CN103111333A - Preparation method and application of ionic liquid and metal dual-modified sepiolite - Google Patents
Preparation method and application of ionic liquid and metal dual-modified sepiolite Download PDFInfo
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Abstract
The invention relates to a preparation method and application of ionic liquid and metal dual-modified sepiolite. The preparation method comprises the following steps of: firstly carrying out hydrothermal-hydrochloric acid method pretreatment on the sepiolite serving as a raw material, then carrying out metal modification on the sepiolite by adopting an impregnation method, and then modifying the metal-loaded sepiolite by utilizing tetraalkyl ammonium halide/caprolactam ionic liquid to obtain the ionic liquid and metal dual-modified sepiolite. When the ionic liquid and the metal dual-modified sepiolite are used in the absorption-catalytic oxidation process of sulfur dioxide, the catalyst can perform high-efficiency absorption and catalytic oxidation on sulfur dioxide, sulfur trioxide is absorbed by 95% sulfuric acid, and sulfur resources are recycled. The preparation method is simple in process, modification cost is low, and application operation is simple and convenient. By utilizing the technology, recycling of the sepiolite and harmlessness and reduction of the sulfur dioxide can be realized.
Description
Technical field
The invention belongs to nonmetallic ore and atmospheric environment field, be specifically related to preparation method and the application of the two modified meerschaums of a kind of ionic liquid and metal.
Background technology
China is the country take coal as main energy sources, and in energy resource structure, coal accounts for more than 80%.Along with the rapid growth of China's economy, urbanization process is accelerated, and population constantly increases, and to the also hurried rising of demand of the energy, thing followed sulfur dioxide pollution problem highlights day by day.China is the state of first consumption of coal in the world, first sulfur dioxide (SO2) emissions states.The atmosphere pollution of China at present belongs to typical coal-smoke pollution, and control the harm of sulfur dioxide (SO2) emissions and acid rain is the vital task of environmental protection always.Propose SO2 emissions in 2015 in " national environmental protection " 12 " planning " and reduced 8% than 2010.The industrial SO in the whole nation
2Discharge capacity accounts for overall more than 70%, therefore controls flue gas desulfurization and can effectively control sulfur dioxide pollution, the harm of control acid rain.
Researched and developed out over one hundred kind of flue gas desulfurization technique both at home and abroad: calcium method, ammonia process, charcoal method, magnesium method and sodium method etc.Charcoal method desulfur technology is because having the following advantages: do not need to add desulfurizing agent at any time in system, sorbent consumption is few, and operating cost is low; Desulfurization product can be recycled with various ways such as the concentrated sulfuric acid, sulfuric acid, sulphur, adapts to the different market demands, and equipment is relatively less, and technological process is simple, is considered to have the flue gas desulfurization technique of prospect, has become the important technology that various countries competitively research and develop.But because there are the shortcomings such as desulfurization capacity is low, desulfurization rate slow, replacement cost is higher in common active carbon, hindered its industry to apply, but domestic sepiolite aboundresources, wide material sources, function admirable, price is cheaply a lot of compared to active carbon, and easily regeneration.
Sepiolite be a kind of have a layer chain structure contain Shuifu County's magnesium silicate clay, belong to nonmetallic mineral, 50 many places, the sepiolite place of production have been found in the whole nation, approximately 1,200 ten thousand tons of reserves.The carrier that is used as industrial catalyst based on its huge surface area and multi-cellular structure more.Extremely weak and be rich in impurity due to natural sea afrodite self acidity, can not nonoculture be generally that catalyst uses.Most scholar's research are found can optimize its performance by the modification to sepiolite, make it to be applicable to all kinds of catalytic reactions, enlarge its range of application.Summing up domestic and international research can find out, the method for modifying of sepiolite mainly comprises sour modification, ion-exchanged, organic coordination compound modification and mineral modified etc., but all perfect not.Though the acid modification can increase heat endurance and the specific area of sepiolite, the structure of sepiolite is easily destroyed; Although ion-exchanged has overcome sour modification to the sepiolite structural damage, can not be used for specific area that changes sepiolite etc.
Summary of the invention
The present invention provides preparation method and the application of the two modified meerschaums of a kind of ionic liquid and metal for solving the problems of the prior art.It has advantages of that adsorption capacity is large, desulfurization rate fast, the Catalytic Oxygen rate is high, and is extensive in the application prospect of air purification field.。
The present invention is achieved by following technical scheme:
Preparation method and the application of the two modified meerschaums of a kind of ionic liquid and metal, it comprises the following steps:
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite; Described concentration of hydrochloric acid calculates with percent by volume.
B. metal-modified: adopt infusion process to step a gained hydro-thermal-salt acid treatment sepiolite carries out metal-modified, it is 2 ~ 6h in 15 ~ 25% metal-nitrate solutions that hydro-thermal-salt acid treatment sepiolite is immersed in mass fraction, filter, filter cake equal-volume water washing 3 times, dry 550 ℃ of roasting 4h under nitrogen protection afterwards obtain metal-modified sepiolite;
C. ion liquid modified: it is in 1 ~ 30% caprolactam-quaternary alkylammonium halides ionic liquid acetone soln that the metal-modified sepiolite that step b is obtained is impregnated into mass fraction, covered metal-modified sepiolite for well with liquid level, normal temperature dipping 18 ~ 30h, filter, with isopyknic acetone washing leaching cake 3 times, dry 24h, 35 ℃ of vacuum drying 6h get the two modified meerschaum catalyst of ionic liquid and metal;
Described ionic liquid is caprolactam-quaternary alkylammonium halides ionic liquid;
D. the caprolactam of step c gained-quaternary alkylammonium halides ionic liquid and the two modified meerschaum catalyst of metal are put into adsorption tower, at the sulfur dioxide gas 3h of 10 ~ 80 ℃ of absorption-catalytic oxidation 1000 ~ 5000ppm, 95% sulfuric acid absorption of the gas after absorption-catalytic oxidation.
Described metal nitrate is a kind of in copper nitrate, ferric nitrate, nickel nitrate, barium nitrate, plumbi nitras, cobalt nitrate or manganese nitrate.
in described ionic liquid, the tetraalkyl halogeno-amine is tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, TBAB, four pentyl ammonium chloride, the four pentyl ammonium bromide, four hexyl ammonium chlorides, four hexyl ammonium bromides, four heptyl ammonium chlorides, four heptyl ammonium bromides, four octyl group ammonium chlorides, four octyl group ammonium bromides, four nonyl ammonium chlorides, four nonyl ammonium bromides, a kind of in four decyl ammonium chlorides or four decyl ammonium bromides.
Preferably, preparation method and the application of the two modified meerschaums of described a kind of ionic liquid and metal, it comprises following concrete steps:
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
Described concentration of hydrochloric acid calculates with percent by volume;
B is metal-modified: it is 2h in 20% copper nitrate solution that the sepiolite that step a is obtained is immersed in by mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the copper modified meerschaum;
C is ion liquid modified: under room temperature, react with TBAB respectively with caprolactam, generating caprolactam-TBAB is the ionic liquid of 2:1 in mass ratio.The preparation mass fraction is 20% caprolactam-TBAB ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 30h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-TBAB and copper;
D puts into adsorption tower with two modified meerschaums, the sulfur dioxide gas 3h of 80 ℃ of absorption-catalytic oxidation 1000ppm, 95% sulfuric acid absorption of the gas after absorption-catalytic oxidation.
The inventive method is first carried out metal-modified to sepiolite, main purpose is to strengthen the catalysed oxidn of sepiolite; Then with caprolactam-quaternary alkylammonium halides ionic liquid, the sepiolite of carried metal is carried out modification, to increase the specific area of catalyst, strengthen its absorption property, improve the utilization rate of sepiolite, for the development of sepiolite flue gas desulfurization technique lays the foundation.
The present invention compared with prior art has following significant advantage:
1, raw material resources of the present invention are abundant, and are cheap, therefore product of the present invention compared with prior art greatly reduces cost.
2, caprolactam-quaternary alkylammonium halides ionic liquid is compared with former sepiolite with the two modified meerschaums of metal and is had advantages of that adsorption capacity is large, desulfurization rate fast, the Catalytic Oxygen rate is high.
3, this method has realized innoxious, minimizing and the resource of resource, the sulfur dioxide of sepiolite nonmetallic ore, has good economic benefit, environmental benefit and social benefit.
4, the present invention prevents and has controlled the sulfur dioxide pollution problem, reduces desulphurization cost, improves the sepiolite utilization rate, has realized the comprehensive utilization of resource, and extensive in the air purification field application prospect, social benefit is remarkable.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: be 4h in 20% copper nitrate solution with the sepiolite impregnating effect mark of step a gained, filter, filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the copper modified meerschaum;
C is ion liquid modified: under room temperature, react with tetrabutylammonium chloride respectively with caprolactam, generate tetrabutylammonium chloride/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 10% caprolactam-TBAB ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 24h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-tetrabutylammonium chloride and copper;
D puts into adsorption tower with caprolactam-tetrabutylammonium chloride and the two modified meerschaums of copper of step c gained, the sulfur dioxide gas 3h of 40 ℃ of absorption-catalytic oxidation 2000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 98.91%, and catalytic oxidation efficient can reach 57.35%.
Embodiment 2
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 2h in 20% copper nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the copper modified meerschaum;
C is ion liquid modified: under room temperature, react with the four pentyl ammonium bromide respectively with caprolactam, generate caprolactam/four pentyl ammonium bromide (2:1 mass ratio) ionic liquid.The preparation mass fraction is 10% caprolactam-four pentyl ammonium bromide ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 30h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-four pentyl ammonium bromide and copper;
D puts into adsorption tower with two modified meerschaums, the sulfur dioxide gas 3h of 80 ℃ of absorption-catalytic oxidation 1000ppm, and 95% sulfuric acid absorption of the gas after absorption-catalytic oxidation, absorption-catalysis gross efficiency can reach 97.95%, and catalytic oxidation efficient can reach 57.24%.
Embodiment 3
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 5h in 18% nickel nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the nickel modified meerschaum;
C is ion liquid modified: under room temperature, react with tetraethylammonium bromide respectively with caprolactam, generate tetraethylammonium bromide/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 5% caprolactam-TBAB ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 18h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-TBAB and nickel;
D puts into adsorption tower with caprolactam-TBAB and the two modified meerschaums of nickel, the sulfur dioxide gas 3h of 50 ℃ of absorption-catalytic oxidation 4000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 96.23%, and catalytic oxidation efficient can reach 53.81%.
Embodiment 4
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 6h in 25% barium nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the barium modified meerschaum;
C is ion liquid modified: under room temperature, react with etamon chloride respectively with caprolactam, generate etamon chloride/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 10% caprolactam-etamon chloride ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 24h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of etamon chloride/caprolactam and barium;
D puts into adsorption tower with caprolactam-TBAB and the two modified meerschaums of barium, the sulfur dioxide gas 3h of 40 ℃ of absorption-catalytic oxidation 1000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 83.93%, and catalytic oxidation efficient can reach 30.28%.
Embodiment 5
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 4h in 20% manganese nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the manganese modified meerschaum;
C is ion liquid modified: under room temperature, react with etamon chloride respectively with caprolactam, generate etamon chloride/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 10% caprolactam-etamon chloride ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 30h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-etamon chloride and manganese;
D puts into adsorption tower with caprolactam-etamon chloride and the two modified meerschaums of manganese, the sulfur dioxide gas 3h of 10 ℃ of absorption-catalytic oxidation 1000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 86.11%, and catalytic oxidation efficient can reach 31.56%.
Embodiment 6
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 3h in 25% cobalt nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain cobalt improved sepiolite;
C is ion liquid modified: under room temperature, react with 4 bromide respectively with caprolactam, generate 4 bromide/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 20% caprolactam-4 bromide ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 36h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-4 bromide and cobalt;
D puts into adsorption tower with caprolactam-4 bromide and the two modified meerschaums of cobalt, the sulfur dioxide gas 3h of 70 ℃ of absorption-catalytic oxidation 3000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 93.61%, and catalytic oxidation efficient can reach 50.24%.
Embodiment 7
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
B is metal-modified: it is 6h in 17% lead nitrate solution that the sepiolite that step a is obtained is immersed in mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain plumbous modified meerschaum;
C ionic liquid: under room temperature, react with tetramethyl ammonium chloride respectively with caprolactam, generate tetramethyl ammonium chloride/caprolactam (2:1 mass ratio) ionic liquid.The preparation mass fraction is 20% caprolactam-tetramethyl ammonium chloride ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 24h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain caprolactam-tetramethyl ammonium chloride and plumbous two modified meerschaum;
D puts into adsorption tower with caprolactam-tetramethyl ammonium chloride and plumbous two modified meerschaum, the sulfur dioxide gas 3h of 20 ℃ of absorption-catalytic oxidation 5000ppm, gas after absorption-catalytic oxidation 95% sulfuric acid absorption, absorption-catalysis gross efficiency can reach 88.75%, and catalytic oxidation efficient can reach 46.92%.
Claims (4)
1. preparation method and the application of the two modified meerschaums of an ionic liquid and metal, is characterized in that, it comprises the following steps:
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
Described concentration of hydrochloric acid calculates with percent by volume;
B. metal-modified: adopt infusion process to step a gained hydro-thermal-salt acid treatment sepiolite carries out metal-modified, it is 2 ~ 6h in 15 ~ 25% metal-nitrate solutions that hydro-thermal-salt acid treatment sepiolite is immersed in mass fraction, filter, filter cake equal-volume water washing 3 times, dry 550 ℃ of roasting 4h under nitrogen protection afterwards obtain metal-modified sepiolite;
C. ion liquid modified: it is in 1 ~ 30% caprolactam-quaternary alkylammonium halides ionic liquid acetone soln that the metal-modified sepiolite that step b is obtained is impregnated into mass fraction, covered metal-modified sepiolite for well with liquid level, normal temperature dipping 18 ~ 30h, filter, with isopyknic acetone washing leaching cake 3 times, dry 24h, 35 ℃ of vacuum drying 6h get the two modified meerschaum catalyst of ionic liquid and metal;
Described ionic liquid is caprolactam-quaternary alkylammonium halides ionic liquid;
D. the caprolactam of step c gained-quaternary alkylammonium halides ionic liquid and the two modified meerschaum catalyst of metal are put into adsorption tower, at the sulfur dioxide gas 3h of 10 ~ 80 ℃ of absorption-catalytic oxidation 1000 ~ 5000ppm, 95% sulfuric acid absorption of the gas after absorption-catalytic oxidation.
2. preparation method and the application of the two modified meerschaums of a kind of ionic liquid as claimed in claim 1 and metal, is characterized in that, described metal nitrate is a kind of in copper nitrate, ferric nitrate, nickel nitrate, barium nitrate, plumbi nitras, cobalt nitrate or manganese nitrate.
3. preparation method and the application of the two modified meerschaums of ionic liquid as claimed in claim 1 or 2 and metal, it is characterized in that, in described ionic liquid, the tetraalkyl halogeno-amine is tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, TBAB, four pentyl ammonium chloride, the four pentyl ammonium bromide, four hexyl ammonium chlorides, four hexyl ammonium bromides, four heptyl ammonium chlorides, four heptyl ammonium bromides, four octyl group ammonium chlorides, four octyl group ammonium bromides, four nonyl ammonium chlorides, four nonyl ammonium bromides, a kind of in four decyl ammonium chlorides or four decyl ammonium bromides.
4. preparation method and the application of the two modified meerschaums of a kind of ionic liquid as claimed in claim 1 and metal, is characterized in that, it comprises following concrete steps:
A. pretreatment: original sepiolite is mixed with the water of 10 times of quality the autoclave of packing into, and 150 ℃ are stirred 3h, and suction filtration at 105 ℃ of dry 4h, is pulverized and namely obtained the hydrothermal treatment consists sepiolite; Then be that 6% hydrochloric acid reacts 6h with the mass fraction of gained hydrothermal treatment consists sepiolite and 10 times of quality under 25 ℃, suction filtration is washed to neutrality, and 110 ℃ of dry 4h obtain hydro-thermal-salt acid treatment sepiolite;
Described concentration of hydrochloric acid calculates with percent by volume;
B is metal-modified: it is 2h in 20% copper nitrate solution that the sepiolite that step a is obtained is immersed in by mass fraction, filters, and filter cake is with equal-volume water washing 3 times, dry after under nitrogen protection 550 ℃ of roasting 4h, obtain the copper modified meerschaum;
C is ion liquid modified: under room temperature, react with TBAB respectively with caprolactam, generating caprolactam/TBAB is the ionic liquid of 2:1 in mass ratio.The preparation mass fraction is 20% caprolactam-TBAB ionic liquid acetone soln.The sepiolite that step b is obtained is impregnated in the ionic liquid acetone soln, covers active carbon for well with liquid level, and normal temperature dipping 30h filters, and with isopyknic acetone washing leaching cake 3 times, dries 24h, 35 ℃ of vacuum drying 6h in the vacuum electric heating air dry oven.Finally obtain the two modified meerschaums of caprolactam-TBAB and copper;
D puts into adsorption tower with two modified meerschaums, the sulfur dioxide gas 3h of 80 ℃ of absorption-catalytic oxidation 1000ppm, 95% sulfuric acid absorption of the gas after absorption-catalytic oxidation.
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