CN114904487A - Adsorbent for separating chloropropane and chloropropene mixed gas, and preparation method and separation method thereof - Google Patents

Adsorbent for separating chloropropane and chloropropene mixed gas, and preparation method and separation method thereof Download PDF

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CN114904487A
CN114904487A CN202210155439.6A CN202210155439A CN114904487A CN 114904487 A CN114904487 A CN 114904487A CN 202210155439 A CN202210155439 A CN 202210155439A CN 114904487 A CN114904487 A CN 114904487A
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adsorbent
chloropropene
transition metal
chloropropane
metal salt
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CN114904487B (en
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李英波
王晓天
罗海燕
刘会洲
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Institute of Process Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/067—Allyl chloride; Methallyl chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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Abstract

The invention provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereofAnd a separation method, the adsorbent is composed of transition metal ions and organic ligands; the structural formula of the adsorbent is M (C) 7 O 5 H 4 )·2H 2 O, wherein M is a transition metal ion; the pore diameter of the adsorbent is
Figure DDA0003512348500000011
The adsorbent is a three-dimensional net structure; the adsorbent disclosed by the invention shows selective adsorption on chloropropene with smaller molecular dynamics size, and chloropropane with larger molecular size is excluded from a pore channel, so that the adsorption separation of chloropropene and chloropropane in mixed gas is realized, and the selective separation efficiency is high; the preparation method is simple, raw materials are easy to obtain, the cost is low, the service life is long, the regeneration is easy, the reutilization is realized, and the method has a remarkable industrial application prospect.

Description

Adsorbent for separating chloropropane and chloropropene mixed gas, and preparation method and separation method thereof
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to an adsorbent for separating a mixed gas of chloropropane and chloropropene, and a preparation method and a separation method thereof.
Background
Chloropropene (C) 3 H 5 Cl) is an important organic chemical raw material, can be used for preparing Epoxy Chloropropane (ECH) and further synthesizing products such as epoxy resin, chlorohydrin rubber and the like; in industrial applications, the purity of the raw chloropropene is very demanding (polymer grade), and the purity of the raw material directly affects the quality of the final product. At present, the production method of chloropropene mainly comprises the following steps: high temperature chlorination processes and oxidative chlorination processes. Although these two processes can obtain chloropropene products with higher purity, they are still far from the polymerization grade purity, mainly because the production process inevitably generates a series of other impurities, and the most difficult is chloropropane. In addition, in the production process of industrial products, chloropropene is excessive and needs to be recycled, and the problem of cyclic accumulation of chloropropane also exists. Therefore, chloropropane impurities in the starting materials and reaction intermediates need to be separated from the chloropropenes.
For the separation of olefins and paraffins, the most mature process at present is a multistage rectification process. CN111100683A discloses a method for separating long-chain alkane and olefin from Fischer-Tropsch synthetic oil, which comprises the following steps: firstly, introducing the raw material into a pre-adsorption tower filled with a deoxygenation adsorbent to perform adsorption separation to remove oxygen-containing compounds in the raw material, so that the mass fraction of the oxygen-containing compounds is reduced to be below 0.1%; then sending the obtained material into a simulated moving bed adsorption separation system filled with an alkane and alkene separation adsorbent to carry out alkane and alkene adsorption separation, selectively separating alpha-olefin and alkane to obtain two streams, wherein one stream is rich in alpha-olefin components, and the other stream is rich in alkane components; finally, feeding the alpha-olefin-rich component into a rectification unit, cutting the desorbent and the alpha-olefin to obtain the alpha-olefin and the desorbent, and recycling the desorbent to a desorbent storage tank; sending the alkane-rich component into a rectification unit for cutting to obtain a desorbent and long-chain alkane cutting; the method can obtain long-chain alpha-olefin with high added value by two-stage series adsorption separation process.
CN103864554A discloses a method for separating alkane, alkene and arene from a hydrocarbon mixture by extractive distillation, which relates to a method for separating hydrocarbon by extractive distillation, comprising the following steps: in a first extractive distillation tower, extracting and rectifying a hydrocarbon mixture raw material by using an extracting agent, and separating the raw material into aromatic hydrocarbon and a non-aromatic hydrocarbon mixture rich in alkane and olefin; in the second extractive distillation tower, under the action of an extracting agent, the separation of alkane and olefin in the non-aromatic hydrocarbon mixture rich in alkane and olefin is realized; taking out alkane products from a reflux pump of the second extractive distillation tower, taking out alkene products from a reflux pump of the primary regeneration tower, obtaining aromatic hydrocarbon mixture products from the tower top of the first extractant recovery tower, and recovering and recycling the extractant; the method overcomes the defects that only aromatic hydrocarbon and non-aromatic hydrocarbon products can be obtained through extraction, rectification and separation in the prior art, and the further separation of olefin and alkane high value-added products in the non-aromatic hydrocarbon cannot be realized. However, the cryogenic distillation method consumes a large amount of energy, for example, separation of propylene and propane by distillation usually requires more than 120 trays in the distillation column, the height of the column is up to 90 m, the reflux ratio is more than 10, and auxiliary processes such as pressurization, refrigeration and the like are required, so that separation of olefin and alkane is classified as one of seven energy-intensive separation processes; compared with propylene and propane, the chloropropene and chloropropane with chloro groups have more similar physical and chemical properties such as boiling points, molecular sizes and the like, are more difficult to separate, and have higher energy consumption.
Therefore, it is urgently needed to develop a separation method of chloropropene and chloropropane mixed gas with high efficiency and low energy consumption.
Disclosure of Invention
The invention aims to provide an adsorbent for separating a mixed gas of chloropropane and chloropropene, a preparation method and a separation method thereof, wherein the adsorbent consists of transition metal ions and organic ligands; the structural formula of the adsorbent is M (C) 7 O 5 H 4 )·2H 2 O, wherein M is a transition metal ion; the pore diameter of the adsorbent is
Figure BDA0003512348480000021
The adsorbent is a three-dimensional net structure; the adsorbent disclosed by the invention shows selective adsorption on chloropropene with smaller molecular dynamics size, and chloropropane with larger molecular size is excluded from a pore channel, so that the adsorption separation of chloropropene and chloropropane in mixed gas is realized, and the selective separation efficiency is high; the preparation method is simple, raw materials are easy to obtain, the cost is low, the service life is long, the regeneration is easy, the reutilization is realized, and the method has a remarkable industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide an adsorbent for separating a mixed gas of chloropropane and chloropropene, which is composed of transition metal ions and organic ligands; the structural formula of the adsorbent is M (C) 7 O 5 H 4 )·2H 2 O, wherein M is a transition metal ion; the pore diameter of the adsorbent is
Figure BDA0003512348480000031
The adsorbent is a three-dimensional network structure.
The adsorbent is a three-dimensional network structure formed by organic ligands and transition metal ions through coordination bonds or intermolecular forces, and the pore diameter of the adsorbent is
Figure BDA0003512348480000032
From the view of the dynamic size of the molecule, the minimum molecular dynamic size of chloropropene and chloropropane is respectively
Figure BDA0003512348480000033
And
Figure BDA0003512348480000034
wherein, chloropropene has smaller size, can enter the pore channel of the adsorbent and interact with functional groups on the surface of the pore channel, and chloropropane with larger molecular size can not enter the pore channel. The invention leads the synthetic aperture to be equal to
Figure BDA0003512348480000035
The adsorbent has obvious difference on the adsorption quantity of two molecules, when single-component static adsorption is carried out, the ultramicropore metal organic framework material has very obvious adsorption effect on chloropropene, the highest adsorption quantity can reach 2mmol/g at the temperature of 30 ℃, but the adsorption on chloropropane is almost not carried out, the highest adsorption quantity is only 0.5mmol/g, the selective adsorption on the chloropropene is shown, and the adsorption separation on the chloropropene and chloropropane is further realized; during the dynamic adsorption of the mixed components, the ultra-microporous metal organic framework material has small adsorption capacity to chloropropane, chloropropane flows out from the outlet of the tower firstly, and the ultra-microporous metal organic framework material has strong action to chloropropane and large adsorption capacity, so that the ultra-microporous metal organic framework material adsorbed with chloropropene flows out from the outlet of the tower for a longer time.
It is worth noting that the pore size of the adsorbent is
Figure BDA0003512348480000041
For example, can be
Figure BDA0003512348480000042
Figure BDA0003512348480000043
Figure BDA0003512348480000044
Etc. if the pore diameter is larger than
Figure BDA0003512348480000045
The chloropropane can also diffuse into the pore channels of the adsorbing material, so that the selectivity of the adsorbing material is reduced; if the pore diameter is smaller than
Figure BDA0003512348480000046
This results in too high diffusion resistance of chloropropene, and further results in a decrease in the amount of adsorbent adsorbed.
As a preferred embodiment of the present invention, the transition metal ion comprises Co 2+ 、Ni 2+ 、Fe 2+ Or Mg 2+ Any one or a combination of at least two of the above, typical but non-limiting examples of which include Co 2+ And Ni 2+ Combination of (A) and (B), Co 2+ And Fe 2+ Combination of (A) and (B), Co 2+ And Mg 2+ Combination of (A) and (B), Ni 2+ And Fe 2+ Combination of (A) and (B), Ni 2+ And Mg 2+ Combination of (1), Fe 2+ And Mg 2+ Combinations of (a) and (b).
Preferably, the organic ligand is gallic acid.
The second purpose of the present invention is to provide a method for preparing the adsorbent, which comprises the following steps:
mixing transition metal salt, organic ligand and alkali solution, and sequentially carrying out reaction and vacuum activation to obtain an adsorbent;
wherein the molar ratio of the transition metal salt to the organic ligand is 1 (0.5-1.5); the molar ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10).
It is to be noted that the molar ratio of the transition metal salt to the organic ligand is 1 (0.5-2), and may be, for example, 1:0.5, 1:0.7, 1:0.9, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2, etc.; the molar ratio of the transition metal salt to the base in the alkaline solution is 1 (0.05-10), and examples thereof include 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, and 1:10, but are not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
As a preferred embodiment of the present invention, the metal cation of the transition metal salt comprises Co 2+ 、Ni 2+ 、Fe 2+ Or Mg 2+ Any one or a combination of at least two of the above, typical but non-limiting examples of which include Co 2+ And Ni 2+ Combination of (A) and (B), Co 2+ And Fe 2+ Combination of (A) and (B), Co 2+ And Mg 2+ Combination of (A) and (B), Ni 2+ And Fe 2+ Combination of (A) and (B), Ni 2+ And Mg 2+ Combination of (1), Fe 2+ And Mg 2+ A combination of (1); the anion of the transition metal salt comprises Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of the above, typical but non-limiting examples of which include Cl - And NO 3 - Combination of (A) and (B), Cl - And SO 4 2- Combination of (A) and (B), NO 3 - And SO 4 2- A combination of (a) and (b).
It is worth to say that the invention controls the pore diameter of the obtained adsorbent at the same time by regulating the type of the transition metal salt
Figure BDA0003512348480000051
Preferably, the organic ligand is gallic acid.
Preferably, the concentration of the alkali in the alkali solution is 0.01-0.5 mol/L; for example, the concentration may be 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, etc., but the concentration is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the solvent of the alkali solution comprises deionized water.
Preferably, the base in the base solution comprises any one of NaOH, KOH or LiOH or a combination of at least two of which typical but non-limiting examples include NaOH and KOH combinations, NaOH and LiOH combinations, KOH and LiOH combinations.
In a preferred embodiment of the present invention, the mixing is performed by stirring.
Preferably, the stirring speed is 500-1000rpm, such as 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, etc., but it is not limited to the enumerated values, and other unrecited values within the above-mentioned range of values are also applicable.
As a preferred embodiment of the present invention, the reaction temperature is 100-140 ℃, and may be, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ or the like, but is not limited to the values listed, and other values not listed in the above range are also applicable.
Preferably, the reaction time is 24-72h, such as 24h, 28h, 30h, 32h, 35h, 38h, 40h, 43h, 45h, 47h, 50h, 52h, 56h, 60h, 62h, 65h, 67h, 70h, 72h, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferred technical solution of the present invention, the preparation method further comprises: after the reaction, the reaction product of the reaction is washed prior to the vacuum activation.
Preferably, the detergent used for washing comprises ethanol.
In a preferred embodiment of the present invention, the temperature of the vacuum activation is 50 to 150 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ and the like, and more preferably 100 ℃ to 140 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ and the like, but is not limited to the values listed, and other values not listed in the above range of values are also applicable.
Preferably, the vacuum activation time is 18 to 48 hours, such as 18 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, 48 hours, etc., more preferably 24 to 32 hours, such as 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, etc., but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
stirring and mixing transition metal salt, gallic acid and 0.01-0.5mol/L alkali solution at the rotating speed of 500-; activating in vacuum at 50-150 deg.C for 18-48h to obtain adsorbent;
wherein the molar ratio of the transition metal salt to the gallic acid is 1 (0.5-2); the molar ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10); the metal cation of the transition metal salt comprises Co 2+ 、Ni 2+ 、Fe 2+ Or Mg 2+ Any one or a combination of at least two of them, and the anion of the transition metal salt includes Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of; the alkali in the alkali solution comprises any one or a combination of at least two of NaOH, KOH or LiOH.
The invention also aims to provide a method for separating a mixed gas of chloropropane and chloropropene by using the adsorbent, which comprises the following steps: the adsorbent is put into the chloropropene and chloropropane mixed gas, and is subjected to adsorption separation at 0-50 ℃ and 10-500 kPa.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) the aperture of the adsorbent for separating the mixed gas of chloropropane and chloropropene is
Figure BDA0003512348480000071
The chloropropene with small molecular dynamics size is selectively adsorbed, and chloropropane with large molecular size is excluded from the pore channel, so that the adsorption separation of chloropropene and chloropropane in the mixed gas is realized, and the selective separation efficiency is high;
(2) the adsorbent for separating the mixed gas of chloropropane and chloropropene has the advantages of simple preparation method, easily obtained raw materials, low cost, long service life, easy regeneration, reutilization and obvious industrial application prospect.
Drawings
FIG. 1 is a graph of the penetration of the adsorbent described in example 1 at 30 ℃ for chloropropenes and chloropropanes;
FIG. 2 is an adsorption isotherm of chloropropenes and chloropropanes at 30 ℃ for the adsorbent described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000072
The adsorbent is a three-dimensional net structure; the preparation method comprises the following steps:
adding CoCl 2 Stirring and mixing gallic acid and 0.05mol/L KOH aqueous solution at the rotating speed of 800rpm, reacting for 24 hours at the temperature of 120 ℃, and cleaning by using ethanol; activating in vacuum at 120 deg.c for 24 hr to obtain adsorbent;
wherein, CoCl 2 The molar ratio of the gallic acid to the gallic acid is 1: 2; CoCl 2 And KOH in a molar ratio of 1: 0.5.
Example 2
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Mg (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000081
The adsorbent is a three-dimensional net structure; the preparation process described with reference to example 1 differs only in that: adding CoCl 2 Substitution to MgCl 2 。
Example 3
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Ni (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000082
The adsorbent is a three-dimensional net structure; the preparation process described with reference to example 1 differs only in that: adding CoCl 2 Replacement by NiCl 2 。
Example 4
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000083
The adsorbent is a three-dimensional net structure; the preparation described with reference to example 1 differs only in that the concentration of the KOH solution is 0.1 mol/L.
Example 5
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000091
The adsorbent is a three-dimensional net structure; the preparation method comprises the following steps:
adding CoCl 2 Stirring and mixing gallic acid and 0.5mol/L KOH aqueous solution at the rotating speed of 500rpm, reacting for 72 hours at the temperature of 100 ℃, and cleaning by using ethanol; activating in vacuum for 18h at the temperature of 150 ℃ to obtain an adsorbent;
wherein, CoCl 2 The molar ratio of the gallic acid to the gallic acid is 1: 1; CoCl 2 And KOH in a 1:10 molar ratio.
Example 6
The embodiment provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000092
The adsorbent is a three-dimensional net structure; the preparation method comprises the following steps:
adding CoCl 2 Stirring and mixing gallic acid and 0.01mol/L KOH aqueous solution at the rotating speed of 1000rpm, reacting for 48h at 140 ℃, and cleaning by using ethanol; activating in vacuum for 48h at 50 ℃ to obtain an adsorbent;
wherein, CoCl 2 The molar ratio of the gallic acid to the gallic acid is 1: 0.5; CoCl 2 And KOH in a molar ratio of 1: 0.05.
Comparative example 1
The comparative example provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, and the structural formula of the adsorbent is Zn (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000093
The adsorbent is a three-dimensional net structure; the preparation method comprises the following steps:
reacting ZnCl 2 Gallic acid, 0.05mol/L KOH aqueous solution at 800rpmStirring and mixing, reacting for 24 hours at 120 ℃, and cleaning by using ethanol; activating in vacuum at 120 deg.C for 24 hr to obtain adsorbent;
wherein, ZnCl 2 The molar ratio of the gallic acid to the gallic acid is 1: 2; ZnCl 2 And KOH in a molar ratio of 1: 0.5.
Comparative example 2
The comparative example provides an adsorbent for separating a mixed gas of chloropropane and chloropropene and a preparation method thereof, and the structural formula of the adsorbent is Mn (C) 7 O 5 H 4 )·2H 2 O, the pore diameter of the adsorbent is
Figure BDA0003512348480000101
The adsorbent is of a three-dimensional net structure; the preparation method comprises the following steps:
mixing MnCl 2 Stirring and mixing gallic acid and 0.05mol/L KOH aqueous solution at the rotating speed of 800rpm, reacting for 24 hours at the temperature of 120 ℃, and cleaning by using ethanol; activating in vacuum at 120 deg.c for 24 hr to obtain adsorbent;
wherein, MnCl 2 The molar ratio of the gallic acid to the gallic acid is 1: 2; MnCl 2 And KOH in a molar ratio of 1: 0.05.
The adsorbents obtained in the above examples and comparative examples are tested for the adsorption amount and separation selectivity of chloropropene and chloropropane, and the test methods are as follows:
adsorption capacity: measuring the adsorption isotherm of the adsorbent to each gas by a full-automatic volumetric method gas adsorption instrument (Microtracbel BELSORP-max), thereby measuring the adsorption capacity;
separation selectivity: the formula for calculating the separation selectivity of the adsorbent to the chloropropene is as follows:
Figure BDA0003512348480000102
q 1 and q is 2 Means that the adsorbent is in p 1 And p 2 The equilibrium adsorption capacity under partial pressure, and the separation selectivity is the selectivity of the adsorbent under the partial pressure of 101 kPa;
the results of the adsorption amounts and adsorption selectivities of chloropropenes and chloropropanes in the above examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0003512348480000103
Figure BDA0003512348480000111
The following points can be derived from table 1:
(1) as can be seen from examples 1-6, the adsorbent prepared by the invention shows preferential adsorption to chloropropene, the adsorption quantity to chloropropene is obviously greater than that of chloropropane, the adsorption separation of chloropropene and chloropropane in the mixed gas is realized, and the selective separation efficiency is high;
(2) as can be seen from the examples 1-3, the species of the transition metal ions in the adsorbent realizes the regulation and control of the adsorption performance, the pore diameters of the examples 1-3 are reduced in sequence, and the adsorption amounts of the transition metal ions to the chloropropene and the chloropropane are reduced in sequence;
(3) comparing example 1 with example 4, it can be seen that Co (C) was synthesized at different alkali contents 7 O 5 H 4 )·2H 2 The adsorption performance of O to chloropropene is not greatly different;
(4) comparing example 1 with comparative examples 1 and 2, it can be seen that the pore diameter of the adsorbent in comparative example 1 is
Figure BDA0003512348480000112
Less than preferred in the present invention
Figure BDA0003512348480000113
The diffusion resistance of chloropropene is too large, and the adsorption quantity of the adsorbent is reduced; since the pore diameter of the adsorbent in comparative example 2 was
Figure BDA0003512348480000114
Beyond the preferred aspects of the invention
Figure BDA0003512348480000115
The chloropropane can also diffuse into the pore channels of the adsorbing material, so that the selectivity of the adsorbing material is reduced.
Application example 1
The adsorbent Co (C) obtained in example 1 was subjected to 7 O 5 H 4 )·2H 2 And O is filled into an adsorption column with the inner diameter of 5mm, nitrogen is used as carrier gas at the temperature of 30 ℃, mixed gas of chloropropene and chloropropane with the mass ratio of 1:1 is introduced into the adsorption column at the speed of 3mL/min to be contacted with an adsorbent, the chloropropene in the mixed gas is adsorbed under the pressure of 350kPa, gas phase detection is carried out on the effluent gas by using a gas chromatograph, the chloropropane penetration is determined when the concentration of the chloropropane is suddenly increased by testing, and the adsorption separation of the chloropropene and chloropropane mixed gas is completed when the chloropropene penetrates.
The penetration curve of the chloropropene and the chloropropane obtained in the application example is shown in figure 1, and as can be seen from figure 1, the chloropropane breaks through in about 5 minutes and keeps for a period of time; the chloropropene broke through in about 13 minutes and finally reached equilibrium.
The adsorption isotherms of the present application at 30 ℃ for chloropropene and chloropropane are shown in fig. 2, and it can be seen from fig. 2 that the adsorption amount of the adsorbent for chloropropene is significantly increased with the increase in pressure, but the adsorption amount for chloropropane is very low.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃, the chloropropene gas is obtained, the purity of the chloropropene obtained by testing the application example is more than 99.99%, and the adsorption column can be recycled.
Application example 2
The adsorbent Mg (C) obtained in example 2 7 O 5 H 4 )·2H 2 O is filled into an adsorption column with the inner diameter of 5mm, helium is taken as carrier gas at the temperature of 45 ℃, the mixed gas of chloropropene and chloropropane with the mass ratio of 1:1 is introduced into the adsorption column at the speed of 3mL/min and is adsorbedContacting with a solvent, adsorbing chloropropene in the mixed gas under the condition of 100kPa, carrying out gas phase detection on the gas flowing out by adopting a gas chromatograph, testing to obtain that the chloropropane penetrates when the concentration of chloropropane is suddenly increased, and finishing the adsorption separation of the chloropropene and the chloropropane mixed gas when the chloropropene penetrates.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 3
The adsorbent obtained in example 3 was Ni (C) 7 O 5 H 4 )·2H 2 And O is filled into an adsorption column with the inner diameter of 5mm, helium is used as carrier gas at the temperature of 20 ℃, mixed gas of chloropropene and chloropropane with the mass ratio of 1:1 is introduced into the adsorption column at the speed of 3mL/min to be contacted with an adsorbent, the chloropropene in the mixed gas is adsorbed under the pressure of 200kPa, gas phase detection is carried out on the effluent gas by using a gas chromatograph, the chloropropane penetration is determined when the concentration of the chloropropane is suddenly increased by testing, and the adsorption separation of the chloropropene and chloropropane mixed gas is completed when the chloropropene penetrates.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 4
The adsorbent Co (C) obtained in example 1 was used in the same manner as in application example 1 7 O 5 H 4 )·2H 2 O is used for separating the mixed gas of chloropropene and chloropropane, and the difference is only that: introducing the mixed gas of chloropropene and chloropropane into an adsorption column at the speed of 1mL/min to contact with the adsorbent.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 5
The adsorbent Co (C) obtained in example 1 was used in the same manner as in application example 1 7 O 5 H 4 )·2H 2 O is used for separating the mixed gas of chloropropene and chloropropane, and the difference is only that: introducing the mixed gas of chloropropene and chloropropane into an adsorption column at the speed of 2mL/min to contact with the adsorbent.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 6
The adsorbent Co (C) obtained in example 1 was used in the same manner as in application example 1 7 O 5 H 4 )·2H 2 O is used for separating the mixed gas of chloropropene and chloropropane, and the difference is only that: the mass ratio of the chloropropene to the chloropropane in the mixed gas of the chloropropene and the chloropropane is 9: 1.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 7
The adsorbent Co (C) obtained in example 1 was used in the same manner as in application example 1 7 O 5 H 4 )·2H 2 O is used for separating the mixed gas of chloropropene and chloropropane, and the difference is only that: the temperature of the mixed gas of chloropropene and chloropropane is replaced by 40 ℃ from 30 ℃.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is more than 99.99%, and an adsorption column can be recycled.
Application example 8
The adsorbent Co (C) obtained in example 1 was used in the same manner as in application example 1 7 O 5 H 4 )·2H 2 O is used for separating the mixed gas of chloropropene and chloropropane, and the difference is only that: the inner diameter of the adsorption column was changed from 5mm to 10 mm.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃, the chloropropene gas is obtained, the purity of the chloropropene obtained by testing the application example is more than 99.99%, and the adsorption column can be recycled.
Comparative application example 1
Adsorbent Zn (C) obtained in comparative example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 And O is used for separating the mixed gas of chloropropene and chloropropane.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is 99.8%, and the adsorption column can be recycled.
Comparative application example 2
Adsorbent Mn (C) obtained in comparative example 2 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 And O is used for separating the mixed gas of chloropropene and chloropropane.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the adsorbent is desorbed after the chloropropene is adsorbed by vacuumizing at 100 ℃ to obtain chloropropene gas, the purity of the chloropropene obtained by testing is 98%, and the adsorption column can be recycled.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The adsorbent for separating the mixed gas of chloropropane and chloropropene is characterized by consisting of transition metal ions and organic ligands; the structural formula of the adsorbent is M (C) 7 O 5 H 4 )·2H 2 O, wherein M is a transition metal ion; the pore diameter of the adsorbent is
Figure FDA0003512348470000011
The adsorbent is a three-dimensional network structure.
2. The sorbent according to claim 1, wherein the transition metal ions comprise Co 2+ 、Ni 2+ 、Fe 2+ Or Mg 2+ Any one or a combination of at least two of them;
preferably, the organic ligand is gallic acid.
3. A method for preparing the adsorbent according to claim 1 or 2, wherein the method comprises the steps of:
mixing transition metal salt, organic ligand and alkali solution, and sequentially carrying out reaction and vacuum activation to obtain an adsorbent;
wherein the molar ratio of the transition metal salt to the organic ligand is 1 (0.5-2); the molar ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10).
4. The method according to claim 3, wherein the metal cation of the transition metal salt comprises Co 2 + 、Ni 2+ 、Fe 2+ Or Mg 2+ Or a combination of at least two thereof, the anion of the transition metal salt includes Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of;
preferably, the organic ligand is gallic acid;
preferably, the concentration of the alkali in the alkali solution is 0.01-0.5 mol/L;
preferably, the solvent of the alkali solution comprises deionized water;
preferably, the base in the base solution comprises any one or a combination of at least two of NaOH, KOH or LiOH.
5. The production method according to claim 3 or 4, wherein the mixing is performed by stirring;
preferably, the rotation speed of the stirring is 500-.
6. The method according to any one of claims 3 to 5, wherein the reaction temperature is 100 ℃ to 140 ℃;
preferably, the reaction time is 24-72 h.
7. The production method according to any one of claims 3 to 6, characterized by further comprising: washing the reaction product of the reaction after the reaction and before the vacuum activation;
preferably, the detergent used for washing comprises ethanol.
8. The method according to any one of claims 3 to 7, wherein the temperature of the vacuum activation is 50 to 150 ℃, more preferably 100-140 ℃;
preferably, the vacuum activation time is 18-48h, more preferably 24-32 h.
9. The method according to any one of claims 3 to 8, characterized by comprising the steps of:
stirring and mixing transition metal salt, gallic acid and 0.01-0.5mol/L alkali solution at the rotating speed of 500-; activating in vacuum at 50-150 deg.C for 18-48h to obtain adsorbent;
wherein the molar ratio of the transition metal salt to the gallic acid is 1 (0.5-2); the molar ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10); the metal cation of the transition metal salt comprises Co 2+ 、Ni 2+ 、Fe 2+ Or Mg 2+ Any one or a combination of at least two of them, and the anion of the transition metal salt includes Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of; the alkali in the alkali solution comprises any one of NaOH, KOH or LiOH or the combination of at least two of the NaOH, the KOH or the LiOH.
10. A separation method of a mixed gas of chloropropane and chloropropene by using the adsorbent of claim 1 or 2, characterized in that the separation method comprises the following steps: placing the adsorbent in a mixed gas of chloropropene and chloropropane, and performing adsorption separation at 0-50 deg.C under 10-500 kPa.
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