CN113233989B - 1, 4-trihydroxyethylbenzdiammonium sulfate, 1,3, 5-trihydroxyethylbenztriammonium sulfate, synthesis and application thereof - Google Patents
1, 4-trihydroxyethylbenzdiammonium sulfate, 1,3, 5-trihydroxyethylbenztriammonium sulfate, synthesis and application thereof Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 68
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006467 substitution reaction Methods 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 238000005349 anion exchange Methods 0.000 claims abstract description 5
- -1 1,3, 5-trihydroxyethylbenzyl triammonium sulfate Chemical compound 0.000 claims description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- CZNJCCVKDVCRKF-UHFFFAOYSA-N Benzyl sulfate Chemical compound OS(=O)(=O)OCC1=CC=CC=C1 CZNJCCVKDVCRKF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003546 flue gas Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000002608 ionic liquid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OXSWKJLAKXNIFG-UHFFFAOYSA-N azane sulfuric acid Chemical compound N.N.N.OS(O)(=O)=O OXSWKJLAKXNIFG-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004970 halomethyl group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IMWCLXNSHVPEEI-UHFFFAOYSA-N benzoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)C1=CC=CC=C1 IMWCLXNSHVPEEI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229940006280 thiosulfate ion Drugs 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses 1, 4-trihydroxyethylbenzdiammonium sulfate, 1,3, 5-trihydroxyethylbenztriammonium sulfate and application thereof in synthesis and adsorption of sulfur dioxide. The synthesis of 1, 4-trihydroxyethylbenzediammonium sulfate and 1,3, 5-trihydroxyethylbenzediammonium sulfate is carried out by substitution reaction of 1, 4-para-dihalobenzediamine or 1,3, 5-tri (halogenated methyl) benzene with triethanolamine and anion exchange with sulfuric acid 2 Flue gas treatment and SO recovery 2 Etc. actual requirements.
Description
Technical Field
The invention relates to a sulfur dioxide adsorption material and a preparation method and application thereof, in particular to 1, 4-trihydroxyethylbenzediammonium sulfate, 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate, a method for synthesizing the 1, 4-trihydroxyethylbenzediammonium sulfate or the 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate by using 1, 4-p-dihalobenzethonium or 1,3, 5-tri (halogenated methyl) benzene, triethanolamine, sulfuric acid and the like as main raw materials through steps of substitution reaction, ion exchange and the like, and an application of using the 1, 4-trihydroxyethylbenzethonium sulfate or the 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate as a sulfur dioxide adsorption material, belonging to the technical field of sulfur dioxide waste gas treatment.
Background
Sulfur dioxide (chemical formula SO) 2 ) Is colorless gas, has strong pungent smell and is one of the main pollutants in the atmosphere. Is easy to combine with water vapor in the atmosphere to form sulfurous acid, which is one of the main substances causing acid rain due to atmospheric pollution. Sulfur dioxide can be oxidized into sulfur trioxide in the presence of nitrogen dioxide or under other certain catalytic conditions, so that sulfuric acid is easily generated, and the sulfuric acid causes harm to the surrounding environment, organisms and the like due to extremely high corrosivity. But at the same time, the sulfur dioxide is also an important chemical raw material and is mainly used for producing sulfuric acid; the application of the product is quite wide, and the product can be used as an insecticide, a bactericide, a bleaching agent, a reducing agent and the like to serve the production and life of human beings.
SO in industrial production flue gas 2 The source of the sulfur is mainly formed by oxidation reaction of sulfur components contained in fossil fuels, particularly in the processes of coal combustion and ore pyrometallurgy and air. SO in tail gas 2 The random discharge without treatment not only causes environmental pollution such as atmosphere and the like, but also causes SO 2 This industrial raw material resource is extremely wasted. At present, the industry can treat SO in the flue gas 2 The removing method mainly comprises an acid-base neutralization reaction method, a physical chemical adsorption method and the like. Wherein the acid-base neutralization reaction method mainly utilizes alkaline substances such as limestone, lime, caustic soda, ammonia water and the like and SO 2 The reaction is used for removing, and the physical and chemical adsorption method mainly adopts ionic liquid to remove SO 2 To complete. Acid-base neutralization method although eliminating SO 2 But at the same time SO 2 Other substances, SO, are also formed 2 The value of the gypsum cannot be utilized, and the formed sulfate such as gypsum, mirabilite and the like not only causes the saturated and excessive gypsum market to be difficult to digest, but also under a certain condition, the desulfurized gypsum cannot be effectively utilized due to the reduced quality, and secondary pollution is easily formed due to improper disposal. The cost of sodium hydroxide and ammonia water desulphurization is relatively high, the economy is not good, and ammonia is easy to escape into the air to cause secondary pollution. Physical and chemical adsorption processes, e.g. ionic liquid SO removal 2 Although effective in eliminating SO 2 Pollution to atmosphere and recovery of SO 2 But the ionic liquid ratio in the market is presentThe ionic liquid is expensive, so that the use cost is high, the ionic liquid has certain requirements on the use environment, if the dust in the flue gas is large, the ionic liquid is polluted, the environment influence resistance is low, and the use range of the ionic liquid is limited.
Disclosure of Invention
Aiming at the defects of the method for treating sulfur dioxide flue gas in the prior art, the invention aims to provide 1, 4-trihydroxyethylbenzediammonium sulfate or 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate, wherein the two quaternary ammonium salts have ionic liquid characteristics, show better adsorption capacity to sulfur dioxide, have the characteristics of higher adsorption saturation, stronger adsorption capacity, good performance stability, easy desorption and the like, and have absolute cost advantage compared with the existing ionic liquid.
The second purpose of the invention is to provide a method for synthesizing 1, 4-trihydroxyethylbenzediammonium sulfate or 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate, which uses raw materials such as 1, 4-p-dihalobenzethonium or 1,3, 5-tri (halogenated methyl) benzene, triethanolamine, sulfuric acid and the like as conventional chemical raw materials, is cheap and easy to obtain, has simple steps and mild conditions, and is beneficial to large-scale production.
The third purpose of the invention is to provide the application of the 1, 4-trihydroxyethylbenz diammonium sulfate or the 1,3, 5-trihydroxyethylbenz triammonium sulfate as the sulfur dioxide adsorbing material, the two quaternary ammonium salts have better adsorption capacity to sulfur dioxide, have the characteristics of higher adsorption saturation, stronger adsorption capacity, good performance stability, easy desorption, repeated use, low application cost and the like, and the requirement of SO-containing sulfur dioxide adsorbing material in the market is met 2 Flue gas treatment and SO recovery 2 Etc. actual requirements.
In order to achieve the technical purpose, the invention provides 1, 4-trihydroxyethyl benzyl diammonium sulfate which has a structure shown in a formula 1:
the invention also provides 1,3, 5-trihydroxyethyl benzyl triammonium sulfate which has a structure shown in a formula 2:
the sulfate of 1, 4-trihydroxyethylbenzediammonium and the sulfate of 1,3, 5-trihydroxyethylbenzethediammonium of the invention have higher adsorption capacity to sulfur dioxide, mainly utilizes the combination of the nitrogen positive ions thereof with sulfur dioxide to generate sulfonate or sulfite, the combination has smaller strength, and can carry out reverse reaction under the heating condition so as to release sulfur dioxide, while the sulfate of 1, 4-trihydroxyethylbenzediammonium and the sulfate of 1,3, 5-trihydroxyethylbenzethediammonium respectively contain two and three nitrogen positive ions which can act with two or three sulfur dioxide molecules and have good sulfur dioxide combination capacity, and the hydroxyethyl can influence the combination capacity of the nitrogen positive ions with the sulfur dioxide and endow the sulfate of 1, 4-trihydroxyethylbenzethediammonium and 1 with the ammonium group of 1, 4-trihydroxyethylbenzethediammonium, the performance of the 3, 5-trihydroxyethyl benzyl triammonium sulfate ionic liquid is improved, and the solubility of the ionic liquid in water is improved.
The anions of the 1, 4-trihydroxyethylbenzdiammonium sulfate and the 1,3, 5-trihydroxyethylbenztriammonium sulfate are sulfate radicals, and halogen anions in 1, 4-halogenated trihydroxyethylbenzdimonium salt and 1,3, 5-halogenated trihydroxyethylbenztriazolium salt are converted into sulfate radicals, so that the direct reaction of halide salt and sulfur dioxide can be avoided to generate sulfonate, part of halide ions are released, and the sulfonate is easy to generate disproportionation reaction under the heating condition: 4HSO 3 - ＝HSO 4 - +SO 4 2- +S 2 O 3 2- +H + +H 2 O; generate thiosulfate ion, and thiosulfate ion's existence can influence the ability of absorbing the sulfur dioxide once more of quaternary ammonium salt to influence the regeneration performance of adsorbing material, can generate the elemental sulfur solid even, the partial halogen ion of release accumulates to a certain extent simultaneously and can cause the corruption or cause environmental pollution to equipment, converts halogen atom into sulfate ion, can prolong sulfur dioxide adsorbing material's life.
The invention also provides a synthesis method of the 1, 4-trihydroxyethyl benzyl diammonium sulfate, which comprises the following steps:
1) carrying out substitution reaction on 1, 4-p-benzyl dihalide and triethanolamine to obtain 1, 4-halogenated trihydroxyethyl benzyl diammonium salt;
2) and (3) carrying out anion exchange on the 1, 4-halogenated trihydroxyethylbenzyl diammonium salt and sulfuric acid to obtain 1, 4-trihydroxyethylbenzyl diammonium sulfate.
As a preferred embodiment, the conditions of the substitution reaction are: and carrying out reflux reaction for 7-10 h at the temperature of 70-95 ℃ in an acetonitrile solvent. The most preferred substitution reaction conditions are: and carrying out reflux reaction for 8-9 h at the temperature of 80-90 ℃.
In a preferred embodiment, the molar ratio of the 1, 4-para-dihalobenzyl to the triethanolamine is 1:2 to 2.3.
As a preferable scheme, the dosage of the sulfuric acid is 3 to 6 percent in excess relative to the molar quantity of the 1, 4-halogenated trihydroxyethyl benzyl diammonium salt. The slightly excessive sulfuric acid can ensure that the halogen ions in the 1, 4-halogenated trihydroxyethyl benzyl diammonium salt are completely replaced by sulfate ions.
The invention also provides a synthesis method of the 1,3, 5-trihydroxyethyl benzyl triammonium sulfate, which comprises the following steps:
1)1,3, 5-tri (halogenated methyl) benzene and triethanolamine carry out substitution reaction to obtain 1,3, 5-halogenated trihydroxyethylbenzyl triammonium salt;
2) and (3) carrying out anion exchange on the 1,3, 5-halogenated trihydroxyethyl benzyl triammonium salt and sulfuric acid to obtain 1,3, 5-trihydroxyethyl benzyl triammonium sulfate.
As a preferred embodiment, the conditions of the substitution reaction are: and carrying out reflux reaction for 7-10 h at the temperature of 70-95 ℃ in an acetonitrile solvent. The most preferred substitution reaction conditions are: and carrying out reflux reaction for 8-9 h at the temperature of 80-90 ℃.
In a preferred embodiment, the molar ratio of 1,3, 5-tri (halomethyl) benzene to triethanolamine is 1:3 to 3.4.
As a preferable scheme, the dosage of the sulfuric acid is 3 to 6 percent excessive relative to the molar quantity of the 1,3, 5-halogenated trihydroxyethylbenzyl triammonium salt.
The invention also provides application of the 1, 4-trihydroxyethyl benzyl diammonium sulfate serving as a sulfur dioxide adsorbing material.
The invention also provides application of the 1,3, 5-trihydroxyethyl benzyl triammonium sulfate serving as a sulfur dioxide adsorption material.
The 1, 4-trihydroxyethyldiammonium benzyl sulfate or 1,3, 5-trihydroxyethyltriammonium benzyl sulfate provided by the invention is directly dissolved into water to be used as a sulfur dioxide absorption liquid, and the concentration of the 1, 4-trihydroxyethyldiammonium benzyl sulfate or 1,3, 5-trihydroxyethyltriammonium benzyl sulfate in the sulfur dioxide absorption liquid is controlled to be 15-30%.
The 1, 4-trihydroxyethylbenzdiammonium sulfate or 1,3, 5-trihydroxyethylbenztriammonium sulfate provided by the invention can realize the desorption of sulfur dioxide under the condition of heating to about 100 ℃ after adsorbing the sulfur dioxide to saturation.
The preparation method of 1, 4-trihydroxyethylbenzdiammonium sulfate or 1,3, 5-trihydroxyethylbenztriammonium sulfate provided by the invention specifically comprises the following main steps:
(1) Adding 1, 4-p-dihalobenzyl or 1,3, 5-tri (halogenated methyl) benzene into an acetonitrile solvent, fully stirring and uniformly dispersing; the mass ratio of the 1, 4-p-dihalobenzyl or 1,3, 5-tri (halogenated methyl) benzene to the acetonitrile is 1: 2.5 to 2.8;
(2) adding triethanolamine, stirring and heating to 70-95 ℃ for refluxing for 7-10 h, wherein the reaction equation is as follows: if 1, 4-para-dihalo-benzyl is used as a raw material, the molar ratio of 1, 4-para-dihalo-benzyl to triethanolamine is 1: 2-2.3, and if 1,3, 5-tri (halomethyl) benzene is used as a raw material, the molar ratio of 1,3, 5-tri (halomethyl) benzene to triethanolamine is 1: 3-3.4; the halogen element in the 1, 4-p-dihalogen benzyl and 1,3, 5-tri (halogenated methyl) benzene can be common halogen such as chlorine, bromine, iodine and the like;
or,
(3) naturally cooling to room temperature, generating a large amount of 1, 4-halogenated trihydroxyethylbenzethonium white precipitate or 1,3, 5-halogenated trihydroxyethylbenzethonium white precipitate, filtering to obtain a filter cake, and washing the filter cake for 2-5 times by using an acetonitrile solution;
(4) drying the filter cake for 7-10 hours at 40-60 ℃ under vacuum to obtain 1, 4-halogenated trihydroxyethylbenz diammonium or 1,3, 5-halogenated trihydroxyethylbenz triammonium;
(5) under the condition of stirring, slowly adding concentrated sulfuric acid into water, then adding 1, 4-halogenated trihydroxyethyldiammonium benzoate or 1,3, 5-halogenated trihydroxyethyltriammonium benzoate, and fully stirring to obtain a 1, 4-trihydroxyethyldiammonium benzoate sulfate solution or a 1,3, 5-trihydroxyethyltriammonium benzoate sulfate solution, wherein the reaction equation is as follows:
Or,
compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) in the synthesis process of the 1, 4-trihydroxyethyldiammonium benzyl sulfate or 1,3, 5-trihydroxyethyltriammonium benzyl sulfate, common commercial reagents such as 1, 4-p-dihalobenzyl, 1,3, 5-tri (halogenated methyl) benzene, acetonitrile, triethanolamine, sulfuric acid and the like are used as main raw materials, so that the source is rich and the cost is low.
2) The synthesis process of the 1, 4-trihydroxyethylbenzediammonium sulfate or 1,3, 5-trihydroxyethylbenzethonium triamide sulfate has the advantages of simple steps, mild conditions, easy control of operation and low cost, and is favorable for large-scale production.
3) The 1, 4-trihydroxyethyldiammonium benzyl sulfate or 1,3, 5-trihydroxyethyltriammonium benzyl sulfate has a special molecular structure, has ionic liquid properties, is stable in compound structure and physicochemical properties, can bear high temperature below 150 ℃ without decomposition, is strong in environmental adaptation capability, is strong in pollution resistance in the using process and the like.
4) The 1, 4-trihydroxyethylbenzediammonium sulfate or 1,3, 5-trihydroxyethylbenzethonium triammonium sulfate has a large number of functional groups with adsorption activity, has higher adsorption capacity on sulfur dioxide, higher adsorption saturation, large adsorption amount per unit product, easy desorption, and can realize complete desorption under the conditions of lower temperature and normal pressure, the desorbed material can be reused, the adsorption performance is not obviously reduced, the material consumption cost can be reduced, and the like, and the requirement of SO-containing materials in the market can be met 2 Flue gas treatment and SO recovery 2 Etc. actual requirements.
In conclusion, the invention has good economic value and social value and is easy to popularize and apply.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 4-trihydroxyethyl benzyl diammonium chloride prepared in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of 1, 4-trihydroxyethyl benzyl diammonium chloride prepared in example 1.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 1,3, 5-trihydroxyethylbenzethonium bromide prepared in example 2.
FIG. 4 is the nuclear magnetic carbon spectrum of 1,3, 5-trihydroxyethylbenzethonium bromide prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the claims.
The chemical raw materials mentioned in the following examples are common commercial raw materials unless otherwise specified.
Example 1
In the embodiment, the compound is prepared by using 1, 4-p-dichlorobenzyl, acetonitrile, triethanolamine, sulfuric acid and the like as main raw materials and through a chemical synthesis method under certain conditions. The method specifically comprises the following main steps:
(1) adding 1 part of 1, 4-p-dichlorobenzyl into 2.5 parts of acetonitrile solution, fully stirring and uniformly dispersing;
(2) then adding 2.2 parts of triethanolamine, stirring simultaneously, and heating to 80 ℃ for refluxing for 8 hours, wherein the reaction equation is as follows:
(3) Naturally cooling to room temperature, generating a large amount of 1, 4-trihydroxyethylbenzethonium chloride white precipitate, filtering to obtain a filter cake, and washing the filter cake with acetonitrile solution for 3 times;
(4) drying the filter cake for 8 hours at the temperature of 50 ℃ under vacuum to obtain 1, 4-trihydroxyethyldiammonium benzyl chloride;
(5) under the condition of stirring, slowly adding 3-6% of excessive concentrated sulfuric acid into water, then adding 1, 4-chlorinated trihydroxyethyldiammonium benzyl, and fully stirring to obtain a 50% concentration 1, 4-trihydroxyethyldiammonium sulfate solution, wherein the reaction equation is as follows:
(6) diluting with water to 25% concentration to obtain the product capable of efficiently adsorbing SO 2 The adsorbent of (1).
(7) The use method and the process of the 1, 4-trihydroxyethyl benzyl diammonium sulfate solution are as follows:
200mL of water solution of 25 mass percent of 1, 4-trihydroxyethyl benzyl diammonium sulfate is filled into a gas collecting bottle, and SO is contained in a lead smelting plant 2 The tail gas is led out from the flue gas pipeline by a hose, connected with a gas collecting bottle and connected with the hose to the gas inlet of the gas collecting bottle, and then connected with a pipeline. Weighing the weight increase condition of the gas collection bottle at intervals, recording the total weight increase mass to obtain SO of an aqueous solution of 1, 4-trihydroxyethylbenzendiammonium sulfate with the sulfur dioxide adsorption amount of 11.30g and the mass fraction of 1, 4-trihydroxyethylbenzendiammonium of 25 percent, wherein the weight of the gas collection bottle is not increased any more, and the total weight increase mass is recorded 2 The adsorption capacity was 56.5 g/L. And heating the adsorption material with saturated adsorption to 100 ℃ for desorption, and recording the integral weight loss of the gas collection bottle as 10.84g after heating for 1.5h, wherein the desorption rate is 95.9%.
Desorbing the 1, 4-trihydroxyethylRepeatedly using diammonium benzyl sulfate solution to adsorb SO 2 The capacity cases are shown in the following table:
example 2
In the embodiment, 1,3, 5-tri (bromomethyl) benzene, acetonitrile, triethanolamine, sulfuric acid and the like are used as main raw materials and are prepared by a chemical synthesis method under certain conditions. The method specifically comprises the following main steps:
(1) adding 1 part of 1,3, 5-tri (bromomethyl) benzene into 2.6 parts of acetonitrile solution, fully stirring and uniformly dispersing;
(2) then adding 3.3 parts of triethanolamine, stirring simultaneously, and heating to 80 ℃ for refluxing for 8 hours, wherein the reaction equation is as follows:
(3) naturally cooling to room temperature, generating a large amount of 1,3, 5-trihydroxyethylbenzyl triammonium bromide white precipitate, filtering to obtain a filter cake, and washing the filter cake with acetonitrile solution for 3 times;
(4) drying the filter cake for 8 hours at the temperature of 50 ℃ under vacuum to obtain 1,3, 5-trihydroxyethylbenztrityl ammonium bromide;
(5) under the condition of stirring, slowly adding excessive concentrated sulfuric acid with the concentration of 3-6% into water, then adding 1,3, 5-trihydroxyethylbenztrityl ammonium bromide, and fully stirring to obtain a 1,3, 5-trihydroxyethylbenztrityl ammonium sulfate solution with the concentration of 50%, wherein the reaction equation is as follows:
(6) Diluting with water to 25% concentration to obtain the product capable of efficiently adsorbing SO 2 The adsorbent of (1).
(7) The use method and the process of the 1,3, 5-trihydroxyethylbenztrityl ammonium sulfate solution are as follows:
200mL of 1,3, 5-trihydroxyethyl benzyl triammonium sulfate aqueous solution with the mass fraction of 25% is filled into a gas collecting bottle, and SO is contained in a lead smelting plant 2 The tail gas is led out from the flue gas pipeline by a hose, connected with a gas collecting bottle and connected with the hose to the gas inlet of the gas collecting bottle, and then connected with a pipeline. Weighing the weight increase condition of the gas collection bottle at intervals, recording the total weight increase mass to obtain SO of an aqueous solution of 1,3, 5-trihydroxyethylbenztrionium sulfate with sulfur dioxide adsorption amount of 10.78g and 1,3, 5-trihydroxyethylbenztrionium mass fraction of 25% 2 The adsorption capacity was 53.9 g/L. And heating the adsorption material with saturated adsorption to 100 ℃ for desorption, and recording the integral weight loss of the gas collection bottle as 10.50g after heating for 1.5h, wherein the desorption rate is 97.4%.
The desorbed 1,3, 5-trihydroxyethylbenzyl tri-ammonium sulfate solution is used for a plurality of times to adsorb SO 2 The capacity cases are shown in the following table:
Claims (10)
1. 1, 4-trihydroxyethylbenzyldiammonium sulfate is characterized in that: has a structure shown in formula 1:
2. 1,3, 5-trihydroxyethylbenzyl triammonium sulfate is characterized in that: has a structure shown in formula 2:
3. The method for synthesizing 1, 4-trihydroxyethyldiammonium benzyl sulfate as recited in claim 1, characterized in that: the method comprises the following steps:
1) carrying out substitution reaction on 1, 4-p-benzyl dihalide and triethanolamine to obtain 1, 4-halogenated trihydroxyethyl benzyl diammonium salt;
2) and (3) carrying out anion exchange on the 1, 4-halogenated trihydroxyethylbenzyl diammonium salt and sulfuric acid to obtain 1, 4-trihydroxyethylbenzyl diammonium sulfate.
4. The method for synthesizing 1, 4-trihydroxyethyldiammonium benzyl sulfate according to claim 3, wherein the method comprises the following steps: the conditions of the substitution reaction are as follows: carrying out reflux reaction in an acetonitrile solvent at the temperature of 70-95 ℃ for 7-10 h; the molar ratio of the 1, 4-para-dihalogen benzyl to the triethanolamine is 1: 2-2.3.
5. The method for synthesizing 1, 4-trihydroxyethyldiammonium benzyl sulfate according to claim 3, wherein the method comprises the following steps:
the dosage of the sulfuric acid is 3 to 6 percent excessive relative to the molar quantity of the 1, 4-halogenated trihydroxyethyl benzyl diammonium salt.
6. The method for synthesizing 1,3, 5-trihydroxyethyl benzyl triammonium sulfate as recited in claim 2, which is characterized in that: the method comprises the following steps:
1)1,3, 5-tri (halogenated methyl) benzene and triethanolamine carry out substitution reaction to obtain 1,3, 5-halogenated trihydroxyethylbenzyl triammonium salt;
2) And (3) carrying out anion exchange on the 1,3, 5-halogenated trihydroxyethyl benzyl triammonium salt and sulfuric acid to obtain 1,3, 5-trihydroxyethyl benzyl triammonium sulfate.
7. The method for synthesizing 1,3, 5-trihydroxyethyl benzyl triammonium sulfate as recited in claim 6, wherein the method comprises the following steps: the conditions of the substitution reaction are as follows: carrying out reflux reaction in an acetonitrile solvent at the temperature of 70-95 ℃ for 7-10 h;
the molar ratio of the 1,3, 5-tri (halogenated methyl) benzene to the triethanolamine is 1: 3-3.4.
8. The method for synthesizing 1,3, 5-trihydroxyethyl benzyl triammonium sulfate as recited in claim 6, wherein the method comprises the following steps: the dosage of the sulfuric acid is 3 to 6 percent excessive relative to the molar quantity of the 1,3, 5-halogenated trihydroxyethyl benzyl triammonium salt.
9. The application of 1, 4-trihydroxyethyldiammonium benzoate as recited in claim 1, characterized in that: the sulfur dioxide adsorbent is applied as a sulfur dioxide adsorbing material.
10. The application of the 1,3, 5-trihydroxyethyl benzyl triammonium sulfate as recited in claim 2, which is characterized in that: the sulfur dioxide adsorbent is applied as a sulfur dioxide adsorbing material.
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