CN114433026B - SO (SO) device 2 Adsorption material and preparation method thereof - Google Patents

SO (SO) device 2 Adsorption material and preparation method thereof Download PDF

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Publication number
CN114433026B
CN114433026B CN202011198075.7A CN202011198075A CN114433026B CN 114433026 B CN114433026 B CN 114433026B CN 202011198075 A CN202011198075 A CN 202011198075A CN 114433026 B CN114433026 B CN 114433026B
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adsorption
organic framework
metal organic
sodium sulfite
framework material
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CN114433026A (en
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汪鹏
赵磊
王学海
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25Coated, impregnated or composite adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to an SO 2 The adsorption material and the preparation method thereof are that sodium sulfite and disodium ethylenediamine tetraacetate are loaded on carbonized metal organic framework material, and the loading amount of the sodium sulfite is not higher than 10 percent by mass, preferably 2 to 7 percent by mass; the loading of disodium ethylenediamine tetraacetate is not higher than 5%, preferably 1% -3%. The invention is SO obtained by modifying MOFs material and loading sodium sulfite and disodium ethylene diamine tetraacetate 2 Adsorption material with higher SO 2 Adsorption capacity and selectivity, especially for water, oxygen and SO 2 Selective adsorption of exhaust gas.

Description

SO (SO) device 2 Adsorption material and preparation method thereof
Technical Field
The invention belongs to the technical field of sulfur-containing flue gas treatment, and in particular relates to an SO 2 An adsorption material and a preparation method thereof.
Background
Fossil fuels (coal, petroleum, etc.) contain significant amounts of sulfur and direct combustion results in high levels of SO in flue gases 2 。SO 2 The 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 life of human beings. At present, widely adopted SO 2 The removal method is classified into wet desulfurization technology and dry desulfurization technology. Wet desulfurizing is carried out by contacting alkali liquid with fume, and reacting SO 2 The solution is converted into sulfite and sulfate which are dissolved in water, and the sulfate-containing solution is further treated to achieve the purpose of desulfurization. Dry desulfurization mainly uses the adsorption property of porous material to make SO 2 Separating from waste gas, and desorbing for regeneration or oxidizing for conversion into SO after saturation 3 Eluting.
In the wet desulfurization technology applied in industry, SO can be absorbed by sodium sulfite solution 2 Realizing SO removal from waste gas 2 . The dry flue gas desulfurization method widely used in industry uses activated carbon material as an adsorption oxidant through adsorption-oxidation-sulfuric acidSO is removed in the processes of chemical-alkaline washing and the like 2 . SO in S-Zorb flue gas in petroleum refining industry 2 Concentration of>1%, more suitable for SO 2 And desorbing and recovering the adsorbed sulfur. The adsorption material applied in the traditional desulfurization process has oxidation performance and is easy to carry out SO 2 Oxidation to SO 3 Is not suitable for adsorbing-desorbing and recycling SO in S-Zorb flue gas 2 . In addition, O in S-Zorb flue gas 2 The content is low (the volume concentration is generally lower than 0.1 percent), SO is not suitable 2 Oxidation to SO 3 Is processed according to the processing mode of the system.
The metal organic framework Materials (MOFs) are organic macromolecular porous materials, and metals and organic ligands are combined into the macromolecular porous materials with infinite topological structures through coordination, so that the metal organic framework materials have rich micropore structures and high specific surface areas. However, the metal organic framework material takes metal as a central node, contains metal oxide and adsorbs SO 2 Is easy to cause chemical reaction at the same time, thus being suitable for low concentration SO-containing 2 Chemisorption of the gas. And the adsorption effect is reduced when water and oxygen exist in the waste gas.
Disclosure of Invention
Aiming at the defects of the existing adsorption material, the invention provides an SO 2 An adsorption material and a preparation method thereof. The invention is SO obtained by modifying MOFs material and loading sodium sulfite and disodium ethylene diamine tetraacetate 2 Adsorption material with higher SO 2 Adsorption capacity and selectivity, especially for water, oxygen and SO 2 Selective adsorption of exhaust gas.
SO provided by the invention 2 The adsorption material is characterized in that sodium sulfite and disodium ethylenediamine tetraacetate are loaded on the carbonized metal organic framework material, and the loading amount of the sodium sulfite is not higher than 10% by mass, preferably 2% -7%; the loading of disodium ethylenediamine tetraacetate is not higher than 5%, preferably 1% -3%.
In the adsorption material, the metal organic framework material is a zinc-based metal organic framework material, such as at least one of MOFs series, and particularly at least one of MOF-5, MOF-74 and the like. Further, the specific surface area of the metal organic framework material is 800-1800m 2 Per g, pore volume of 0.8-1.2cm 3 /g。
In the adsorption material, 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 carbonized metal organic framework material does not contain metal elements.
The invention also provides the SO 2 The preparation method of the adsorption material comprises the following steps:
(1) Taking a zinc-based metal organic framework material as a matrix, and carbonizing at a certain temperature to obtain a carbonized metal organic framework material;
(2) Preparing sodium sulfite and disodium ethylenediamine tetraacetate impregnating solution, impregnating the carbonized metal organic framework material therein, and drying after impregnation to obtain SO 2 An adsorbent material.
In the preparation method of the invention, the metal organic framework material is a zinc-based metal organic framework material, such as at least one of MOFs series, and particularly at least one of MOF-5, MOF-74 and the like. Further, the specific surface area of the metal organic framework material is 800-1800m 2 Per g, pore volume of 0.8-1.2cm 3 /g。
In the invention, the carbonization conditions are as follows: in the presence of nitrogen, the carbonization temperature is 900-1150 ℃ and the carbonization time is 5-10 hours. The carbonized metal organic framework material almost contains no metal elements.
In the invention, in the impregnating solution in the step (2), the mass concentration of sodium sulfite is less than 6%, preferably 1.2% -4%, and the mass concentration of disodium ethylenediamine tetraacetate is 1% -10%.
In the present invention, the immersion time is 1 to 5 hours. After the impregnation is completed, drying is carried out at 100-120 ℃ for 6-10 hours in the presence of nitrogen.
SO according to the invention 2 The adsorption material is applicable to the application of water, oxygen and SO 2 SO in exhaust gas 2 In which SO 2 The volume concentration of (2) is more than 1%, preferably 1% to 5%. The adsorption conditions are as follows: the adsorption temperature is 5-25 ℃, and the space velocity of the adsorption volume is 100-1000 h -1 The adsorption pressure is 0.1-0.3MPa。
Compared with the prior art, the invention has the following advantages:
(1) The invention is SO obtained by modifying MOFs material and loading sodium sulfite and disodium ethylene diamine tetraacetate 2 Adsorption material with higher SO 2 Adsorption capacity and selectivity, especially for water, oxygen and O 2 SO in the exhaust gas of (2) 2 Selective adsorption.
(2) During the penetration time, SO 2 The adsorption capacity of the catalyst is 130-265 mg/g, which is more than 2.5 times of that of commercial active carbon and more than 2 times of that of MOFs material.
(3) SO of the invention 2 The adsorption material can be regenerated by heating desorption, and the adsorption capacity can be stabilized to be more than 85% of the initial adsorption capacity after repeated cyclic adsorption-desorption, SO as to solve SO in the flue gas in the petroleum refining industry 2 The adsorption and recycling have important functions.
Detailed Description
The SO of the present invention is further illustrated by the following examples 2 An adsorption material, a preparation method and application thereof. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The specific surface area and pore volume of the material in the invention are N 2 And (5) testing and analyzing an adsorption and desorption curve by using an adsorption instrument. The content of the metal element was analyzed by ICP method. SO in gas 2 The content was analyzed by an instrument (Emerson X-STREAM). Setting adsorption outlet SO 2 Penetration concentration (typically below 50 mg/m 3 ) SO on activated carbon 2 The adsorption capacity is calculated by the following formula:
wherein: q is sulfur capacity, mg/g; q is the total flow of the inlet mixed gas, and mL/min; c (C) 0 Is an inlet SO 2 Concentration, mg/L; c (C) i For the ith sampling outlet SO 2 Concentration, 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 adsorption material and g.
Example 1
MOF-5 is used as matrix, and the specific surface area is 1655 m 2 Per gram, pore volume of 1.13 cm 3 /g, zn content 31.2%. Carbonizing at 1000 ℃ for 6 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% and disodium ethylenediamine tetraacetate solution with the mass concentration of 5%, soaking for 1h in an equal volume, and drying at 120 ℃ for 6h in the presence of nitrogen after soaking to obtain SO 2 The loading of the adsorption material of sodium sulfite is 5% and the loading of disodium ethylenediamine tetraacetate is 2%.
Example 2
The preparation method is the same as in example 1, except that SO is obtained 2 The loading of sodium sulfite in the adsorption material is 1%, and the loading of disodium ethylenediamine tetraacetate is 3%.
Example 3
The preparation method is the same as in example 1, except that SO is obtained 2 The sodium sulfite loading in the adsorption material is 7%, and the disodium ethylenediamine tetraacetate loading is 1.0%.
Example 4
MOF-74 is taken as a matrix, and the specific surface area is 852 to 852 m 2 Per gram, pore volume of 1.02. 1.02 cm 3 /g, zn content 29.2%. Carbonizing for 10 hours at 900 ℃ 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% and disodium ethylenediamine tetraacetate solution with the mass concentration of 5%, soaking for 1h in an equal volume, and drying at 120 ℃ for 6h in the presence of nitrogen after soaking to obtain SO 2 The adsorption material has sodium sulfite loading of 5% and disodium ethylenediamine tetraacetate loading of 5%.
Comparative example 1
The difference from example 1 is that: and no disodium ethylenediamine tetraacetate is loaded.
Comparative example 2
The difference from example 1 is that: sodium sulfite was not loaded.
Comparative example 3
The difference from example 1 is that: the metal organic framework material is not carbonized.
The adsorption materials prepared in the examples and comparative examples of the present invention were subjected to adsorption performance test. Wherein SO in the flue gas 2 Is 3% by volume, 5% by water vapor and 5% by oxygen. The adsorption conditions are as follows: the adsorption temperature is 20 ℃ and the adsorption airspeed is 800h -1 The adsorption pressure is normal pressure and 0.2MPaG, and the adsorption outlet concentration is 50 mg/m 3 As the penetration time. The test results are shown in Table 1.
TABLE 1 different SOs 2 Adsorption capacity of adsorbent Material (mg/g)

Claims (14)

1. SO (SO) device 2 The adsorption material is characterized in that: sodium sulfite and disodium ethylenediamine tetraacetate are loaded on the carbonized metal organic framework material, wherein the loading amount of the sodium sulfite is not higher than 10% by mass, and the loading amount of the disodium ethylenediamine tetraacetate is not higher than 5%; the metal organic framework material is at least one of MOFs.
2. The adsorbent material of claim 1, wherein: the loading of the sodium sulfite is 2-7% by mass, and the loading of the disodium ethylenediamine tetraacetate is 1-3%.
3. The adsorbent material of claim 1, wherein: the metal organic framework material is at least one of MOF-5 and MOF-74.
4. According to claim 1-3, characterized in that: the specific surface area of the metal organic framework material is 800-1800m 2 Per g, pore volume of 0.8-1.2cm 3 /g。
5. The adsorbent material of claim 1, wherein: the carbonized metal organic framework material is carbonized at 900-1150 ℃ in the presence of nitrogen for 5-10 hours.
6. The SO as claimed in any one of claims 1 to 5 2 The preparation method of the adsorption material is characterized by comprising the following steps:
(1) Taking a metal organic framework material as a matrix, and carbonizing at a certain temperature to obtain a carbonized metal organic framework material; the metal organic framework material is at least one of MOFs;
(2) Preparing sodium sulfite and disodium ethylenediamine tetraacetate impregnating solution, impregnating the carbonized metal organic framework material therein, and drying after impregnation to obtain SO 2 An adsorbent material.
7. The method of manufacturing according to claim 6, wherein: the metal organic framework material is at least one of MOF-5 and MOF-74.
8. The method of manufacturing according to claim 6, wherein: the carbonization conditions are as follows: in the presence of nitrogen, the carbonization temperature is 900-1150 ℃ and the carbonization time is 5-10 hours.
9. The method of manufacturing according to claim 6, wherein: in the impregnating solution in the step (2), the mass concentration of sodium sulfite is less than 6%, and the mass concentration of disodium ethylenediamine tetraacetate is 1% -10%.
10. The method of manufacturing according to claim 9, wherein: in the impregnating solution in the step (2), the mass concentration of the sodium sulfite is 1.2-4%.
11. The method of manufacturing according to claim 6, wherein: the dipping time is 1-5 hours, and the dipping is carried out and then the drying is carried out for 6-10 hours at 100-120 ℃ in the presence of nitrogen.
12. The SO of any one of claims 1 to 5 2 The application of the adsorption material is characterized in that: is suitable for containing water, oxygen and SO 2 SO in exhaust gas 2 In which SO 2 Is greater than 1% by volume.
13. The use according to claim 12, characterized in that: SO (SO) 2 The volume concentration of (2) is 1-5%.
14. The use according to claim 12, characterized in that: the adsorption temperature is 5-25 ℃, and the space velocity of the adsorption volume is 100-1000 h -1 The adsorption pressure is 0.1-0.3 MPa.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2452957A1 (en) * 1979-04-06 1980-10-31 Inst Francais Du Petrole Sepg. hydrogen sulphide and nitrogen oxide simultaneously - from gas mixts., using chelated iron salt with iron at least, partly ter-valent
CN103058229A (en) * 2013-01-21 2013-04-24 福建省邵武市榕丰化工有限公司 Application for disodium edetate dehydrate
CN103657341A (en) * 2013-12-10 2014-03-26 陕西省石油化工研究设计院 Anti-oxidation type SO2 absorbing recycle agent
CN106823693A (en) * 2017-03-28 2017-06-13 中北大学 A kind of deep desulfuration absorbent for smoke-gas wet desulfurization
CN111375383A (en) * 2018-12-31 2020-07-07 中国石油化工股份有限公司 SO (SO)2Preparation method and application of adsorbing material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2452957A1 (en) * 1979-04-06 1980-10-31 Inst Francais Du Petrole Sepg. hydrogen sulphide and nitrogen oxide simultaneously - from gas mixts., using chelated iron salt with iron at least, partly ter-valent
CN103058229A (en) * 2013-01-21 2013-04-24 福建省邵武市榕丰化工有限公司 Application for disodium edetate dehydrate
CN103657341A (en) * 2013-12-10 2014-03-26 陕西省石油化工研究设计院 Anti-oxidation type SO2 absorbing recycle agent
CN106823693A (en) * 2017-03-28 2017-06-13 中北大学 A kind of deep desulfuration absorbent for smoke-gas wet desulfurization
CN111375383A (en) * 2018-12-31 2020-07-07 中国石油化工股份有限公司 SO (SO)2Preparation method and application of adsorbing material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"N-Doped Porous Carbon Derived by Direct Carbonization of Metal-Organic Complexes Crystal Materials for SO2 Adsorption";Ani Wang等;《Cryst. Growth Des.》;第1973-1984页 *

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