CN107552006B - Porous solid supported metal-based ionic liquid for enriching HCl gas - Google Patents
Porous solid supported metal-based ionic liquid for enriching HCl gas Download PDFInfo
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Abstract
The invention discloses a porous solid load metal-based ionic liquid for enriching HCl gas, which is mainly used for HCl/C2H2HCl gas is enriched in industrial tail gas generated in the synthesis of vinyl chloride by the hydrochlorination of mixed gas or acetylene; or in HCl/C2H2And (3) enriching HCl gas in the mixed feed gas and catalyzing acetylene hydrochlorination reaction. The porous solid supported metal-based ionic liquid consists of a porous solid carrier and an active component supported on the porous solid carrier, wherein the active component is metal-based ionic liquid, and the metal-based ionic liquid is a compound of ionic liquid and metal chloride. The compound ionic liquid adopted by the invention has excellent selective adsorption performance on HCl, the adsorption rate of HCl can reach 99.5% to the maximum, and the purity of HCl gas obtained by adsorbing and enriching HCl gas and desorbing the HCl gas can reach 99.99% to the maximum.
Description
Technical Field
The invention relates to the field of gas enrichment, in particular to a porous solid supported metal-based ionic liquid for enriching HCl gas.
Background
In the industry of the hydrochlorination of acetylene to vinyl chloride, there are mixed gases containing HCl, e.g. HCl/C2H2Mixed gases, vinyl chloride industrial off-gases, etc., in which separation of HCl gas is a problem. In the industry, the HCl in the tail gas of vinyl chloride industry is usually absorbed and removed by lye, the method is simple, but the HCl is converted into chloride with low added value and cannot be recycled, and the discharge of waste liquid is increased.
The adsorption separation method is a common method for separating and recovering valuable gases from mixed gases, and the method relies on selective adsorption of specific gases by an adsorption material and realizes adsorption and desorption regeneration along with temperature and pressure changes, wherein the adsorption material is the key.
The most commonly used adsorbent material is molecular sieves. Chinese patent CN106794443A discloses a novel Carbon Molecular Sieve (CMS) as a gas adsorption separation material comprising a molecular sieve having an average pore size in the range of
To
The microporous carbonized vinylidene chloride copolymer of (1). The ability of these materials to separate gas mixtures including, for example, propane/propylene, nitrogen/methane, and ethane/ethylene. Chinese patent CN106799202A discloses a molecular sieve adsorbent for gas separation and a preparation method thereof. It has RHO molecular sieve configuration and chemical composition molar ratio of X2O3：mYO2：nM2O, wherein X is a trivalent element, Y is a tetravalent element, and M is a monovalent element or a monovalent cation. The molecular sieve is synthesized by a hydrothermal method by adopting initial gel prepared by mixing crown ether, alkali, water, a silicon source and an aluminum source. Compared with the traditional molecular sieves which preferentially adsorb nitrogen, such as Li exchange X type molecular sieves, the molecular sieve has higher tetravalent element Y content and is less influenced by the corrosion action of water vapor; compared with the traditional RHO molecular sieve, the molecular sieve can preferentially adsorb a large amount of nitrogen in nitrogen-oxygen separation and preferentially adsorb a large amount of oxygen in oxygen-argon separation. When the molecular sieve is applied to the air separation process, the molecular sieve has high stability and high separation performance, so that the production efficiency of the PSA air separation process can be ensured.
The metal organic framework material also has better gas adsorption and separation effects. For example, chinese patent CN106807330A discloses a Metal Organic Framework (MOFs) as an adsorbent, which is a porous structure material formed by coordination and complexation of metal ions and organic ligands in a solvent. The MOFs material can be used in the rapid pressure swing adsorption separation process with a short cycle period, greatly improves the processing capacity of a unit volume device, and is suitable for the purification processes of separation, purification, concentration, purification and the like of gas mixtures with large air volumes. However, the patent does not specify such suctionThe range of use of the materials does not indicate the effect of adsorption separation on the HCl-containing mixed gas. Chinese patent CN106699817A discloses a preparation method and application of a metal organic framework material. Comprises 1) adding cobalt nitrate hexahydrate and 5- (4- (5-tetrazolyl) phenyl) isophthalic acid into a mixed solvent of N, N-dimethylformamide and water, and uniformly stirring to obtain a mixed solution; 2) placing the mixed solution in a closed high-pressure reaction kettle, heating to 100-110 ℃, preserving heat, and then cooling to room temperature to obtain a reaction product; 3) filtering the obtained reaction product to obtain red blocky crystals, and 4) exchanging the red blocky crystals with methanol, and then heating the red blocky crystals in vacuum at 220 ℃ for 5-7 hours to obtain the metal organic framework material. The metal organic framework material is used for CO and CO2To CO in the mixed gas2Selective adsorption separation. Chinese patent CN105944680A discloses a metal-organic framework material for adsorbing and separating propylene and propyne, which is a metal-organic framework material adsorbent containing anions, and the adsorbent is a highly ordered microporous organic-inorganic hybrid material with an adjustable pore diameter of 0.4-1.2 nm. The pore volume is 0.1-1.2cm3The/g is adjustable. The large number of anionic active sites and their highly ordered spatial arrangement make them exhibit excellent properties for the adsorption of propyne. Thereby having high propine selectivity and adsorption capacity and being a potential separation and purification technology of propylene and propine.
Ionic liquids can also be used for gas adsorption separations. Chinese patent CN104277880A discloses a method for absorbing and separating light hydrocarbon from dry gas or industrial tail gas by using ionic liquid. Taking ionic liquid or a mixed solvent of the ionic liquid and a molecular solvent as an absorbent, contacting with dry gas or industrial tail gas, absorbing to obtain absorption liquid containing light hydrocarbon, and then desorbing and separating to obtain the light hydrocarbon; the light hydrocarbon is alkane or alkene mainly containing C2-C4. The absorbent has high light hydrocarbon solubility and separation selectivity, can realize high-efficiency separation and recovery of light hydrocarbons, and has a maximum comprehensive recovery rate of 98.5%.
In HCl/C2H2HCl is absorbed in HCl-containing mixed gas such as mixed gas and industrial tail gas from chloroethylene synthesis by acetylene hydrochlorination, and then the HCl is enriched or separated and recoveredIt is very significant. However, no adsorbent having a high selective adsorption effect on HCl in a mixed gas containing HCl has been reported so far.
In addition, in reactions involving HCl-containing gases, excess HCl is often required to increase the conversion of another more valuable reactant, such as C2H2HCl/C in the hydrochlorination of HCl to vinyl chloride2H2The molar ratio is generally greater than 1. If the HCl/C in the reaction environment of hydrogen chloride and acetylene can be improved2H2The molar ratio of the raw material gas can also achieve the reaction effect of excessive HCl in the mixed raw material gas of acetylene and hydrogen chloride. At present, no public reports in the technical field are found.
Disclosure of Invention
The invention provides a material for adsorbing/enriching HCl gas, and the material is applied to HCl/C2H2HCl is absorbed in industrial tail gas generated in the synthesis of vinyl chloride by the hydrochlorination of mixed gas and acetylene, and then the HCl is separated and recovered; or to HCl/C2H2HCl is enriched in the mixed feed gas and efficient acetylene hydrochlorination is carried out.
The invention comprises the following technical scheme:
the invention provides a material for adsorbing/enriching HCl gas, namely application of porous solid supported metal-based ionic liquid in HCl gas enrichment; the porous solid supported metal-based ionic liquid consists of a porous solid carrier and an active component supported on the porous solid carrier,
the porous solid carrier is selected from one of activated carbon, mesoporous carbon, carbon nano tubes, silicon oxide, aluminum oxide, titanium oxide, molecular sieves, metal organic framework compounds and covalent organic framework compounds, and is preferably activated carbon; the active component is metal-based ionic liquid which is a compound of ionic liquid and metal chloride; the ionic liquid is imidazole, pyridine, quaternary phosphonium or pyrrolidine ionic liquid;
further, the cation of the ionic liquid is N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, 1-butyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-ethyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole, 1-butyl-2, 3-dimethylimidazole, 1-butyl-3-methylimidazole, tributylmethylphosphine, tributylethylphosphine, tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, N-butylpyrrolidine, N-butyl-3-methylimidazole, 1-hexyl-3-methylimidazole, tributylethylphosphine, tetrabutylphosphine, tributyldodecylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylphosphine, triphenylbenzylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylbromomethylphosphine, triphenylmethoxyphosphine, triphenylethoxycarbonylmethylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylvinylphosphine, tetraphenylphosphine; the anion of the ionic liquid is chloride ion, bromide ion, trifluoromethanesulfonimide or iminium radical;
the metal chloride is one or more of gold chloride, palladium chloride, ruthenium chloride, platinum chloride, copper chloride, aluminum chloride, indium chloride, mercury chloride, bismuth chloride, ferric chloride, manganese chloride, barium chloride and calcium chloride, and preferably is gold chloride, palladium chloride, ruthenium chloride, copper chloride, aluminum chloride, indium chloride, ferric chloride and barium chloride.
Further, the invention provides a preparation method of the porous solid supported metal-based ionic liquid, which comprises the following steps: (1) respectively heating the ionic liquid and the metal chloride at 80-200 ℃ for 3-20 h; uniformly mixing the heated ionic liquid and metal chloride, heating to 60-200 ℃, stirring for 0.5-6 h, melting until transparent clear liquid is obtained, stopping heating, preparing metal-based ionic liquid, and transferring to a closed container for sealed storage; based on the total mass of the obtained metal-based ionic liquid, the mass usage of the metal chloride accounts for 0.01-10% of the total mass, and the balance is the ionic liquid;
(2) firstly, vacuum drying the porous solid at 60-120 ℃ for 3-20 h; dissolving the metal-based ionic liquid prepared in the step (1) in a solvent, dropwise adding the solvent in which the metal-based ionic liquid is dissolved into a porous solid carrier at 0-100 ℃ under the action of ultrasonic waves, uniformly mixing, and then soaking for 1-12 hours under the action of ultrasonic waves; and then heating the porous solid supported metal-based ionic liquid in vacuum at the temperature of 100-200 ℃ for 12-24 hours to obtain the porous solid supported metal-based ionic liquid.
Further, the mass ratio of the metal-based ionic liquid to the porous solid is 0.05-0.5: 1.
the porous solid has a thickness of at least 50m2A BET specific surface area of at least 300m2BET specific surface area/g; has a pore volume of at least 0.2mL/g, preferably at least 0.35 mL/g.
Further, the solvent is water, fatty alcohol, acetonitrile, hydrochloric acid, toluene, benzene, acetone, cyclohexane, DMF, NMP, aqua regia, organic aqua regia, nitrobenzene, tetrahydrofuran, propanethiol, thiourea, methyl chloride, carbon disulfide or hydrogen peroxide.
Further, the mass ratio of the solvent to the metal-based ionic liquid is recommended to be 0.5-5: 1.
specifically, the preparation method of the porous solid supported metal-based ionic liquid of the present invention is preferably performed as follows: (1) respectively heating the ionic liquid and the metal chloride at 95-170 ℃ for 7-18 h; uniformly mixing the heated ionic liquid and metal chloride, heating to 70-170 ℃, stirring for 2-6 h, melting until transparent clear liquid is obtained, stopping heating, preparing metal-based ionic liquid, and transferring the metal-based ionic liquid into a closed container for sealed storage; based on the total mass of the obtained metal-based ionic liquid, the mass usage of the metal chloride accounts for 1-6.5% of the total mass, and the balance is the ionic liquid;
(2) firstly, vacuum drying the porous solid at 60-120 ℃ for 3-18 h; dissolving the metal-based ionic liquid prepared in the step (1) in a solvent, dropwise adding the solvent in which the metal-based ionic liquid is dissolved into a porous solid carrier at the temperature of 20-55 ℃ under the action of ultrasonic waves, uniformly mixing, and then soaking for 2-5 hours under the action of ultrasonic waves; and then heating the porous solid supported metal-based ionic liquid in vacuum at the temperature of 100-190 ℃ for 12-20 h to obtain the porous solid supported metal-based ionic liquid.
Furthermore, the porous solid supported metal-based ionic liquid can be applied to HCl/C2H2Synthesis of chloroethylene by hydrochlorination of mixed gas or acetyleneEnriching HCl in the alkene industrial tail gas; or to HCl/C2H2And (3) enriching HCl in the mixed feed gas and catalyzing acetylene hydrochlorination.
The porous solid supported metal-based ionic liquid can be applied to HCl/C2H2The method for enriching HCl in the mixed gas comprises the following steps: filling the porous solid supported metal-based ionic liquid in the invention into a fixed bed reactor, and then introducing HCl/C at a lower adsorption operation temperature2H2The mixed gas is adsorbed at low temperature, and very high HCl/C can be achieved in the porous solid load metal-based ionic liquid2H2A ratio; and using HCl and C2H2The difference of the acting force of the HCl and the ionic liquid (the acting force of the HCl and the ionic liquid is much higher than that of C)2H2Acting force with ionic liquid), and then acting on the porous solid loaded with metal-based ionic liquid after adsorbing the mixed gas through microwave, so as to selectively load trace C2H2Desorbing the gas from the ionic liquid, and retaining most HCl in the ionic liquid; and then the temperature is increased and the pressure is reduced, and HCl is desorbed to obtain high-purity HCl gas.
Specifically, the porous solid supported metal-based ionic liquid is filled in a fixed bed reactor, and HCl/C is introduced at a lower adsorption operation temperature of 0-80 DEG C2H2The mixed gas is subjected to low-temperature adsorption, and trace C is selectively removed by microwave2H2Desorbing gas from the ionic liquid; then HCl can be desorbed at high temperature and low pressure to obtain high-purity HCl, so that HCl enrichment is realized;
the HCl/C2H2Initial HCl/C in gas mixture2H2The ratio is 0.3-1.2: 1;
the volume airspeed of the mixed gas is 10-500 h-1；
The low-temperature adsorption operation pressure is 0.1-1.1 MPa;
the microwave action operating temperature is 0-80 ℃;
the microwave action operation time is 0.5-8 h;
the desorption operation pressure after low-temperature adsorption is 0.01-0.05 MPa;
the desorption operation temperature after low-temperature adsorption is 40-140 ℃.
Furthermore, the porous solid supported metal-based ionic liquid can be applied to HCl/C2H2The method for enriching HCl in the mixed raw material gas and catalyzing acetylene hydrochlorination reaction comprises the following steps:
filling the porous solid supported metal-based ionic liquid into a fixed bed reactor, and then introducing HCl/C at a higher adsorption operation temperature of 100-200 DEG C2H2Adsorbing the mixed raw material gas, and taking the porous solid loaded metal-based ionic liquid after adsorbing HCl as a catalyst for acetylene hydrochlorination to realize HCl enrichment and acetylene hydrochlorination;
the HCl/C2H2Initial HCl/C in mixed feed gas2H2The ratio is 0.3-1.2: 1;
the volume airspeed of the mixed gas is 10-500 h-1；
The hydrochlorination reaction is carried out at the operating temperature of 100-200 ℃ after the high-temperature adsorption;
the operating pressure for carrying out the hydrochlorination reaction of acetylene after high-temperature adsorption is 0.1-0.5 MPa.
The method for enriching HCl in industrial tail gas generated in the synthesis of vinyl chloride by acetylene hydrochlorination by using the porous solid supported metal-based ionic liquid comprises the following steps: porous solid load metal base ionic liquid is used as an adsorbent, the adsorbent is loaded into a fixed bed absorption tower, acetylene is introduced to synthesize industrial tail gas of vinyl chloride through hydrochlorination, and the porous solid load metal base ionic liquid can effectively adsorb HCl in the mixed gas; selectively mixing trace chloroethylene and C by microwave2H2Desorbing the impurity gas from the ionic liquid; then desorbing HCl to obtain high-purity HCl gas, so as to realize HCl enrichment;
the volume content of HCl in the industrial tail gas is 0.01-50%;
the volume airspeed of the industrial tail gas is 10-500 h-1；
The operation temperature for adsorbing HCl is 0-120 ℃;
the HCl adsorption operation pressure is 0.1-1.1 MPa;
the microwave action operating temperature is 0-80 ℃;
the microwave action operation time is 0.5-8 h;
the operation temperature for desorbing HCl is 80-220 ℃;
the HCl desorption operation pressure is 0.01-0.05 MPa;
by adopting the porous solid supported metal-based ionic liquid as the adsorbent, HCl/C can be effectively adsorbed2H2HCl in industrial tail gas generated in vinyl chloride synthesis through hydrochlorination of mixed gas and acetylene is adsorbed and enriched, the adsorption recovery rate can reach 99.5% to the maximum, and the purity of the obtained HCl is high and can reach 99.99% to the maximum. The porous solid supported ionic liquid can be used as a catalyst for acetylene hydrochlorination, has the effect of enriching HCl, can realize high-efficiency acetylene hydrochlorination, and can realize acetylene conversion rate>99.5% selectivity>99.96%, and the stability can reach at least 12 months.
Compared with the prior art, the invention has the following advantages:
the compound ionic liquid adopted by the invention has excellent selective adsorption performance on HCl and can effectively adsorb HCl/C2H2HCl is separated and enriched from industrial tail gas generated in the synthesis of vinyl chloride by hydrochlorinating mixed gas and acetylene, and the highest adsorption rate of HCl can reach 99.5%.
Secondly, the porous solid material of the invention is loaded with metal-based ionic liquid, so that the porous solid material can absorb HCl in an absorption tower, and has the advantages of convenient operation, good separation effect and simple desorption.
Thirdly, the HCl gas obtained after adsorption, enrichment, desorption and desorption has high purity which can reach 99.99 percent at most.
The porous solid material loaded composite ionic liquid can also be used as a catalyst for acetylene hydrochlorination reaction and can be used in HCl/C2H2The HCl is enriched and the concentration is carried out when the ratio is 1:1High efficiency acetylene hydrochlorination.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
100g of N-hexylpyridinium chloride ionic liquid and 5g of copper chloride were heated at 80 ℃ for 20 hours, respectively. Uniformly mixing 100g of N-hexylpyridinium chloride ionic liquid and 5g of copper chloride, putting the mixture into a beaker, heating the mixture to 100 ℃, stirring the mixture for 2 hours, melting the mixture until transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
The columnar active carbon is selected as a carrier, the particle size is 20 meshes, the ash content is 6.0wt percent, and the specific surface area is 800m2The pore volume is 0.20mL/g, and the activated carbon is dried in vacuum at 100 ℃ for 24 hours. Dissolving 5g of the metal-based ionic liquid in 20g of water, dropwise adding a solvent in which the metal-based ionic liquid is dissolved into 100g of an activated carbon carrier at 20 ℃ under the action of ultrasonic waves, uniformly mixing, and soaking for 2 hours under the action of ultrasonic waves; and then heating the mixture for 20 hours in vacuum at the temperature of 100 ℃ to obtain the porous solid supported metal-based ionic liquid A.
2g of load type metal-based ionic liquid material A is loaded into a fixed bed absorption tower, and HCl/C is introduced at the temperature of 20 DEG C2H2Mixing gas, wherein the pressure of the mixed gas is 0.3MPa, the volume content of HCl is 10 percent, and the volume space velocity of the mixed gas is 50h-1(ii) a Adsorbing for 4 h. Stopping introducing the mixed gas, and performing microwave action at 20 ℃ for 2 h; then HCl desorption is carried out, the temperature in the tower is increased to 50 ℃, the pressure is reduced to 0.01MPa, HCl gas with the purity of 99.98 percent is obtained, and the adsorption recovery rate of HCl reaches 99.4 percent.
Example 2
100g of N-butyl-N-methylpyrrolidine bromide ionic liquid and 10g of palladium chloride are heated at 120 ℃ for 16h respectively. Uniformly mixing 100g of N-butyl-N-methylpyrrolidine bromide ionic liquid and 10g of palladium chloride, putting the mixture into a beaker, heating the mixture to 120 ℃, stirring the mixture for 3 hours, melting the mixture until transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Selecting columnar carbon nano-tubes as a carrier, wherein the particle size of the columnar carbon nano-tubes is 80 meshes, the ash content is 3.0 wt%, and the specific surface area is 400m2The pore volume is 0.50mL/g, and the carbon nano tube is dried in vacuum at 110 ℃ for 20 hours. Dissolving 20g of the metal-based ionic liquid in 50g of ethanol, dropwise adding a solvent in which the metal-based ionic liquid is dissolved into 100g of carbon nanotube carrier at 30 ℃ under the action of ultrasonic waves, uniformly mixing, and soaking for 2 hours under the action of ultrasonic waves; and then heating the mixture for 20 hours in vacuum at the temperature of 100 ℃ to obtain the porous solid supported metal-based ionic liquid B.
2g of load type metal-based ionic liquid material B is loaded into a fixed bed absorption tower, and HCl/C is introduced at 10 DEG C2H2Mixing gas, wherein the pressure of the mixed gas is 0.2MPa, the volume content of HCl is 30 percent, and the volume space velocity of the mixed gas is 20h-1(ii) a Adsorbing for 3.5 h. Stopping introducing the mixed gas, and performing microwave action at 10 ℃ for 8 h; then HCl desorption is carried out, the temperature in the tower is raised to 80 ℃, the pressure is reduced to 0.02MPa, HCl gas with the purity of 99.99 percent is obtained, and the adsorption recovery rate of HCl reaches 99.5 percent.
Example 3
100g of 1-propyl-3-methylimidazolium chloride ionic liquid and 7g of ruthenium chloride were heated at 140 ℃ for 14 h. Uniformly mixing 100g of 1-propyl-3-methylimidazolium chloride ionic liquid and 7g of ruthenium chloride, putting the mixture into a beaker, heating the mixture to 130 ℃, stirring the mixture for 4 hours, melting the mixture until a transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Selecting columnar gamma-Al2O3Is a carrier with a particle size of 60 meshes and a specific surface area of 120m2G, pore volume 0.40mL/g, gamma-Al first2O3Drying at 150 deg.C under vacuum for 18 h. Dissolving 25g of the metal-based ionic liquid in 40g of acetone, and dropwise adding a solvent in which the metal-based ionic liquid is dissolved to 100g of gamma-Al at 40 ℃ under the action of ultrasonic waves2O3Uniformly mixing the carrier, and soaking the carrier for 4 hours under the action of ultrasonic waves; and then heating the mixture for 15 hours in vacuum at 105 ℃ to obtain the porous solid supported metal-based ionic liquid C.
2g of load type metal-based ionic liquid material C is loaded into a fixed bed absorption tower, and then acetylene is introduced at 30 ℃ to synthesize industrial tail gas of vinyl chloride through hydrochlorination, wherein the pressure of mixed gas is 1.0MPa, the volume content of HCl is 2.0 percent, and the volume space velocity of the mixed gas is 80h-1(ii) a Adsorbing for 4 h. Stopping introducing the mixed gas, and performing microwave action at 30 ℃ for 4 hours; then HCl desorption is carried out, the temperature in the tower is increased to 190 ℃, the pressure is reduced to 0.02MPa, HCl gas with the purity of 99.94 percent is obtained, and the adsorption recovery rate of HCl reaches 99.2 percent.
Example 4
100g of the trifluoromethanesulfonimide salt of tributylmethylphosphine ionic liquid and 5g of ferric chloride were first heated at 170 ℃ for 14h, respectively. Uniformly mixing 100g of trifluoromethanesulfonimide salt ionic liquid of tributylmethylphosphine and 5g of ferric chloride, putting the mixture into a beaker, heating the mixture to 170 ℃, stirring the mixture for 5 hours, melting the mixture until a transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Selecting columnar SiO2Is a carrier with the particle size of 65 meshes and the specific surface area of 100m2The pore volume is 0.90mL/g, SiO is firstly added2Vacuum drying at 120 deg.C for 5 h. 40g of the metal-based ionic liquid is dissolved in 90g of DMF, and then the solvent in which the metal-based ionic liquid is dissolved is dropwise added to 100g of SiO under the action of ultrasonic waves at 50 DEG C2Uniformly mixing the carrier, and soaking the carrier for 4.5 hours under the action of ultrasonic waves; and then heating the mixture for 8 hours in vacuum at 105 ℃ to obtain the porous solid supported metal-based ionic liquid D.
Loading the loaded metal-based ionic liquid material D into a fixed bed absorption tower, and then introducing acetylene to synthesize industrial tail gas of vinyl chloride through hydrochlorination at 70 ℃, wherein the pressure of mixed gas is 0.5MPa, the volume content of HCl is 2.5%, and the volume space velocity of the mixed gas is 70h-1(ii) a Adsorbing for 4 h. Stopping introducing the mixed gas, and performing microwave action at 70 deg.C for 0.5 h; then HCl desorption is carried out, the temperature in the tower is increased to 180 ℃, the pressure is reduced to 0.01MPa, HCl gas with the purity of 99.92 percent is obtained, and the adsorption recovery rate of HCl reaches 99.5 percent.
Example 5
100g of N-octyl pyridinium chloride ionic liquid and 1g of gold chloride were heated at 95 ℃ for 18h, respectively. Uniformly mixing 100g of N-octyl pyridinium chloride ionic liquid and 1g of gold chloride, putting the mixture into a beaker, heating the mixture to 170 ℃, stirring the mixture for 3 hours, melting the mixture until transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Selecting columnar TiO2Is a carrier with a particle size of 50 meshes and a specific surface area of 150m2Per g, pore volume 0.25mL/g, TiO first2Vacuum drying treatment at 140 deg.C for 13 h. Dissolving 50g of the metal-based ionic liquid in 25g of acetonitrile, and dropwise adding a solvent in which the metal-based ionic liquid is dissolved to 100g of TiO under the action of ultrasonic waves at 30 DEG2Uniformly mixing the carrier, and soaking for 2.5h under the action of ultrasonic waves; and then heating the mixture for 12 hours in vacuum at the temperature of 100 ℃ to obtain the porous solid supported metal-based ionic liquid E.
2g of load type metal-based ionic liquid material E is loaded into a fixed bed reactor, and then HCl/C is introduced2H2Mixing of gases, in which HCl/C2H21/1, the volume space velocity of the mixed gas is 20h-1The reaction temperature is 180 ℃ and the pressure is 0.2 Mpa. The conversion rate of acetylene is 99.99% and the selectivity is 100% at the initial stage of the reaction, and after 9 months of operation, the conversion rate of acetylene is 99.7% and the selectivity is 99.9%.
Example 6
100g of 1-butyl-2, 3-dimethylimidazole trifluoromethanesulfonimide salt ionic liquid, 5g of palladium chloride and 5g of indium chloride were heated at 170 ℃ for 8 h. Uniformly mixing 100g of 1-butyl-2, 3-dimethyl imidazole trifluoromethanesulfonimide salt ionic liquid, 5g of palladium chloride and 5g of indium chloride, putting the mixture into a beaker, heating the mixture to 160 ℃, stirring the mixture for 3.5 hours, melting the mixture until a transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Spherical active carbon is selected as a carrier, the particle size of the carrier is 70 meshes, the ash content is 1.8 percent, and the specific surface area is 1350m2The pore volume is 0.25mL/g, and the activated carbon is dried for 4 hours in vacuum at 150 ℃.5g of the above metal-based ionic liquid was dissolved in 25g of propanethiol and then at 30 deg.CDropwise adding a solvent dissolved with metal-based ionic liquid into 100g of activated carbon carrier under the action of ultrasonic waves, uniformly mixing, and soaking for 5 hours under the action of ultrasonic waves; and then heating the mixture for 13 hours in vacuum at 190 ℃ to obtain the porous solid supported metal-based ionic liquid F.
2g of load type metal-based ionic liquid material F is loaded into a fixed bed reactor, and then HCl/C is introduced2H2Mixing of gases, in which HCl/C2H20.8/1, and the volume space velocity of the mixed gas is 50h-1The reaction temperature is 180 ℃ and the pressure is 0.3 Mpa. The acetylene conversion rate at the initial stage of the reaction is 80%, the selectivity is 100%, and after 9 months of operation, the acetylene conversion rate is 79.9%, and the selectivity is 99.9%.
Example 7
100g of the chloride ionic liquid of tributylhexylphosphine, 1.5g of ruthenium chloride and 4g of aluminum chloride were heated at 200 ℃ for 3 hours, respectively. Uniformly mixing 100g of chloride ionic liquid of tributyl hexyl phosphine, 1.5g of ruthenium chloride and 4g of aluminum chloride, putting the mixture into a beaker, heating the mixture to 200 ℃, stirring the mixture for 2 hours, melting the mixture until transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
Selecting a granular ZSM-5 molecular sieve as a carrier, wherein the grain diameter of the molecular sieve is 10 meshes, and the specific surface area is 400m2The pore volume is 0.5mL/g, and the ZSM-5 molecular sieve is dried in vacuum at 90 ℃ for 18 h. Dissolving 25g of the metal-based ionic liquid in 50g of aqua regia, dropwise adding a solvent in which the metal-based ionic liquid is dissolved into 100g of ZSM-5 molecular sieve carrier at 55 ℃ under the action of ultrasonic waves, uniformly mixing, and then soaking for 5 hours under the action of ultrasonic waves; and then heating the mixture for 18h at 180 ℃ in vacuum to obtain the porous solid supported metal-based ionic liquid G.
2G of load type metal-based ionic liquid material G is loaded into a fixed bed reactor, and then HCl/C is introduced2H2Mixing of gases, in which HCl/C2H20.6/1, and the volume space velocity of the mixed gas is 40h-1The reaction temperature is 160 ℃ and the pressure is 0.4 MPa. The acetylene conversion rate is 60% and the selectivity is 100% in the initial reaction period, and after 9 months of operation, the acetylene conversion rate is 59.8% and the selectivity is 99.9%.
Example 8
100g of tetraphenylphosphine chloride ionic liquid, 0.5g of gold chloride and 6g of barium chloride were heated at 190 ℃ for 12 hours, respectively. Uniformly mixing 100g of tetraphenylphosphine chloride ionic liquid, 0.5g of gold chloride and 6g of barium chloride, putting the mixture into a beaker, heating the mixture to 190 ℃, stirring the mixture for 0.5h, melting the mixture until a transparent liquid is obtained, and stopping heating; transferring the prepared metal-based ionic liquid into a closed container for sealing and storing.
The columnar activated carbon is selected as a carrier, the particle size is 25 meshes, the ash content is 7.1 percent, and the specific surface area is 1100m2The pore volume is 0.55mL/g, and the activated carbon is dried for 5 hours at 120 ℃ in vacuum. Dissolving 15g of the metal-based ionic liquid in 55g of hydrogen peroxide, dropwise adding a solvent in which the metal-based ionic liquid is dissolved into 100g of an activated carbon carrier at 45 ℃ under the action of ultrasonic waves, uniformly mixing, and soaking for 5 hours under the action of ultrasonic waves; and then heating the mixture for 15H in vacuum at 145 ℃ to obtain the porous solid supported metal-based ionic liquid H.
2g of load type metal-based ionic liquid material H is loaded into a fixed bed reactor, and then HCl/C is introduced2H2Mixing of gases, in which HCl/C2H20.3/1, and the volume space velocity of the mixed gas is 70h-1The reaction temperature is 190 ℃ and the pressure is 0.5 Mpa. The acetylene conversion rate is 30% and the selectivity is 100% in the initial reaction period, and after 9 months of operation, the acetylene conversion rate is 29.9% and the selectivity is 99.9%.
Comparative example 1
0.5g of gold chloride was first heated at 95 ℃ for 18 h. Selecting columnar TiO2Is a carrier with a particle size of 50 meshes and a specific surface area of 150m2The pore volume is 0.85mL/g, firstly TiO2Vacuum drying at 100 deg.C for 24 hr. 0.5g of the gold chloride is dissolved in 85g of acetonitrile and the solvent with the gold chloride dissolved therein is added dropwise to 100g of TiO under the action of ultrasonic waves at 30 DEG2Uniformly mixing the carrier, and soaking for 2.5h under the action of ultrasonic waves; then heating the mixture for 12 hours in vacuum at 160 ℃ to obtain a comparative catalyst W.
2g of comparative catalyst W are placed in a fixed-bed reactor and HCl/C is then introduced2H2Mixing of gases, in which HCl/C2H21/1, the volume space velocity of the mixed gas is 20h-1The reaction temperature is 180 ℃ and the pressure is 0.2 Mpa. The conversion rate of acetylene is 95.7% and the selectivity is 99.9% at the initial stage of the reaction, and after 9 months of operation, the conversion rate of acetylene is 36.1% and the selectivity is 97.5%.
Claims (10)
1. The application of a porous solid supported metal-based ionic liquid in HCl gas enrichment is characterized in that the porous solid supported metal-based ionic liquid consists of a porous solid carrier and an active component loaded on the porous solid carrier, wherein the porous solid carrier is selected from one of activated carbon, mesoporous carbon, carbon nano tubes, silicon oxide, aluminum oxide, titanium oxide, molecular sieves, metal organic framework compounds and covalent organic framework compounds; the active component is metal-based ionic liquid which is a compound of ionic liquid and metal chloride, and the cation of the ionic liquid is N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, 1-butyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-ethyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole, 1-butyl-2, 3-dimethylimidazole, 1-butyl-3-methylimidazole, tributylmethylphosphine, tributylethylphosphine, N-propylpyridine, N-methylimidazole, N-propylpyridine, N-, Tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylphosphine, triphenylbenzylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylbromomethylphosphine, triphenylmethoxyphosphine, triphenylethoxycarbonylmethylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylvinylphosphine, tetraphenylphosphine; the anion of the ionic liquid is chloride ion, bromide ion, trifluoromethanesulfonimide or iminium, and the metal chloride is one or more of gold chloride, palladium chloride, ruthenium chloride, platinum chloride, copper chloride, aluminum chloride, indium chloride, mercuric chloride, bismuth chloride, ferric chloride, manganese chloride, barium chloride and calcium chloride; the preparation method of the metal-based ionic liquid comprises the steps of heating the ionic liquid and metal chloride at 80-200 ℃ for 3-20 hours respectively; uniformly mixing the heated ionic liquid and metal chloride, heating to 60-200 ℃, stirring for 0.5-6 h, melting until transparent clear liquid is obtained, stopping heating, preparing metal-based ionic liquid, and transferring to a closed container for sealed storage; based on the total mass of the obtained metal-based ionic liquid, the mass usage of the metal chloride accounts for 0.01-10% of the total mass, and the balance is the ionic liquid;
the porous solid supported metal-based ionic liquid is applied to HCl/C2H2And (3) enriching HCl in the mixed gas: filling the porous solid supported metal-based ionic liquid into a fixed bed reactor, and then introducing HCl/C at a lower adsorption operation temperature of 0-80 DEG C2H2The mixed gas is subjected to low-temperature adsorption, and trace C is selectively removed by microwave2H2Desorbing gas from the ionic liquid; then HCl can be desorbed at high temperature and low pressure to obtain high-purity HCl, so that HCl enrichment is realized;
the HCl/C2H2Initial HCl/C in gas mixture2H2The ratio is 0.3-1.2: 1; the volume space velocity of the mixed gas is 10-500 h-1；
The low-temperature adsorption operation pressure is 0.1-1.1 MPa;
the microwave action operating temperature is 0-80 ℃; the microwave action operation time is 0.5-8 h;
the desorption operation pressure after low-temperature adsorption is 0.01-0.05 MPa; the desorption operation temperature after low-temperature adsorption is 40-140 ℃.
2. The application of claim 1, wherein the porous solid supported metal-based ionic liquid is prepared by a method comprising the following steps: firstly, vacuum drying the porous solid at 60-120 ℃ for 3-20 h; dissolving the metal-based ionic liquid prepared in the method in claim 1 in a solvent, then dropwise adding the solvent in which the metal-based ionic liquid is dissolved into a porous solid carrier at 0-100 ℃ under the action of ultrasonic waves, uniformly mixing, and then soaking for 1-12 hours under the action of ultrasonic waves; and then heating the porous solid supported metal-based ionic liquid in vacuum at the temperature of 100-200 ℃ for 12-24 hours to obtain the porous solid supported metal-based ionic liquid.
3. Use according to claim 2, characterized in that: the mass ratio of the metal-based ionic liquid to the porous solid is 0.05-0.5: 1.
4. use according to claim 2, characterized in that: the solvent is water, fatty alcohol, acetonitrile, hydrochloric acid, toluene, benzene, acetone, cyclohexane, DMF, NMP, aqua regia, organic aqua regia, nitrobenzene, tetrahydrofuran, propanethiol, thiourea, methyl chloride, carbon disulfide or hydrogen peroxide.
5. Use according to claim 2, characterized in that: the mass ratio of the solvent to the metal-based ionic liquid is 0.5-5: 1.
6. the application of a porous solid supported metal-based ionic liquid in HCl gas enrichment is characterized in that the porous solid supported metal-based ionic liquid consists of a porous solid carrier and an active component loaded on the porous solid carrier, wherein the porous solid carrier is selected from one of activated carbon, mesoporous carbon, carbon nano tubes, silicon oxide, aluminum oxide, titanium oxide, molecular sieves, metal organic framework compounds and covalent organic framework compounds; the active component is metal-based ionic liquid which is a compound of ionic liquid and metal chloride, and the cation of the ionic liquid is N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, 1-butyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-ethyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole, 1-butyl-2, 3-dimethylimidazole, 1-butyl-3-methylimidazole, tributylmethylphosphine, tributylethylphosphine, N-propylpyridine, N-methylimidazole, N-propylpyridine, N-, Tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylPhosphine, triphenylbenzylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylbromomethylphosphine, triphenylmethoxy phosphine, triphenylethoxycarbonylmethylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylvinylphosphine, tetraphenylphosphine; the anion of the ionic liquid is chloride ion, bromide ion, trifluoromethanesulfonimide or iminium, and the metal chloride is one or more of gold chloride, palladium chloride, ruthenium chloride, platinum chloride, copper chloride, aluminum chloride, indium chloride, mercuric chloride, bismuth chloride, ferric chloride, manganese chloride, barium chloride and calcium chloride; the preparation method of the metal-based ionic liquid comprises the steps of heating the ionic liquid and metal chloride at 80-200 ℃ for 3-20 hours respectively; uniformly mixing the heated ionic liquid and metal chloride, heating to 60-200 ℃, stirring for 0.5-6 h, melting until transparent clear liquid is obtained, stopping heating, preparing metal-based ionic liquid, and transferring to a closed container for sealed storage; based on the total mass of the obtained metal-based ionic liquid, the mass usage of the metal chloride accounts for 0.01-10% of the total mass, and the balance is the ionic liquid; the porous solid supported metal-based ionic liquid is applied to HCl gas enrichment in industrial tail gas generated in vinyl chloride synthesis through acetylene hydrochlorination: loading porous solid loaded metal-based ionic liquid serving as an adsorbent into a fixed bed absorption tower, introducing acetylene into the fixed bed absorption tower for hydrochlorination to synthesize vinyl chloride industrial tail gas, and adsorbing HCl in the mixed gas by using the porous solid loaded metal-based ionic liquid; selectively mixing trace chloroethylene and C by microwave2H2Desorbing impurity gas from the ionic liquid; then desorbing HCl to obtain high-purity HCl gas, so as to realize HCl enrichment; the volume content of HCl in the industrial tail gas is 0.01-50%; the volume airspeed of the industrial tail gas is 10-500 h-1(ii) a The operation temperature for adsorbing HCl is 0-120 ℃; the HCl adsorption operation pressure is 0.1-1.1 MPa; the microwave action operating temperature is 0-80 ℃; the microwave action operation time is 0.5-8 h; the operation temperature for desorbing HCl is 80-220 ℃; the HCl desorption operation pressure is 0.01-0.05 MPa.
7. The application of claim 6, wherein the preparation method of the porous solid supported metal-based ionic liquid comprises the steps of firstly, drying the porous solid at 60-120 ℃ in vacuum for 3-20 hours; dissolving the metal-based ionic liquid prepared in the method in claim 6 in a solvent, then dropwise adding the solvent in which the metal-based ionic liquid is dissolved into a porous solid carrier at 0-100 ℃ under the action of ultrasonic waves, uniformly mixing, and then soaking for 1-12 hours under the action of ultrasonic waves; and then heating the porous solid supported metal-based ionic liquid in vacuum at the temperature of 100-200 ℃ for 12-24 hours to obtain the porous solid supported metal-based ionic liquid.
8. The use of claim 7, wherein: the mass ratio of the metal-based ionic liquid to the porous solid is 0.05-0.5: 1.
9. the use of claim 7, wherein: the solvent is water, fatty alcohol, acetonitrile, hydrochloric acid, toluene, benzene, acetone, cyclohexane, DMF, NMP, aqua regia, organic aqua regia, nitrobenzene, tetrahydrofuran, propanethiol, thiourea, methyl chloride, carbon disulfide or hydrogen peroxide.
10. The use of claim 7, wherein: the mass ratio of the solvent to the metal-based ionic liquid is 0.5-5: 1.
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| CN109012751B (en) * | 2018-08-17 | 2021-06-04 | 浙江工业大学 | Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene |
| WO2020048130A1 (en) * | 2018-09-05 | 2020-03-12 | 中国科学院大连化学物理研究所 | Adsorbent, preparation method therefor and use thereof |
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| RU2727378C1 (en) * | 2019-12-27 | 2020-07-21 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ НАУЧНОЕ УЧРЕЖДЕНИЕ "ФЕДЕРАЛЬНЫЙ ИССЛЕДОВАТЕЛЬСКИЙ ЦЕНТР ИНСТИТУТ ЦИТОЛОГИИ И ГЕНЕТИКИ СИБИРСКОГО ОТДЕЛЕНИЯ РОССИЙСКОЙ АКАДЕМИИ НАУК" (ИЦиГ СО РАН) | Carbon-mineral porous sorbent based on aluminum oxide, polydimethylsiloxane and single-wall carbon nanotubes |
| CN112961027B (en) * | 2021-02-24 | 2023-08-01 | 石河子大学 | Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof |
| CN113041827B (en) * | 2021-03-16 | 2022-11-08 | 西安建筑科技大学 | Calcium-based ionic liquid for flue gas desulfurization, desulfurizer and preparation method thereof |
| CN113041826A (en) * | 2021-03-16 | 2021-06-29 | 西安建筑科技大学 | Zinc-based supported desulfurizer for flue gas desulfurization and preparation method thereof |
| CN113559924B (en) * | 2021-07-28 | 2023-10-03 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN114345409A (en) * | 2021-12-23 | 2022-04-15 | 山东鑫泉医药有限公司 | Preparation method of nano-loaded Cu ionic liquid catalyst |
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