CN114904487B - Adsorbent for separating chloropropane and chloropropene mixed gas, preparation method thereof and separation method - Google Patents

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

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CN114904487B
CN114904487B CN202210155439.6A CN202210155439A CN114904487B CN 114904487 B CN114904487 B CN 114904487B CN 202210155439 A CN202210155439 A CN 202210155439A CN 114904487 B CN114904487 B CN 114904487B
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adsorbent
transition metal
chloropropene
chloropropane
metal salt
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CN114904487A (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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention provides an adsorbent for separating chloropropane and chloropropene mixed gas, 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 aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the adsorbent disclosed by the invention shows selective adsorption on chloropropene with smaller molecular dynamic size, and chloropropane with larger molecular size is discharged outside the pore canal, so that the adsorption separation of chloropropene and chloropropane in the 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 recycling is realized, and the preparation method has remarkable industrial application prospect.

Description

Adsorbent for separating chloropropane and chloropropene mixed gas, preparation method thereof and separation method
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to an adsorbent for separating chloropropane and chloropropene mixed gas, a preparation method thereof 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; the purity of the chloropropene raw material is highly required (polymerization grade) in industrial application, and the purity of the raw material directly influences the quality of the final product. At present, the production method of chloropropene mainly comprises the following steps: high temperature chlorination process and oxidative chlorination process. These two processes, although capable of obtaining chloropropene products of higher purity, are at a distance from the polymerization grade purity, mainly because their production inevitably results in a series of other impurities, of which the chloropropane is the most difficult to remove. In addition, in the production process of industrial products, chloropropene is excessive, and needs to be recovered for recycling, so that the problem of recycling accumulation of chloropropane also exists. Thus, it is desirable to separate chloropropane impurities from chloropropene in the starting materials and reaction intermediates.
For the separation of olefins and paraffins, the most sophisticated process is currently the multistage rectification process. CN111100683a discloses a method for separating long-chain alkane-alkene from fischer-tropsch synthesis oil, which comprises: firstly, introducing the raw materials into a pre-adsorption tower filled with a deoxidizing adsorbent for adsorption separation to remove oxygen-containing compounds in the raw materials, so that the mass fraction of the oxygen-containing compounds is reduced to below 0.1%; then the obtained material is sent to a simulated moving bed adsorption separation system filled with alkane-alkene separation adsorbent to carry out alkane-alkene adsorption separation, and two material flows are obtained by selectively separating alpha-alkene and alkane, wherein one material flow is rich in alpha-alkene components, and the other material flow is rich in alkane components; finally, sending the alpha-olefin-rich component into a rectifying unit, and cutting the desorbent and the alpha-olefin to obtain the alpha-olefin and the desorbent, wherein the desorbent is circulated to a desorbent storage tank; delivering the alkane-rich component into a rectifying unit for cutting to obtain a desorbent and long-chain alkane cutting; the method can obtain long-chain alpha-olefin with high added value through two-stage series adsorption separation process.
CN103864554a discloses a process for separating alkanes, alkenes and aromatic hydrocarbons from hydrocarbon mixtures by extractive distillation, which relates to a process for separating hydrocarbons by extractive distillation, comprising the steps of: in the first extraction rectifying tower, extracting and rectifying the hydrocarbon mixture raw material by an extracting agent, and separating the hydrocarbon mixture raw material into aromatic hydrocarbon and a non-aromatic hydrocarbon mixture rich in alkane and alkene; in the second extraction rectifying tower, separating alkane from alkene in the non-aromatic hydrocarbon mixture rich in alkane and alkene under the action of an extracting agent; taking out an alkane product from a reflux pump of the second extraction rectifying tower, taking out an alkene product from a reflux pump of the primary regeneration tower, obtaining an aromatic hydrocarbon mixture product from the top of the first extractant recovery tower, and recycling the extractant; the method overcomes the defect that only aromatic hydrocarbon and non-aromatic hydrocarbon products can be obtained through extraction, rectification and separation in the prior art, and further separation of olefin and alkane high-added-value products in the non-aromatic hydrocarbon cannot be realized. However, the cryogenic rectification method consumes a lot of energy, for example, the separation of propylene and propane in a rectification mode often requires a rectification column with a tray number of more than 120, a column height of up to 90 meters and a reflux ratio of more than 10, and auxiliary pressurization, refrigeration and other processes are also required, so that the 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 similar physical and chemical properties such as boiling point, molecular size and the like, are more difficult to separate and consume higher energy.
Therefore, there is a need 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 chloropropane and chloropropene mixed gas, 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 aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the adsorbent of the invention shows selective adsorption on chloropropene with smaller molecular dynamics size, and chloropropane with larger molecular size is discharged outside the pore canal, thereby realizing the aim of mixing the chloropropene and the chloropropene in the gas mixtureThe adsorption separation of chloropropane has high selective separation efficiency; 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 recycling is realized, and the preparation method has remarkable industrial application prospect.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
an object of the present invention is to provide an adsorbent for separating a mixed gas of chloropropane and chloropropene, which comprises transition metal ions and an organic ligand; 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 aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure.
The adsorbent is a three-dimensional network structure formed by organic ligand and transition metal ions through coordination bonds or intermolecular forces, and the aperture of the adsorbent isFrom the viewpoint of the molecular dynamic size, the minimum molecular dynamic sizes of chloropropene and chloropropane are +.>And->Wherein, chloropropene has smaller size, can enter the pore canal of the adsorbent and interact with the functional groups on the surface of the pore canal, while chloropropane with larger molecular size can not enter the interior of the pore canal. The invention is based on the sieving action of the pore canal size of the material on chloropropene and chloropropane, so that the synthetic pore diameter is +.>The adsorbent has obvious difference to the adsorption quantity of two molecules, and the ultra-microporous metal organic framework material is opposite to the single-component static adsorptionThe chloropropene has very obvious adsorption effect, the highest adsorption capacity can reach 2mmol/g under the condition of 30 ℃, but the chloropropane is hardly adsorbed, the highest adsorption capacity is only 0.5mmol/g, the selective adsorption of the chloropropene is shown, and the adsorption separation of the chloropropene and the chloropropane is further realized; when the dynamic adsorption of the mixed components is carried out, because the adsorption capacity of the ultra-microporous metal organic frame material to chloropropane is small, chloropropane can flow out of the tower outlet first, and the ultra-microporous metal organic frame material has strong effect on chloropropene and large adsorption capacity, the time for the ultra-microporous metal organic frame material adsorbed with chloropropene to flow out of the tower outlet is longer, and after the adsorption of the ultra-microporous metal organic frame material used in the adsorption separation method provided by the invention is saturated, regeneration can be realized only by heating to 50-150 ℃ under the condition of vacuum or inert atmosphere and keeping for 2-10 hours, thereby realizing the adsorption separation of chloropropene and chloropropane.
It is worth noting that the pore size of the adsorbent isFor example, it can be +.> Etc. if the pore size is greater than + ->The chloropropane can also diffuse into the pore canal of the adsorption material, so that the selectivity of the adsorption material is reduced; if the pore diameter is smaller than +.>This leads to excessive chloropropene diffusion resistance and further to a decrease in the adsorption amount of the adsorbent.
As a preferable technical scheme of the inventionThe transition metal ions include Co 2+ 、Ni 2+ 、Fe 2+ Or Mg (Mg) 2+ Any one or a combination of at least two, examples of which include Co 2+ And Ni 2+ Co 2+ And Fe (Fe) 2+ Co 2+ And Mg (magnesium) 2+ Is a combination of Ni 2+ And Fe (Fe) 2+ Is a combination of Ni 2+ And Mg (magnesium) 2+ Is a combination of Fe 2+ And Mg (magnesium) 2+ Is a combination of (a) and (b).
Preferably, the organic ligand is gallic acid.
The second object of the present invention is to provide a method for producing the adsorbent according to one of the objects, comprising the steps of:
mixing transition metal salt, an organic ligand and an 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 mole ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10).
It is worth noting that the molar ratio of the transition metal salt to the organic ligand is 1 (0.5-2), 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 alkali in the alkali solution is 1 (0.05-10), for example, may be 1:0.05,1:0.1,1:0.5,1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9,1:10, etc., but not limited to the recited values, and other non-recited values within the above range are equally 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 (Mg) 2+ Any one or a combination of at least two, examples of which include Co 2+ And Ni 2+ Co 2+ And Fe (Fe) 2+ Co 2+ And Mg (magnesium) 2+ Is a combination of Ni 2+ And Fe (Fe) 2+ Is a combination of Ni 2+ And Mg (magnesium) 2+ Is a group of (2)Mixing Fe 2+ And Mg (magnesium) 2+ Is a combination of (a); the anions of the transition metal salt comprise Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two, examples of which include Cl - And NO 3 - Is a combination of (1) and (2) Cl - And SO 4 2- NO 3 - And SO 4 2- Is a combination of (a) and (b).
It is worth noting that the invention controls the pore diameter of the obtained adsorbent by regulating the type of the transition metal salt
Preferably, the organic ligand is gallic acid.
Preferably, the concentration of the alkali in the alkali solution is 0.01-0.5mol/L; for example, it 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 not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges may be similarly applied.
Preferably, the solvent of the alkaline solution comprises deionized water.
Preferably, the base in the alkaline solution comprises any one or a combination of at least two of NaOH, KOH or LiOH, typical but non-limiting examples of which include a combination of NaOH and KOH, a combination of NaOH and LiOH, a combination of KOH and LiOH.
As a preferable technical scheme of the invention, the mixing mode is stirring.
Preferably, the stirring speed is 500 to 1000rpm, for example, 500rpm,550rpm,600rpm,650rpm,700rpm,750rpm,800rpm,850rpm,900rpm,950rpm,1000rpm, etc., but the stirring speed is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned ranges are also applicable.
In a preferred embodiment of the present invention, the reaction temperature is 100 to 140 ℃, for example, 100 ℃,105 ℃,110 ℃,115 ℃,120 ℃,125 ℃,130 ℃,135 ℃,140 ℃, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are equally applicable.
Preferably, the reaction time is 24 to 72 hours, for example, 24 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, 43 hours, 45 hours, 47 hours, 50 hours, 52 hours, 56 hours, 60 hours, 62 hours, 65 hours, 67 hours, 70 hours, 72 hours, etc., but not limited to the recited values, and other non-recited values within the above range are equally applicable.
As a preferable technical scheme of the invention, the preparation method further comprises the following steps: after the reaction, the reaction product of the reaction is washed before the vacuum activation.
Preferably, the detergent used for the washing comprises ethanol.
In a preferred embodiment of the present invention, the vacuum activation temperature may be, for example, 50 to 150 ℃,60 ℃,70 ℃,80 ℃,90 ℃,100 ℃,110 ℃,120 ℃,130 ℃,140 ℃,150 ℃, etc., and more preferably 100 to 140 ℃, for example, 100 ℃,105 ℃,110 ℃,115 ℃,120 ℃,125 ℃,130 ℃,135 ℃,140 ℃, etc., but not limited to the above-mentioned values, and other non-cited values within the above-mentioned numerical ranges are equally applicable.
Preferably, the vacuum activation time is 18 to 48 hours, for example, 18 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, 48 hours, etc., more preferably 24 to 32 hours, for example, 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 non-recited values within the above range are equally applicable.
As a preferable 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 500-1000rpm, reacting at 100-140 deg.C for 24-72h, and cleaning with ethanol; vacuum activating at 50-150deg.C for 18-48 hr to obtain adsorbent;
wherein the mol ratio of the transition metal salt to the gallic acid is 1 (0.5-2);the mol ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10); the metal cations of the transition metal salt include Co 2+ 、Ni 2+ 、Fe 2+ Or Mg (Mg) 2+ Any one or a combination of at least two of the above, the anions of the transition metal salt comprise Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of the following; the alkali in the alkali solution comprises any one or a combination of at least two of NaOH, KOH or LiOH.
It is a third object of the present invention to provide a separation method of an adsorbent for a mixed gas of chloropropane and chloropropene, comprising the steps of: the adsorbent is placed in the mixed gas of chloropropene and chloropropane, and is subjected to adsorption separation at 0-50 ℃ and 10-500 kPa.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) The aperture of the adsorbent for separating the chloropropane and chloropropene mixed gas isThe chloropropene with smaller molecular dynamics size shows selective adsorption, and chloropropane with larger molecular size is discharged outside the pore canal, 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 chloropropane and chloropropene mixed gas has the advantages of simple preparation method, easily obtained raw materials, low cost, long service life, easy regeneration, repeated use and obvious industrial application prospect.
Drawings
FIG. 1 is a graph showing the penetration of the adsorbents described in example 1 over chloropropene and chloropropane at 30 ℃;
FIG. 2 is an adsorption isotherm of the adsorbent of example 1 for chloropropene and chloropropane at 30 ℃.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method comprises the following steps:
CoCl is to be processed 2 Stirring and mixing gallic acid and 0.05mol/L KOH aqueous solution at a rotating speed of 800rpm, reacting at 120 ℃ for 24 hours, and cleaning by using ethanol; vacuum activating at 120deg.C for 24 hr to obtain adsorbent;
wherein, coCl 2 And gallic acid in a molar ratio of 1:2; coCl 2 And KOH was present in a molar ratio of 1:0.5.
Example 2
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the structural formula of the adsorbent is Mg (C 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method described with reference to example 1 differs only in that: coCl is to be processed 2 Replacement with MgCl 2 。
Example 3
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereofIn the method, the structural formula of the adsorbent is Ni (C) 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method described with reference to example 1 differs only in that: coCl is to be processed 2 Replaced by NiCl 2 。
Example 4
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method described in reference to example 1 differs only in that the concentration of KOH solution is 0.1mol/L.
Example 5
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the structural formula of the adsorbent is Co (C 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method comprises the following steps:
CoCl is to be processed 2 Stirring and mixing gallic acid and 0.5mol/L KOH aqueous solution at a rotating speed of 500rpm, reacting at 100 ℃ for 72 hours, and cleaning by using ethanol; vacuum activating at 150deg.C for 18 hr to obtain adsorbent;
wherein, coCl 2 And gallic acid in a molar ratio of 1:1; coCl 2 And KOH was present in a molar ratio of 1:10.
Example 6
The embodiment provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the adsorbentIs of the structure Co (C) 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method comprises the following steps:
CoCl is to be processed 2 Stirring and mixing gallic acid and 0.01mol/L KOH aqueous solution at a rotating speed of 1000rpm, reacting at 140 ℃ for 48 hours, and cleaning by using ethanol; vacuum activating at 50deg.C for 48 hr to obtain adsorbent;
wherein, coCl 2 And gallic acid in a molar ratio of 1:0.5; coCl 2 And KOH was present in a molar ratio of 1:0.05.
Comparative example 1
The comparative example provides an adsorbent for separating chloropropane and chloropropene mixed gas and a preparation method thereof, wherein the structural formula of the adsorbent is Zn (C) 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure; the preparation method comprises the following steps:
ZnCl 2 Stirring and mixing gallic acid and 0.05mol/L KOH aqueous solution at a rotating speed of 800rpm, reacting at 120 ℃ for 24 hours, and cleaning by using ethanol; vacuum activating at 120deg.C for 24 hr to obtain adsorbent;
wherein ZnCl 2 And gallic acid in a molar ratio of 1:2; znCl 2 And KOH was present 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, wherein the structural formula of the adsorbent is Mn (C 7 O 5 H 4 )·2H 2 O, the aperture of the adsorbent isThe adsorbent isIs of a three-dimensional net structure; the preparation method comprises the following steps:
MnCl is added to 2 Stirring and mixing gallic acid and 0.05mol/L KOH aqueous solution at a rotating speed of 800rpm, reacting at 120 ℃ for 24 hours, and cleaning by using ethanol; vacuum activating at 120deg.C for 24 hr to obtain adsorbent;
wherein MnCl 2 And gallic acid in a molar ratio of 1:2; mnCl 2 And KOH was present in a molar ratio of 1:0.05.
The adsorbents obtained in the above examples and comparative examples were tested for the adsorption amount and separation selectivity of chloropropene and chloropropane by the following methods:
adsorption amount: measuring adsorption isotherms of the adsorbents to the gases by a full-automatic capacity gas adsorption instrument (Microtracbel BELSORP-max), so as to measure adsorption quantity;
separation selectivity: the calculation formula of the separation selectivity of the adsorbent to chloropropene is as follows:
q 1 and q 2 Refers to the adsorbent at p 1 And p 2 Equilibrium adsorption capacity under partial pressure, separation selectivity is the selectivity of the adsorbent under 101kPa partial pressure;
the results of the test of the adsorption amounts and adsorption selectivities of chloropropene and chloropropane in the above examples and comparative examples are shown in Table 1.
TABLE 1
From table 1, the following points can be found:
(1) As can be seen from examples 1-6, the adsorbent prepared by the invention shows preferential adsorption of chloropropene, the adsorption quantity of chloropropene is obviously larger 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) It can be seen from examples 1-3 that the types of transition metal ions in the adsorbents realize the regulation and control of adsorption performance, and the pore diameters of examples 1-3 are sequentially reduced, and the adsorption amounts of chloropropene and chloropropane are sequentially reduced;
(3) Comparing example 1 with example 4, it can be seen that Co (C 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 since the pore size of the adsorbent in comparative example 1 isLess than the preferred->The diffusion resistance of chloropropene is overlarge, and the adsorption amount of the adsorbent is reduced; since the pore diameter of the adsorbent in comparative example 2 is +.>Is beyond the preferred->Can cause chloropropane to also diffuse into the pores of the adsorbent material, resulting in reduced selectivity of the adsorbent material.
Application example 1
The adsorbent Co (C) obtained in example 1 7 O 5 H 4 )·2H 2 O is put into an adsorption column with the inner diameter of 5mm, nitrogen is used as carrier gas at the temperature of 30 ℃, the mixed gas of chloropropene and chloropropane with the mass ratio of 1:1 is introduced into the adsorption column to contact with the adsorbent at the speed of 3mL/min, the chloropropene in the mixed gas is adsorbed under the pressure of 350kPa, and the discharged gas is treatedAnd (3) carrying out gas phase detection by adopting a gas chromatograph, wherein when the concentration of the chloropropane is suddenly increased, the chloropropane is penetrated, and when the chloropropane is penetrated, the adsorption separation of the chloropropene and the chloropropane mixed gas is completed.
The penetration curves of the chloropropene and the chloropropane obtained in the application example are shown in figure 1, and as can be seen from figure 1, the chloropropane breaks through in about 5 minutes and is maintained for a period of time; chloropropene breaks through in about 13 minutes and finally reaches equilibrium.
The adsorption isotherm of the present application example for chloropropene and chloropropane at 30 ℃ is shown in fig. 2, and it can be seen from fig. 2 that the adsorption amount of the adsorbent for chloropropene increases significantly with increasing 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 gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 2
The adsorbent obtained in example 2 was subjected to Mg (C) 7 O 5 H 4 )·2H 2 O is put into an adsorption column with the inner diameter of 5mm, helium is used 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 to contact with an adsorbent at the speed of 3mL/min, the chloropropene in the mixed gas is adsorbed under the pressure of 100kPa, the gas phase detection is carried out on the discharged gas by adopting a gas chromatograph, and when the concentration of the chloropropane is suddenly increased, the chloropropane penetration is obtained, and the adsorption separation of the chloropropene and the chloropropane mixed gas is completed when the chloropropene is penetrated.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 3
The adsorbent Ni (C) obtained in example 3 7 O 5 H 4 )·2H 2 O is put into an adsorption column with the inner diameter of 5mm, helium is used as carrier gas at 20 ℃, the mixed gas of chloropropene and chloropropane with the mass ratio of 1:1 is introduced into the adsorption column to contact with an adsorbent at the speed of 3mL/min, the chloropropene in the mixed gas is adsorbed under the pressure of 200kPa, the gas phase detection is carried out on the discharged gas by adopting a gas chromatograph, and when the concentration of the chloropropane is suddenly increased, the chloropropane penetration is obtained, and the adsorption separation of the chloropropene and the chloropropane mixed gas is completed when the chloropropene is penetrated.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 4
The adsorbent Co (C) obtained in example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 O is used to separate the mixed gas of chloropropene and chloropropane, differing only in: the mixed gas of chloropropene and chloropropane is introduced into an adsorption column to contact with the adsorbent at a speed of 1 mL/min.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 5
The adsorbent Co (C) obtained in example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 O is used to separate the mixed gas of chloropropene and chloropropane, differing only in: the mixed gas of chloropropene and chloropropane is introduced into an adsorption column to contact with the adsorbent at a speed of 2 mL/min.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 6
The adsorbent Co (C) obtained in example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 O is used to separate the mixed gas of chloropropene and chloropropane, differing only in: 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 gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 7
The adsorbent Co (C) obtained in example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 O is used to separate the mixed gas of chloropropene and chloropropane, differing only in: the temperature of the mixed gas for adsorption separation of chloropropene and chloropropane is changed from 30 ℃ to 40 ℃.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Application example 8
The adsorbent Co (C) obtained in example 1 was prepared by the method described in application example 1 7 O 5 H 4 )·2H 2 O is used to separate the mixed gas of chloropropene and chloropropane, differing only in: the inner diameter of the adsorption column is replaced by 10mm from 5 mm.
The gas flowing out of the application example is detected and analyzed by a gas chromatograph, the gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is tested to be more than 99.99%, and the adsorption column can be recycled.
Comparative application example 1
The adsorbent Zn (C) obtained in comparative example 1 was treated by the method described in application example 1 7 O 5 H 4 )·2H 2 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 gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is 99.8% after testing, and the adsorption column can be recycled.
Comparative application example 2
The 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 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 gas chromatograph is vacuumized at 100 ℃ to desorb the adsorbent after the chloropropene is adsorbed, so that the chloropropene gas is obtained, the purity of the chloropropene obtained in the application example is 98% after testing, and the adsorption column can be recycled.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (16)

1. An adsorbent for separating chloropropane and chloropropene mixed gas, which is characterized by comprising 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 aperture of the adsorbent isThe adsorbent is of a three-dimensional net structure;
the transition metal ion is Co 2+ And/or Mg 2+ ；
The preparation method of the adsorbent comprises the following steps:
mixing transition metal salt, an organic ligand and an 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 mol ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10);
the temperature of the reaction is 100-140 ℃;
the reaction time is 24-72h;
the metal cation of the transition metal salt is Co 2+ And/or Mg 2+ The anions of the transition metal salt comprise Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of the following;
the organic ligand is gallic acid.
2. A method of preparing the adsorbent of claim 1, comprising the steps of:
mixing transition metal salt, an organic ligand and an 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 mol ratio of the transition metal salt to the alkali in the alkali solution is 1 (0.05-10);
the temperature of the reaction is 100-140 ℃;
the reaction time is 24-72h;
the metal cation of the transition metal salt is Co 2+ And/or Mg 2+ The anions of the transition metal salt comprise Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of these.
3. The method of claim 2, wherein the organic ligand is gallic acid.
4. The method according to claim 2, wherein the concentration of the alkali in the alkali solution is 0.01 to 0.5mol/L.
5. The method of claim 2, wherein the solvent of the alkaline solution comprises deionized water.
6. The method of claim 2, wherein the alkali in the alkaline solution comprises any one or a combination of at least two of NaOH, KOH, or LiOH.
7. The method of claim 2, wherein the mixing is by stirring.
8. The method according to claim 7, wherein the stirring speed is 500 to 1000rpm.
9. The production method according to claim 2, characterized in that the production method further comprises: after the reaction, the reaction product of the reaction is washed before the vacuum activation.
10. The method of claim 9, wherein the washing detergent comprises ethanol.
11. The method of claim 2, wherein the vacuum activation temperature is 50-150 ℃.
12. The method of claim 11, wherein the vacuum activation temperature is 100-140 ℃.
13. The method of claim 2, wherein the vacuum activation is for 18-48 hours.
14. The method of claim 13, wherein the vacuum activation is for a period of 24-32 hours.
15. The preparation method according to claim 2, characterized in that the preparation method comprises the steps of:
stirring and mixing transition metal salt, gallic acid and 0.01-0.5mol/L alkali solution at 500-1000rpm, reacting at 100-140 deg.C for 24-72h, and cleaning with ethanol; vacuum activating at 50-150deg.C for 18-48 hr to obtain adsorbent;
wherein the mol ratio of the transition metal salt to the gallic acid is 1 (0.5-2); the mol 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 is Co 2+ And/or Mg 2+ The anions of the transition metal salt comprise Cl - 、NO 3 - Or SO 4 2- Any one or a combination of at least two of the following; the alkali in the alkali solution comprises any one or a combination of at least two of NaOH, KOH or LiOH.
16. A separation method of the adsorbent of claim 1 for a mixed gas of chloropropane and chloropropene, comprising the steps of: the adsorbent is placed in the mixed gas of chloropropene and chloropropane, and is subjected to adsorption separation at 0-50 ℃ and 10-500 kPa.
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