CN106824064A - The method that bivalve layer ZSM 5 molecular sieve adsorptions remove sulfur dioxide in flue gas - Google Patents
The method that bivalve layer ZSM 5 molecular sieve adsorptions remove sulfur dioxide in flue gas Download PDFInfo
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- CN106824064A CN106824064A CN201710239688.2A CN201710239688A CN106824064A CN 106824064 A CN106824064 A CN 106824064A CN 201710239688 A CN201710239688 A CN 201710239688A CN 106824064 A CN106824064 A CN 106824064A
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- molecular sieve
- flue gas
- zsm
- sulfur dioxide
- bivalve
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 85
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003546 flue gas Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 title abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 3
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 12
- 230000023556 desulfurization Effects 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000779 smoke Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 206010037423 Pulmonary oedema Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 206010006451 bronchitis Diseases 0.000 description 2
- 208000005333 pulmonary edema Diseases 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000241 respiratory effect Effects 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- VNODFDYEKIODIQ-UHFFFAOYSA-N C(CC)Br(CCC)(CCC)CCC Chemical compound C(CC)Br(CCC)(CCC)CCC VNODFDYEKIODIQ-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010023845 Laryngeal oedema Diseases 0.000 description 1
- 208000009612 Laryngismus Diseases 0.000 description 1
- 206010023891 Laryngospasm Diseases 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 206010044038 Tooth erosion Diseases 0.000 description 1
- 206010070841 Upper respiratory tract irritation Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 201000009267 bronchiectasis Diseases 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 208000036595 non-bacterial tooth erosion Diseases 0.000 description 1
- -1 nonferrous smelting Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002685 pulmonary effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- 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
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses the method that a kind of bivalve layer ZSM 5 molecular sieve adsorptions remove sulfur dioxide in flue gas, comprise the following steps：The molecular sieves of ZSM 5 are prepared as raw material with TPAOH, citric acid, tetraethyl orthosilicate, NaOH first, then the molecular sieves of obtained ZSM 5 and alkaline substance solution reaction are obtained the bivalve layer molecular sieves of ZSM 5, finally by the molecular sieves of obtained ZSM 5 and smoke contacts desulfurization.The method desulfuration efficiency is high, and the obtained bivalve layer molecular sieves of ZSM 5 are big with the contact area of flue gas, and adsorption capacity is big, and preparation cost is low.
Description
Technical field：
The present invention relates to air contaminant treatment field, it is specifically related in the layer ZSM-5 molecular sieve adsorbing and removing flue gas of bivalve
The method of sulfur dioxide.
Background technology：
The source of SO2 is divided into two major classes in air:Natural origin and artificial source.Natural source discharge capacity is accounted in air
The 1/3 of SO2 total amounts, including the SO2 ejected during volcano eruption, the H2S of marsh, depression, continental shelf etc. release enter air
The SO2 being oxidized afterwards, the sulfate aerosol that sulfurous organic compound is bacterially decomposed and ocean is formed is in an atmosphere through one
SO2 that series changes and produces etc..Naturally-produced SO2 belongs to global distribution, is discharged with low concentration in wide region, in air
In be easy to dilute and be cleaned, typically not into serious atmosphere pollution, acid rain phenomenon will not be produced.Artificial source discharge capacity is accounted for greatly
The 2/3 of SO2 total amounts in gas, including fossil fuel more than the 3/4 of source (account for artificial) and sulphur-containing substance industrial processes, arrange
High-volume larger industrial production sector has thermal power plant, steel, nonferrous smelting, chemical industry, oil refining, cement plant etc..And anthropogenic discharge
SO2 compares concentration, is occupied an leading position city of the ball surface less than 1% and industrial area overhead is taken up an area, be cause atmosphere pollution and
Produce the main cause of acid rain.
SO2 is a kind of colourless toxic gas for having an intense irritation smell, with polarity, and is highly soluble in water, at 20 DEG C,
IL water can dissolve the SO2 of 39.4L, and its aqueous solution is referred to as sulfurous acid (H2SO3), actually a kind of hydrate SO27H2O,
Sulfurous acid is subsequently oxidized into sulfuric acid, and concentration more suboxides are faster.Can to be combined into gas with moisture and grit molten for SO2 in an atmosphere
Glue, and gradually it is oxidized to sulfuric acid or sulfate.The harm that SO2 is produced mainly includes two aspects：First is the harm to human body；
Second is the harm to ecological environment.On the one hand influences of the SO2 to health mainly enter human body by respiratory system,
With respiratory apparatus effect, cause or aggravate respiratory illness.SO2 has strong pungent stimulation to conjunctiva and upper respiratory tract mucosa
Property, bronchitis, pneumonia can be caused after suction, severe patient can cause pulmonary edema and respiratory paralysis.SO2 concentration in an atmosphere reaches
0.02mg/L, can produce harm to body, when concentration is more than 0.3mg/L, may cause death.On the other hand, greatly
SO2 in gas can be oxidized to form SO3, and SO3 meets water vapour and forms sulfuric acid mist, and the sulfate that sulfuric acid mist is formed with small dust
Hazard ratio SO2 directly endangers also big.Can cause upper respiratory tract irritation after sulfuric acid mist suction, severe one occur expiratory dyspnea and
Pulmonary edema；Laryngospasm or glottic oedema can be caused during high concentration and fatal.Long Term Contact sulfuric acid mist or steam, can cause tooth erosion
The pulmonary lesions such as disease, chronic bronchitis, bronchiectasis.SO2 is also produced indirectly after forming acid rain to health simultaneously
Influence.Acid rain makes the surface water into acidity, and the tenor in underground water also increases, in drinking this water or edible acidity river
Fish can produce harm to health.Therefore, the emission reduction research of sulfur dioxide becomes the focus of research, and in China's dioxy
The emission reduction policy for changing sulphur is mainly focused on the raising of energy efficiency and the popularization of flue gas desulfurization technique.Wherein, flue gas takes off after burning
Sulphur is the most studied, technology that progress is also most fast in SO2 emission-reduction technologies, and being also current large-scale commercial unique in the world should
Desulfurization technology.Wherein desulfurization of flue gas by adsorption technology, is one kind of most most study.Desulfurization of flue gas by adsorption technology is to utilize porous
Solid absorbent processes sulfur-containing smoke gas, contained SO2 components in flue gas is adsorbed on the surface of solids, to reach flue gas desulfurization
Purpose.The advantage of desulfurization of flue gas by adsorption technology is:There is purification efficiency very high to low concentration SO 2, equipment is simple, easy to operate,
It is capable of achieving to automatically control, can effectively reclaims SO2, realizes changing waste into resources.The key of desulfurization of flue gas by adsorption technology technology is absorption
The selection of agent.
ZSM-5 molecular sieve is an important microporous solids material, and it is widely used in the absorption and separation of gas.By
There is good porous and permeability, larger specific surface area and pore volume in it, the scavenger of SO2, Er Qiefen is often used as
Son sieve desulfurization greatly reduces the waste of water and the consumption of the energy, becomes the new selection of one kind of control SO2.But it is conventional at present
ZSM-5 molecular sieve, micro channel is narrow, has larger resistance to mass tranfer in adsorbing and removing sulfur dioxide, and influence molecule expands
Dissipate, so as to have impact on the effect of desulfurization.
The content of the invention：
It is an object of the invention to provide a kind of method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas,
, using bivalve layer ZSM-5 molecular sieve, it is bigger with the contact area of flue gas, is conducive to the diffusion of sulfur dioxide molecule for the method,
Substantially increase the removal efficiency of sulfur dioxide.
To achieve the above object, the present invention uses following technical scheme：
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1-2h are stirred at room temperature, be then transferred to anti-
Answer in kettle, crystallization, centrifuge washing after crystallization, drying and roasting obtains ZSM-5 molecular sieve；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 80-200 DEG C is then heated to, is continued
Stirring reaction 5-200h, after the completion of reaction, centrifuge washing is dried, roasting, obtains bivalve layer ZSM-5 molecular sieve；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 0.5-1.2h is purged with nitrogen at 300-400 DEG C, is then in volume space velocity
3000-5000h-1Under the conditions of be passed through normal pressure flue gas, the titanium dioxide after sulfur dioxide in before processing flue gas and treatment in flue gas
Sulfur content is by gas chromatograph for determination.
As the preferred of above-mentioned technical proposal, in step (1), the TPAOH, deionized water, citric acid,
Tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：(9-9.5)g：(9.95-10.5)g：(0.15-0.36)g：
(19.75-20.05)g：(5.67-6.35)g：(0.302-0.320)g.
Used as the preferred of above-mentioned technical proposal, in step (1), the condition of the roasting is：3- is calcined at 500-600 DEG C
6h。
As the preferred of above-mentioned technical proposal, alkaline matter described in step (2) be quaternary ammonium salt and NaOH by mole
Than being 1:1 mixture, quaternary ammonium salt and potassium hydroxide are in molar ratio 1:One kind in 1 mixture, n-butylamine, quaternary ammonium base or
It is various.
Used as the preferred of above-mentioned technical proposal, the quaternary ammonium salt is 4 bromide, tetraethylammonium bromide, tetrapropyl bromine
Change one or more in ammonium and TBAB.
Used as the preferred of above-mentioned technical proposal, the quaternary ammonium base is TMAH, tetraethyl ammonium hydroxide and four
One or more in butyl ammonium hydroxide.
Used as the preferred of above-mentioned technical proposal, in step (2), the sintering temperature is 500-900 DEG C, and roasting time is 1-
12h。
As the preferred of above-mentioned technical proposal, in step (2), the matter of the ZSM-5 molecular sieve and alkaline substance solution
Amount is than being 1：(4-40).
The invention has the advantages that：
On the one hand, the present invention was added suitable when ZSM-5 molecular sieve is prepared before NaAlO2 and tetraethyl orthosilicate mixing
The citric acid of amount, it can effectively control the speed that molecular sieve is formed, prevent its prepare impurity in the aperture that causes of excessive velocities it is many,
The problems such as aperture is irregular；
On the other hand, obtained ZSM-5 molecular sieve and alkaline substance solution hybrid reaction are obtained bivalve layer by the present invention
ZSM-5 molecular sieve, it is hollow-core construction, and shell is made up of two-layer isomorphism molecular sieve, and cavity structure is formed between shell, and it compares table
Area is big, and adsorption activity center is more, and when being processed for flue gas desulfurization, efficiency high, clearance is big.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1h are stirred at room temperature, be then transferred to reaction
In kettle, crystallization, centrifuge washing after crystallization is dried, and 6h is calcined at 500 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydroxide
Ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9g：9.95g：0.15g：
19.75g：5.67g：0.302g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 80 DEG C are then heated to, continues to stir
Reaction 200h, after the completion of reaction, centrifuge washing is dried, and 12h is calcined at 500 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein,
Alkaline matter is that 4 bromide is in molar ratio 1 with NaOH:1 mixture；ZSM-5 molecular sieve and alkaline matter water
The mass ratio of solution is 1：4；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 0.5h is purged with nitrogen at 300 DEG C, is then 3000h in volume space velocity-1Condition
Under be passed through normal pressure flue gas, the content of sulfur dioxide after sulfur dioxide in before processing flue gas and treatment in flue gas is by gas-chromatography
Instrument is determined.
After measured, the concentration of SO2 is 200ppm, the adsorbance 230mg/g of SO2 in before processing flue gas.
Embodiment 2
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 2h are stirred at room temperature, be then transferred to reaction
In kettle, crystallization, centrifuge washing after crystallization is dried, and 3h is calcined at 600 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydroxide
Ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9.5g：10.5g：0.36g：
20.05g：6.35g：0.320g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 200 DEG C are then heated to, continues to stir
Reaction 5h, after the completion of reaction, centrifuge washing is dried, and 1h is calcined at 900 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein, alkalescence
Material is that 4 bromide is in molar ratio 1 with potassium hydroxide:1 mixture；ZSM-5 molecular sieve and alkaline substance solution
Mass ratio be 1：40；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 1.2h is purged with nitrogen at 400 DEG C, is then 5000h in volume space velocity-1Condition
Under be passed through normal pressure flue gas, the content of sulfur dioxide after sulfur dioxide in before processing flue gas and treatment in flue gas is by gas-chromatography
Instrument is determined.
After measured, the concentration of SO2 is 600ppm, the adsorbance 245mg/g of SO2 in before processing flue gas.
Embodiment 3
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1.2h are stirred at room temperature, be then transferred to anti-
Answer in kettle, crystallization, centrifuge washing after crystallization is dried, and 4h is calcined at 500 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydrogen-oxygen
Change ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9.1g：10.0g：0.2g：
19.95g：5.85g：0.308g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 100 DEG C are then heated to, continues to stir
Reaction 160h, after the completion of reaction, centrifuge washing is dried, and 10h is calcined at 600 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein,
Alkaline matter is n-butylamine；ZSM-5 molecular sieve is 1 with the mass ratio of alkaline substance solution：10；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 1h is purged with nitrogen at 300 DEG C, is then 3500h in volume space velocity-1Under the conditions of
Normal pressure flue gas is passed through, the content of sulfur dioxide after the sulfur dioxide and treatment in before processing flue gas in flue gas is by gas chromatograph
Determine.
After measured, the concentration of SO2 is 300ppm, the adsorbance 275mg/g of SO2 in before processing flue gas.
Embodiment 4
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1.4h are stirred at room temperature, be then transferred to anti-
Answer in kettle, crystallization, centrifuge washing after crystallization is dried, and 4h is calcined at 550 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydrogen-oxygen
Change ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9.2g：10.2g：0.25g：
20.0g：6.0g：0.315g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 130 DEG C are then heated to, continues to stir
Reaction 140h, after the completion of reaction, centrifuge washing is dried, and 8h is calcined at 700 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein, alkali
Property material be TMAH；ZSM-5 molecular sieve is 1 with the mass ratio of alkaline substance solution：20；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 1h is purged with nitrogen at 350 DEG C, is then 4000h in volume space velocity-1Under the conditions of
Normal pressure flue gas is passed through, the content of sulfur dioxide after the sulfur dioxide and treatment in before processing flue gas in flue gas is by gas chromatograph
Determine.
After measured, the concentration of SO2 is 400ppm, the adsorbance 269mg/g of SO2 in before processing flue gas.
Embodiment 5
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1.6h are stirred at room temperature, be then transferred to anti-
Answer in kettle, crystallization, centrifuge washing after crystallization is dried, and 5h is calcined at 550 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydrogen-oxygen
Change ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9.3g：10.3g：0.3g：
20.02g：6.12g：0.315g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 150 DEG C are then heated to, continues to stir
Reaction 100h, after the completion of reaction, centrifuge washing is dried, and 6h is calcined at 800 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein, alkali
Property material be that 4-propyl bromide and NaOH are in molar ratio 1:1 mixture；ZSM-5 molecular sieve is water-soluble with alkaline matter
The mass ratio of liquid is 1：30；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 0.5h is purged with nitrogen at 350 DEG C, is then 4500h in volume space velocity-1Condition
Under be passed through normal pressure flue gas, the content of sulfur dioxide after sulfur dioxide in before processing flue gas and treatment in flue gas is by gas-chromatography
Instrument is determined.
After measured, the concentration of SO2 is 400ppm, the adsorbance 258mg/g of SO2 in before processing flue gas.
Embodiment 6
The method of bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, comprises the following steps：
(1) first by TPAOH and deionized water mixing and stirring, NaAlO2, citric acid are subsequently adding and are mixed
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously after conjunction, after completion of dropping, 1.6h are stirred at room temperature, be then transferred to anti-
Answer in kettle, crystallization, centrifuge washing after crystallization is dried, and 5h is calcined at 600 DEG C, obtains ZSM-5 molecular sieve；Wherein, tetrapropyl hydrogen-oxygen
Change ammonium, deionized water, citric acid, tetraethyl orthosilicate, NaOH：The mass ratio of NaAlO2 is：9.4g：10.4g：0.34g：
20.03g：6.25g：0.317g；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 180 DEG C are then heated to, continues to stir
Reaction 50h, after the completion of reaction, centrifuge washing is dried, and 4h is calcined at 800 DEG C, obtains bivalve layer ZSM-5 molecular sieve；Wherein, alkali
Property material be TBAH；ZSM-5 molecular sieve is 1 with the mass ratio of alkaline substance solution：40；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends dress
Rockfill sand, before being passed through flue gas, molecular sieve 1h is purged with nitrogen at 400 DEG C, is then 4500h in volume space velocity-1Under the conditions of
Normal pressure flue gas is passed through, the content of sulfur dioxide after the sulfur dioxide and treatment in before processing flue gas in flue gas is by gas chromatograph
Determine.
After measured, the concentration of SO2 is 500ppm, the adsorbance 260mg/g of SO2 in before processing flue gas.
Comparative example 1
Citric acid is not added with the preparation of ZSM-5 molecular sieve, other preparation conditions and embodiment 6 are identical.
After measured, the concentration of SO2 is 500ppm in before processing flue gas, and the adsorbance of SO2 is 175mg/g.
Comparative example 2
Citric acid, and the unused alkaline substance solution of ZSM-5 molecular sieve for preparing are not added with the preparation of ZSM- molecular sieves
Treatment, other preparation conditions and embodiment 6 are identical.
After measured, the concentration of SO2 is 500ppm in before processing flue gas, and the adsorbance of SO2 is 102mg/g.
Comparative example 3
The ZSM-5 molecular sieve of preparation not with alkaline substance solution reaction treatment, other preparation conditions and the phase of embodiment 6
Together.
After measured, the concentration of SO2 is 500ppm in before processing flue gas, and the adsorbance of SO2 is 139mg/g.
Claims (8)
1. bivalve layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas method, it is characterised in that comprise the following steps：
(1) first by TPAOH and deionized water mixing and stirring, after being subsequently adding NaAlO2, citric acid mixing
Tetraethyl orthosilicate and NaOH are added dropwise over simultaneously, after completion of dropping, 1-2h are stirred at room temperature, be then transferred to reactor
In, crystallization, centrifuge washing after crystallization, drying and roasting obtains ZSM-5 molecular sieve；
(2) by ZSM-5 molecular sieve and alkaline substance solution mixing and stirring, 80-200 DEG C is then heated to, continues to stir
Reaction 5-200h, after the completion of reaction, centrifuge washing is dried, roasting, obtains bivalve layer ZSM-5 molecular sieve；
(3) bivalve obtained above layer ZSM-5 molecular sieve is encased in continuous fixed bed reactor stage casing, two ends filling stone
Sand, before being passed through flue gas, molecular sieve 0.5-1.2h is purged at 300-400 DEG C with nitrogen, is then 3000- in volume space velocity
5000h-1Under the conditions of be passed through normal pressure flue gas, the content of sulfur dioxide after sulfur dioxide in before processing flue gas and treatment in flue gas
By gas chromatograph for determination.
2. the method for bivalve as claimed in claim 1 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In, in step (1), the TPAOH, deionized water, citric acid, tetraethyl orthosilicate, NaOH, NaAlO2
Mass ratio be：(9-9.5)g：(9.95-10.5)g：(0.15-0.36)g：(19.75-20.05)g：(5.67-6.35)g：
(0.302-0.320)g。
3. the method for bivalve as claimed in claim 1 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In in step (1), the condition of the roasting is：3-6h is calcined at 500-600 DEG C.
4. the method for bivalve as claimed in claim 1 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In：Alkaline matter described in step (2) is that quaternary ammonium salt is in molar ratio 1 with NaOH:1 mixture, quaternary ammonium salt and hydrogen-oxygen
It is in molar ratio 1 to change potassium:One or more in 1 mixture, n-butylamine, quaternary ammonium base.
5. the method for bivalve as claimed in claim 4 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In：The quaternary ammonium salt be 4 bromide, tetraethylammonium bromide, 4-propyl bromide and TBAB in one kind or
It is various.
6. the method for bivalve as claimed in claim 4 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In：The quaternary ammonium base is one or more in TMAH, tetraethyl ammonium hydroxide and TBAH.
7. the method for bivalve as claimed in claim 1 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In：In step (2), the sintering temperature is 500-900 DEG C, and roasting time is 1-12h.
8. the method for bivalve as claimed in claim 1 layer ZSM-5 molecular sieve adsorbing and removing sulfur dioxide in flue gas, its feature exists
In：In step (2), the ZSM-5 molecular sieve is 1 with the mass ratio of alkaline substance solution：(4-40).
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