DMPU pure solvent, a ZIF-8(30 wt%)/DMPU slurry, and a ZIF-8(30 wt%)/DMPU slurry recycle test was carried out. The regeneration condition is that the vacuum is pumped and the desorption is carried out for 30min at the temperature of 20 ℃. The effect of the solvent other than the additive in the gas trapping agent and the solid phase adsorbent and the regeneration performance thereof were examined. The corresponding experimental results are shown in fig. 1.
As can be seen from FIG. 1, the addition of the solid phase adsorbent greatly improves the absorption (adsorption) amount of the slurry to methane, and the solubility coefficient can reach 0.1 mol.L-1·Bar-1The method can be applied to the capture of the methane component in the multi-component gas. In the four-cycle methane absorption-desorption experiment, the adsorption amount of the ZIF-8(30 wt%)/DMPU slurry is unchanged, which shows that the regeneration performance is excellent. In a circulation experiment, the ZIF-8 structure is still kept complete, and DMPU does not enter the ZIF-8 pore canal to occupy the adsorption site, so that the carrier is suitable for being used as a ZIF-8 carrier.
Example 2
This example provides a gas trapping agent, which uses 1, 3-Dimethylpropyleneurea (DMPU) as a main solvent; cyclohexane is taken as a cosolvent (the mass concentration ratio of cyclohexane to DMPU in the solvent is 1: 5); ZIF-8 is used as a solid phase adsorbent.
The viscosity measurements were carried out at room temperature (30 ℃ C.) and at solid content of 20%, 25%, 30%, 35% and 40%, respectively, and the results are shown in Table 1. (viscosity unit: mPas).
Comparative example 1
The comparative example provides a slurry composition without added co-solvent, with DMPU as the main solvent and ZIF-8 as the solid phase adsorbent.
The viscosity measurements were carried out at room temperature (30 ℃ C.) and at solid content of 20%, 25%, 30%, 35% and 40%, respectively, and the results are shown in Table 1. (viscosity unit: mPas).
TABLE 1
40％ 35％ 30％ 25％ 20％
Comparative example 1 70 37 23 14 11
Example 2 35 22 14 11 9
The comparison in table 1 shows that under the same solid phase content, the addition of the cosolvent cyclohexane significantly reduces the viscosity of the system, and is beneficial to gas-liquid mass transfer and operation in a later industrial test separation tower and pipelines. Meanwhile, the reduction amplitude is more obvious at high solid content, which has important significance for improving the solid phase content of the adsorbent and increasing the single-component gas adsorption quantity and the mixed gas separation effect.
Example 3
In this example, the effect of the co-solvent in the gas trapping agent was mainly examined with DMPU, DMPU + H2O (mass concentration ratio of 9:1), DMPU + cyclohexane (mass concentration ratio of 4:1), DMPU + methylcyclohexane (mass concentration ratio of 4:1), DMPU + ethylcyclohexane (mass concentration ratio of 7:3) as a solvent, ZIF-8 as a solid phase adsorbent (mass concentration of 30 wt%), and a kinetic curve of methane absorption (adsorption) under isothermal (20 ℃) conditions was determined. The corresponding absorption (attachment) kinetics are shown in figure 2. Tong (Chinese character of 'tong')By comparing the pressure drop amplitude of different systems in the same time, the absorption (adsorption) rates of the gas of different collectors can be compared, and the larger the pressure drop amplitude is, the higher the absorption rate is. Fig. 2 shows that the addition of cyclohexane and its derivatives can greatly improve the gas-liquid contact efficiency of the system and reduce the equilibrium time. By contrast, the rate did not increase or decrease with the addition of water, which was also less viscous than DMPU.
Example 4
The embodiment provides a gas trapping agent, which takes DMPU as a main solvent; cyclohexane is taken as a cosolvent (the mass fraction is 16%); ZIF-8 is used as an adsorbent (the mass concentration is 30%). This example examines the effect of the addition of the additive cyclohexane on the desorption rate of the trapping agent.
First, the collector slurry system was subjected to ethane solubility curve measurement at isothermal (20 ℃ C.). And (3) carrying out vacuum desorption on the slurry after absorption (adsorption) saturation for 10min and 5min at 20 ℃ respectively to carry out the next group of solubility curve determination experiments. Whether desorption is complete is judged by comparison with the solubility curve of the collector slurry. The corresponding experimental results are shown in fig. 3.
Comparative example 2
The embodiment provides a gas trapping agent without adding a cosolvent, and only uses DMPU as a solvent; ZIF-8 is used as an adsorbent (the mass concentration is 30%).
Similarly, first, the fresh collector slurry system was subjected to an ethane solubility curve measurement at isothermal (20 ℃). And (3) carrying out vacuum desorption on the slurry after absorption (adsorption) saturation for 10min and 5min at 20 ℃ respectively to carry out the next group of solubility curve determination experiments. Whether desorption was complete was judged by comparison with the solubility curve of fresh slurry. The corresponding experimental results are shown in fig. 4.
As can be seen by comparing fig. 3 and 4, on the one hand, the addition of cyclohexane did not affect the ethane adsorption capacity of the slurry, indicating that cyclohexane did not enter the ZIF-8 channels to occupy the adsorption sites. In the desorption efficiency aspect, under the condition that the desorption time is 10min, whether the additive is added or not has little influence on the desorption effect, and the complete desorption is basically achieved. However, when the desorption time is reduced to 5min, the methane absorption (adsorption) amount of the slurry system without adding cyclohexane is obviously reduced, and the trapping agent of the invention can achieve complete regeneration, thereby showing more excellent desorption performance. It is also worth mentioning that the ultimate vacuum of the system of example 4 is-0.09 MPa, while the system of comparative example 2 is-0.1 MPa during the vacuum pumping desorption. The former can effectively reduce the load of the vacuum pump.
Example 5
The embodiment provides a gas trapping agent, which takes DMPU as a main solvent; cyclohexane is taken as a cosolvent (the mass concentration is 16%); ZIF-8 is used as an adsorbent (mass concentration is 35%).
Catalytic dry gas (one of refinery dry gases) (H) is carried out at isothermal temperature (10 deg.C)2：55.9mol％，CH4:13.5mol％，C2H6:3.33mol％，C3H6:0.0114mol％，C3H8:6.13mol％，n-C4:9.89mol％，N2: 11.2 mol%) and the results are shown in table 2. The composition of the feed gas and the balance gas is analyzed by an HP78900 type chromatograph.
As can be seen from Table 2, the single-stage separation of the trapping agent has obvious separation effect, and C in the outlet balance gas2And C2+The component concentration is obviously reduced, wherein n-C4The concentration of (2) is reduced from 9.89 mol% to 0.078 mol%. Meanwhile, the concentration of hydrogen is obviously improved, and the mixed gas plays a role in enriching hydrogen through the slurry system.
TABLE 2
Figure BDA0002266058950000061
The above examples demonstrate that the gas trapping agent of the present invention has low viscosity, fast mass transfer, fast desorption, little bubbling and high slurry regeneration performance.

Claims (10)

1. A gas trapping agent comprising a main solvent, an adsorbent and a co-solvent; wherein the content of the first and second substances,
the main solvent is 1, 3-dimethyl propylene urea;
the adsorbent is a zeolite imidazole ester framework material;
the cosolvent is cyclohexane and/or cyclohexane derivatives.
2. The gas trapping agent according to claim 1, wherein the content of the co-solvent is 1% to 25%, the content of the adsorbent is 10% to 45%, and the balance is the main solvent, based on 100% by mass of the gas trapping agent.
3. The gas trapping agent according to claim 2, wherein the content of the co-solvent is 16%.
4. The gas trap of claim 1, wherein the zeolitic imidazolate framework material is a ZIF-8 zeolitic imidazolate framework material or a ZIF-67 zeolitic imidazolate framework material.
5. The gas trapping agent of claim 1, wherein the cyclohexane derivative is methylcyclohexane and/or ethylcyclohexane.
6. The gas capture agent of claim 1 having a solids content of 10% to 40%.
7. A process for the preparation of a gas trapping agent according to any one of claims 1 to 6, which comprises the steps of:
and uniformly mixing the main solvent and the cosolvent, then adding the adsorbent, mixing and stirring to obtain the gas trapping agent.
8. Use of a gas capture agent according to any of claims 1 to 6 for the separation of target gases in refinery dry gas, natural gas, coke oven gas, flue gas, coal bed gas.
9. The use as claimed in claim 8, wherein the gas trapping agent is used for separating flue gas, and the gas-liquid ratio is 150-200: 1;
when the gas trapping agent is used for separating natural gas, the gas-liquid ratio is 100-150: 1.
10. use according to claim 8, wherein the gas trapping agent is used for separating refinery dry gas and coke oven gas, the gas-liquid ratio is 50-100: 1;
when the gas trapping agent is used for separating coal bed gas, the gas-liquid ratio is 30-60: 1.
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