CN112742160A - Containing SO2Method and apparatus for treating exhaust gas - Google Patents
Containing SO2Method and apparatus for treating exhaust gas Download PDFInfo
- Publication number
- CN112742160A CN112742160A CN201911048423.XA CN201911048423A CN112742160A CN 112742160 A CN112742160 A CN 112742160A CN 201911048423 A CN201911048423 A CN 201911048423A CN 112742160 A CN112742160 A CN 112742160A
- Authority
- CN
- China
- Prior art keywords
- adsorption
- regeneration
- flue gas
- organic framework
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 128
- 238000001179 sorption measurement Methods 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 46
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 28
- 238000011069 regeneration method Methods 0.000 claims abstract description 28
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 23
- 239000002912 waste gas Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 19
- 238000007906 compression Methods 0.000 claims abstract description 16
- 230000006835 compression Effects 0.000 claims abstract description 16
- 238000003795 desorption Methods 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000035515 penetration Effects 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 239000003546 flue gas Substances 0.000 claims description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000013132 MOF-5 Substances 0.000 claims description 4
- 239000013118 MOF-74-type framework Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 2
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 239000003463 adsorbent Substances 0.000 description 17
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000019391 nitrogen oxide Nutrition 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- 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
- B01D53/26—Drying gases or vapours
- B01D53/265—Drying gases or vapours by refrigeration (condensation)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
Abstract
The invention relates to a method for preparing a sulfur-containing organic compound2The waste gas containing sulfur dioxide is compressed and condensed in a compression unit and then enters an adsorption unit for adsorption, and an adsorption material adopted by the adsorption unit is a carbonized metal organic framework material loaded with sodium sulfite and enters a desorption unit for regeneration after adsorption penetration. The invention realizes the control of SO2Effective treatment of exhaust gases, SO2Can be recycled efficiently.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a sulfur dioxide (SO) -containing catalyst2A method and an apparatus for treating exhaust gas.
Background
Fossil fuels (coal, petroleum, etc.) contain a large amount of sulfur, and direct combustion produces a high content of SO2The flue gas of (1). SO (SO)2The excessive discharge of (2) causes a series of environmental problems, and the formed acid rain and photochemical smog bring serious harm to the production and the life of human beings. Currently, widely used SO2The removal method is divided into a wet desulfurization technique and a dry desulfurization technique. The wet desulfurization is mainly characterized in that alkali liquor is contacted with flue gas, and SO is generated through chemical reaction2The sulfite and the sulfate are converted into water and dissolved in the water, and then the sulfate-containing solution is treated to achieve the aim of desulfurization.The dry desulfurization mainly utilizes the adsorption property of porous materials to remove SO2Separated from the waste gas, desorbed and regenerated after saturated adsorption or oxidized to be converted into SO3And (4) eluting.
The dry flue gas desulfurization method widely used in industry uses activated carbon material as an adsorption oxidant to remove SO through the processes of adsorption-oxidation-sulfation-alkali washing and the like2. In the process, the adsorption capacity of the activated carbon is limited, and the treatment process is long. SO in S-Zorb flue gas in petroleum refining industry2Concentration of>1%, SO is more suitable2And desorbing and recovering to prepare sulfur after adsorption.
CN103920365A discloses a method for recovering nitrogen and sulfur dioxide in roasted pyrite furnace gas by variable-frequency and variable-pressure adsorption, which comprises the following process steps: after the furnace gas for roasting the pyrite is subjected to dust removal, purification, drying and cooling, removing dust particles and iron rust through a refined sulfuric acid furnace gas filter made of 200-mesh polytetrafluoroethylene; then the N is realized by a method of frequency conversion and pressure swing adsorption after deep fine dehydration, deoxidation and decarbonation of a fine dehydration tank2With SO2Then obtaining liquid SO by compression or cooling and gas-liquid separation2Separating the separated nitrogen and liquid SO2Bottling for industrial use; SO not separated by liquefaction2Then enters the cycle process of compression or cooling and gas-liquid separation to remove SO in the gas2Continuously separating. The process has long treatment flow, needs multi-stage cooling treatment and has high energy consumption.
CN104043401A discloses a sulfur dioxide adsorbent, comprising: the carrier and triethanolamine loaded on the carrier, wherein the weight ratio of the triethanolamine to the carrier is 0.1: 1-2: 1. It has good adsorption performance and is not easy to desorb. The adsorbent is not suitable for desorption after adsorption, and is not suitable for treating high-concentration SO2Industrial fumes.
CN102039115A discloses a preparation method of an activated carbon adsorbent for adsorbing acidic gas, which comprises the following raw material formula: granular coal-based activated carbon with the benzene absorption rate of more than or equal to 30 percent, sodium carbonate with the mass of 6-12 percent of the coal-based activated carbon, sodium hydroxide with the mass of 4-8 percent of the coal-based activated carbon and distilled water with the mass of 40-60 percent of the coal-based activated carbon; firstly, sodium hydroxide and sodium carbonate are put into distilled water with a certain proportion to be dissolved, then the solution is added into coal charcoal to be uniformly stirred, and the mixture is placed for 10 to 12 hours and then dried. Can adsorb sulfur dioxide or nitrogen oxide in the air, and has high adsorption efficiency and simple preparation process. The adsorption capacity of the adsorbent material needs to be improved.
In addition, the adsorbing material applied in the traditional desulfurization process has oxidation performance and is easy to remove SO2Oxidation to SO3And the active carbon adsorption material is damaged in the regeneration process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst containing SO2A method and an apparatus for treating exhaust gas. The invention combines a novel SO through a cyclic process of compression condensation-adsorption-desorption2Adsorbing material for adsorbing SO2Effective treatment of exhaust gases, SO2Can be recycled efficiently.
The invention provides a catalyst containing SO2The method for treating the waste gas comprises the following steps: the sulfur dioxide-containing waste gas is compressed and condensed in the compression unit and then enters the adsorption unit for adsorption, the adsorption material adopted by the adsorption unit is loaded with sodium sulfite on a carbonized metal organic framework material, and desorption regeneration is carried out after adsorption penetration.
In the invention, the sulfur dioxide-containing waste gas is at least one of S-zorb regeneration flue gas, sulfur recovery device incineration flue gas and catalytic cracking regeneration flue gas, and the S-zorb regeneration flue gas is preferably selected. Further, the waste gas is low-oxygen-content waste gas, the volume concentration of oxygen in the waste gas is lower than 0.1 percent, and SO is2The volume concentration is 0.5% or more, preferably 1% to 10%. According to the characteristics of the waste gas source, the SO is contained2The flue gas needs to be pretreated by dust removal, cooling and the like before compression.
In the invention, the compression unit mainly comprises a compressor and is used for compressing SO2Compressing the waste gas, and controlling the gauge pressure to be 0.1-1.0 MPaG.
In the invention, after compression and condensation or before entering the adsorption unit, the volume concentration of the water vapor in the flue gas is controlled to be 2-5%, which is beneficial to forming a synergistic purification effect with the adsorption effect.
In the invention, the adsorption unit consists of two or more than two adsorption towers and can alternately operate. The adsorption conditions were: the adsorption temperature is 0-40 ℃, the preferred temperature is 5-30 ℃, and the space velocity of the adsorption volume is 100-1000 h-1The adsorption pressure is 0.1-1.0 MPa.
The adsorption material is prepared by loading sodium sulfite on a carbonized metal organic framework material, wherein the loading amount of the sodium sulfite is not higher than 10% by mass, and preferably 2-7% by mass. The metal organic framework material is zinc-based metal organic framework material, such as at least one of MOFs series, ZIFs series and the like, and specifically, such as at least one of MOF-5, MOF-74, ZIF-8, ZIF-7, ZIF-20 and the like. Furthermore, the specific surface area of the metal organic framework material is 1500-1660 m2The pore volume is 1.07-1.15 cm3(ii) in terms of/g. The carbonized metal organic framework material is carbonized at 900-1150 ℃ in the presence of nitrogen, and the carbonization time is 5-10 hours. The metal carbide organic framework material hardly contains metal elements.
The preparation method of the adsorbing material comprises the following steps: taking a zinc-based metal organic framework material as a matrix, and carrying out carbonization treatment at a certain temperature to obtain a carbonized metal organic framework material; preparing sodium sulfite impregnation liquid, loading sodium sulfite by adopting an isovolumetric impregnation method, and drying after impregnation to obtain SO2Adsorbing the material. Mass concentration of sodium sulfite impregnation solution<6 percent, preferably 1.2 to 4 percent, and the dipping time is 1 to 5 hours. And after the impregnation is finished, drying at 100-120 ℃ for 6-10 hours in the presence of nitrogen.
In the present invention, the desorption regeneration may be at least one of heating regeneration, vacuum regeneration under reduced pressure, vacuum thermal regeneration under reduced pressure, and the like, and preferably vacuum thermal regeneration under reduced pressure is used. The absolute pressure of regeneration is maintained at 10-50kPa, the temperature is 180-2A gas.
The invention also provides a product containing SO2The waste gas treating apparatus includes mainly one compressing unit and one adsorbing unit comprising two or more adsorbing towers with loaded loadA carbonized metal organic framework material of sodium sulfite.
Compared with the prior art, the invention has the following advantages: the invention combines a novel SO through a cyclic process of compression condensation-adsorption-desorption2Adsorption of material, in favor of SO2By physical adsorption storage of2And the waste gas is efficiently recycled. Meanwhile, when the volume concentration of the water vapor is controlled to be 2-5%, the adsorbing material does not cause SO due to competitive adsorption2The adsorption quantity is reduced, but a synergistic purification effect is formed, and the SO is increased2Adsorption capacity. In the breakthrough time of the adsorption material of the invention, SO2The adsorption capacity of the catalyst is more than 2.3 times of that of commercial activated carbon, and the adsorption capacity of the catalyst is higher than that of SO in flue gas2Has high selective adsorption effect. After multiple times of cyclic adsorption-desorption, the adsorption capacity can still be stabilized to more than 85% of the initial adsorption capacity.
Drawings
FIG. 1 is a schematic flow diagram of the treatment process of the present invention, wherein: 1-compressor, 2-refrigerating unit, 3-buffer tank, 4-adsorption tower set and 5-SO2An online detector, 6-desorption vacuum pump, 7-heater, 8-heat regeneration vacuum pump.
Detailed Description
The SO-containing compositions of the present invention are further illustrated by the following examples2A method and an apparatus for treating exhaust gas. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the present invention, SO is contained2The waste gas is S-zorb regeneration flue gas, and is subjected to dust removal and cooling pretreatment before compression and condensation, and SO in the waste gas2The volume concentration of the component (A) is 2-5 percent, and the rest components are mainly N2And very small amounts of O2The smoke treatment capacity is 500Nm3/h。
The inventionSO in middle gas2The content was analyzed by an instrument (Emerson X-STREAM). The concentration of the adsorption outlet was set to 50mg/m3Is the penetration time, SO on activated carbon2The adsorption capacity is calculated by the following formula:
in the formula: q is sulfur capacity, mg/g; q is the total flow of the mixed gas at the inlet, mL/min; c0Is an inlet SO2Concentration, mg/L; ciIs the ith sampling outlet SO2Concentration, mg/L; t is the ith sampling time, min; n is the sampling times when the adsorption reaches saturation or within a specified time; m is the loading of the adsorbent material, g.
Example 1
The preparation method of the adsorbing material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655 m2G, pore volume of 1.13 cm3(ii) in terms of/g. Carbonizing at 1000 deg.C for 6 hr in the presence of nitrogen to obtain carbonized material. Placing the carbonized material in sodium sulfite solution, soaking in the same volume, and drying at 120 deg.C under nitrogen to obtain SO2The loading proportion of the adsorbing material and the sodium sulfite is 5 percent. The specific surface area of the prepared material is 2426 m through detection2G, pore volume of 3.27 cm3/g。
According to the process scheme of FIG. 1, SO is first introduced2The flue gas is compressed and condensed, the gauge pressure is controlled to be 0.5MPaG, and the temperature is controlled to be 5 ℃. The compression condensation enters into the adsorption unit after passing through the buffer tank, and the adsorption unit is filled with the carbonized metal organic framework material loaded with sodium sulfite. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 300h-1The adsorption pressure is 0.2-0.3 MPa. The concentration of an adsorption outlet is 50mg/m3Is taken as the penetration time by SO2The online analyzer detects exhaust gas, switches among the adsorption towers in an online control mode, and the penetration time of a single adsorption tower is about 1-3 h. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3. Vacuum desorption is adopted after the adsorption tower penetrates through the adsorption tower, the final absolute pressure of the adsorption tower is 10-50kPa, and the desorption time is the adsorption time60% of the total. Desorbed SO2The gas enters a coupling recovery pipe network. And when the adsorption capacity is reduced to below 85% of the initial adsorption capacity, carrying out primary vacuum thermal regeneration, wherein hot nitrogen is used as a gas source, the regeneration temperature is not more than 300 ℃, and the regeneration absolute pressure is 20-30 KPa.
After 10 times of circulating operation, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, and SO is recovered2About 1.17 tons.
Example 2
The procedure is as in example 1, except that SO is used2The loading of sodium sulfite in the adsorbent material was 1%. After 1 month operation, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, and SO is recovered under the same cycle times2About 0.92 ton.
Example 3
The procedure is as in example 1, except that SO is used2The loading of sodium sulfite in the adsorbent material was 7%. After 1 month operation, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, and SO is recovered under the same cycle times2About 1.12 tons.
Example 4
The procedure is as in example 1, except that SO is used2The loading of sodium sulfite in the adsorbent material was 10%. After 1 month operation, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, and SO is recovered under the same cycle times2About 0.95 ton.
Example 5
The procedure is as in example 1, except that SO is used2The adsorption material takes ZIF-8 as a substrate, and the specific surface area is 1150 m2Per g, pore volume of 0.82 cm3G, Zn content 30.7%. Carbonizing at 1150 ℃ for 5 hours in the presence of nitrogen to obtain the carbonized metal organic framework material. Putting the carbonized metal organic framework material into sodium sulfite solution with the mass concentration of 3%, soaking for 1h in the same volume, and drying for 6h at 120 ℃ in the presence of nitrogen after soaking to obtain SO2And the loading amount of the sodium sulfite on the adsorbing material is 5 percent.
After 1 month of operation, adsorptionThe adsorption capacity of the adsorbent can be stabilized to be more than 83% of the initial adsorption capacity, and the SO can be recovered under the same cycle number2About 0.86 ton.
Example 6
The procedure is as in example 1, except that SO is used2The adsorbing material takes MOF-74 as a matrix and has a specific surface area of 852 m2G, pore volume of 1.02 cm3G, Zn content 29.2%. Carbonizing at 900 ℃ for 10 hours in the presence of nitrogen to obtain the carbonized metal organic framework material. Putting the carbonized metal organic framework material into sodium sulfite solution with the mass concentration of 3%, soaking for 1h in the same volume, and drying for 6h at 120 ℃ in the presence of nitrogen after soaking to obtain SO2And the loading amount of the sodium sulfite on the adsorbing material is 5 percent.
After 1 month operation, the adsorption capacity of the adsorbent can be stabilized to more than 82% of the initial adsorption capacity, and SO is recovered under the same cycle times2About 0.81 ton.
Example 7
The process was carried out as in example 1, except that 5% of the water vapour was present in the flue gas after compression and condensation. After 10 times of circulating operation, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, and SO is recovered2About 1.26 tons.
Comparative example 1
The procedure is as in example 1, except that SO is used2The adsorbing material takes MOF-5 as a matrix and has a specific surface area of 1655 m2G, pore volume of 1.13 cm3G, Zn content 31.2%. Carbonizing at 1000 deg.C for 6 hr in the presence of nitrogen to obtain SO2Adsorbing the material. After 1 month operation, the adsorption capacity of the adsorbent can be stabilized to more than 80% of the initial adsorption capacity, and SO is recovered under the same cycle times2About 0.87 ton.
Comparative example 2
The procedure is as in example 1, except that SO is used2The adsorption material is prepared by soaking commercial activated carbon material in 3% sodium sulfite solution for 1 hr, drying at 120 deg.C for 6 hr in the presence of nitrogen gas to obtain SO2And the loading amount of the sodium sulfite on the adsorbing material is 5 percent. After 1 monthThe operation is carried out, the adsorption capacity of the adsorbent can be stabilized to be more than 75 percent of the initial adsorption capacity, and the SO is recovered under the same cycle times2About 0.55 ton.
Claims (13)
1. Containing SO2The method for treating the exhaust gas is characterized by comprising the following steps: the sulfur dioxide-containing waste gas is compressed and condensed in the compression unit and then enters the adsorption unit for adsorption, the adsorption material adopted by the adsorption unit is loaded with sodium sulfite on a carbonized metal organic framework material, and desorption regeneration is carried out after adsorption penetration.
2. The method of claim 1, wherein: the sulfur dioxide-containing waste gas is at least one of S-zorb regeneration flue gas, sulfur recovery device incineration flue gas and catalytic cracking regeneration flue gas, and the S-zorb regeneration flue gas is preferably selected.
3. The method according to claim 1 or 2, characterized in that: the sulfur dioxide-containing waste gas is low-oxygen-content flue gas, the volume concentration of oxygen in the flue gas is lower than 0.1 percent, and SO is contained in the flue gas2The volume concentration is 0.5% or more, preferably 1% to 10%.
4. The method of claim 1, wherein: the compression unit mainly comprises a compressor and is used for compressing SO2Compressing the waste gas, and controlling the gauge pressure to be 0.1-1.0 MPaG.
5. The method according to claim 1 or 4, characterized in that: after compression and condensation or before entering an adsorption unit, the volume concentration of the water vapor in the flue gas is controlled to be 2-5%.
6. The method of claim 1, wherein: the adsorption unit consists of two or more adsorption towers and alternately operates; the adsorption conditions were: the adsorption temperature is 0-40 ℃, the preferred temperature is 5-30 ℃, and the space velocity of the adsorption volume is 100-1000 h-1The adsorption pressure is 0.1-1.0 MPa.
7. The method of claim 1, wherein: in the adsorbing material, the loading amount of sodium sulfite is not higher than 10% by mass, and preferably 2-7%.
8. The method of claim 1, wherein: the metal organic framework material is zinc-based metal organic framework material, preferably at least one of MOFs series and ZIFs series.
9. The method of claim 8, wherein: the metal organic framework material is at least one of MOF-5, MOF-74, ZIF-8, ZIF-7 and ZIF-20.
10. The method of claim 1, 8 or 9, wherein: the carbonized metal organic framework material is carbonized at 900-1150 ℃ in the presence of nitrogen, and the carbonization time is 5-10 hours.
11. The method of claim 1, wherein: the desorption regeneration adopts at least one of heating regeneration, vacuum regeneration under reduced pressure and vacuum heat regeneration, and preferably adopts vacuum heat regeneration under reduced pressure.
12. The method of claim 1, wherein: the absolute pressure is maintained at 10-50kPa during regeneration, the temperature is 180 ℃ and 300 ℃, and the regeneration time is 2-8 hours.
13. SO-containing composition for use in the method according to claims 1-122The waste gas treating apparatus includes mainly compression unit and adsorption unit, and the adsorption unit consists of two or more adsorption towers filled with organic metal carbide skeleton material loaded with sodium sulfite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911048423.XA CN112742160A (en) | 2019-10-31 | 2019-10-31 | Containing SO2Method and apparatus for treating exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911048423.XA CN112742160A (en) | 2019-10-31 | 2019-10-31 | Containing SO2Method and apparatus for treating exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112742160A true CN112742160A (en) | 2021-05-04 |
Family
ID=75641013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911048423.XA Pending CN112742160A (en) | 2019-10-31 | 2019-10-31 | Containing SO2Method and apparatus for treating exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112742160A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284850A2 (en) * | 1987-03-09 | 1988-10-05 | Uop | Improved adsorptive purification process |
| US5770537A (en) * | 1995-12-04 | 1998-06-23 | General Electric Company | Low-temperature method to regenerate carbon loaded with sulfur compounds |
| CN1275424A (en) * | 2000-05-30 | 2000-12-06 | 费伦 | Novel technology and apparatus for removing SOx like harmful chemical substances from industrial waste gas |
| CN101444699A (en) * | 2008-12-16 | 2009-06-03 | 刘存宝 | Technical method for removing sulfur dioxide in flue gas by using sodium sulfite and equipment thereof |
| CN103920365A (en) * | 2014-04-21 | 2014-07-16 | 广西大学 | Method for recycling nitrogen gas and sulfur dioxide from calcining iron pyrite burner gas through variable-voltage variable-frequency adsorption |
| CN106310943A (en) * | 2016-08-31 | 2017-01-11 | 上海交通大学 | Device for regenerating sodium sulfite desulphurization liquid and recycling sulfur dioxide with sodium sulfite desulphurization liquid and application of device |
| CN106466548A (en) * | 2016-08-30 | 2017-03-01 | 安徽金禾实业股份有限公司 | A kind of processing method of sucralose tail gas |
| US20180214849A1 (en) * | 2017-02-02 | 2018-08-02 | Incheon University Industry Academic Cooperation Foundation | Mof-derived porous carbon materials for carbon dioxide capture |
| CN108751189A (en) * | 2018-07-14 | 2018-11-06 | 泉州师范学院 | The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area |
-
2019
- 2019-10-31 CN CN201911048423.XA patent/CN112742160A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0284850A2 (en) * | 1987-03-09 | 1988-10-05 | Uop | Improved adsorptive purification process |
| US5770537A (en) * | 1995-12-04 | 1998-06-23 | General Electric Company | Low-temperature method to regenerate carbon loaded with sulfur compounds |
| CN1275424A (en) * | 2000-05-30 | 2000-12-06 | 费伦 | Novel technology and apparatus for removing SOx like harmful chemical substances from industrial waste gas |
| CN101444699A (en) * | 2008-12-16 | 2009-06-03 | 刘存宝 | Technical method for removing sulfur dioxide in flue gas by using sodium sulfite and equipment thereof |
| CN103920365A (en) * | 2014-04-21 | 2014-07-16 | 广西大学 | Method for recycling nitrogen gas and sulfur dioxide from calcining iron pyrite burner gas through variable-voltage variable-frequency adsorption |
| CN106466548A (en) * | 2016-08-30 | 2017-03-01 | 安徽金禾实业股份有限公司 | A kind of processing method of sucralose tail gas |
| CN106310943A (en) * | 2016-08-31 | 2017-01-11 | 上海交通大学 | Device for regenerating sodium sulfite desulphurization liquid and recycling sulfur dioxide with sodium sulfite desulphurization liquid and application of device |
| US20180214849A1 (en) * | 2017-02-02 | 2018-08-02 | Incheon University Industry Academic Cooperation Foundation | Mof-derived porous carbon materials for carbon dioxide capture |
| CN108751189A (en) * | 2018-07-14 | 2018-11-06 | 泉州师范学院 | The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area |
Non-Patent Citations (4)
| Title |
|---|
| ANI WANG等: "N‑Doped Porous Carbon Derived by Direct Carbonization of Metal−Organic Complexes Crystal Materials for SO2 Adsorption", 《CRYST. GROWTH DES.》, vol. 19, 5 February 2019 (2019-02-05), pages 1973 - 1984, XP055809953, DOI: 10.1021/acs.cgd.8b01925 * |
| 姚仲鹏著: "《空气净化原理、设计与应用》", 中国科学技术出版社, pages: 139 - 140 * |
| 李一民主编: "《大气污染控制之制备的设计和维护手册》", 30 April 1993, 海洋出版社, pages: 72 * |
| 王吉坤主编: "《铅锌冶炼生产技术手册》", 31 January 2012, 冶金工业出版社, pages: 1124 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1113680C (en) | Temp.-changing adsorption | |
| CN103920365B (en) | Nitrogen in variable-frequency variable-voltage absorption recovery roasting pyrite furnace gas and the method for sulfur dioxide | |
| US20220040634A1 (en) | Method for desulphurizating and denitrating flue gas in integrated manner based on low-temperature adsorption | |
| WO2021232692A1 (en) | Method for low temperature adsorption and desulfurization of flue gas | |
| CN104087354B (en) | A kind of technique utilizing yellow phosphoric tail gas synthetic natural gas | |
| CN111375273B (en) | Treatment method and device for sulfur dioxide-containing waste gas | |
| CN111375271B (en) | Method and device for treating flue gas containing sulfur dioxide | |
| CN114835142B (en) | Method for recovering carbon dioxide from industrial kiln tail gas and producing lithium carbonate | |
| CN111375274B (en) | Containing SO 2 Gas treatment method and apparatus | |
| CN111375270B (en) | Containing SO2Flue gas treatment method and device | |
| CN111375382B (en) | SO (SO) 2 Adsorbing material and preparation method thereof | |
| CN210332252U (en) | To CO in cement kiln tail flue gas2Trapping, concentrating and utilizing system | |
| CN112742160A (en) | Containing SO2Method and apparatus for treating exhaust gas | |
| CN100336588C (en) | Process for regenerating sulfur loading active carbon | |
| CN111375383B (en) | SO (SO) device 2 Preparation method and application of adsorption material | |
| CN116078113A (en) | Method for capturing liquefied flue gas carbon dioxide by utilizing zeolite rotating wheel | |
| CN110756161B (en) | Process method for treating octanol waste gas pollution | |
| CN114433026B (en) | SO (SO) device 2 Adsorption material and preparation method thereof | |
| RU2624297C1 (en) | Method for producing carbon dioxide from flue gases | |
| CN110227337A (en) | CO in a kind of pair of cement kiln end flue gas2Trapping concentrate with utilize system | |
| CN114432870B (en) | FCC regenerated flue gas treatment method and device | |
| CN110755992B (en) | Modified adsorbent and preparation method thereof | |
| CN115178234B (en) | Composite hierarchical pore catalytic-adsorption material and preparation method thereof | |
| CN1140319C (en) | Desulfurizing technology and system with regenerable metal oxide as desulfurizing agent | |
| CN115254023B (en) | Preparation method of metal-loaded alkaline porous biochar and application of metal-loaded alkaline porous biochar in odor adsorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240320 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Country or region after: Zhong Guo Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Country or region before: Zhong Guo Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TA01 | Transfer of patent application right |