CN110102253A - The preparation method of sulfur dioxide adsorbent for smoke gas treatment - Google Patents
The preparation method of sulfur dioxide adsorbent for smoke gas treatment Download PDFInfo
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- CN110102253A CN110102253A CN201910401397.8A CN201910401397A CN110102253A CN 110102253 A CN110102253 A CN 110102253A CN 201910401397 A CN201910401397 A CN 201910401397A CN 110102253 A CN110102253 A CN 110102253A
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003463 adsorbent Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000779 smoke Substances 0.000 title claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229960002788 cetrimonium chloride Drugs 0.000 claims abstract description 12
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 11
- HELABVNXROLNTJ-UHFFFAOYSA-N C[N+](C)(C)C.[Si](O)(O)(O)O Chemical compound C[N+](C)(C)C.[Si](O)(O)(O)O HELABVNXROLNTJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003546 flue gas Substances 0.000 abstract description 26
- 239000007789 gas Substances 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005864 Sulphur Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- 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
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
Abstract
The invention discloses a kind of preparation method of sulfur dioxide adsorbent for smoke gas treatment, the techniques of use are as follows: 4.6-5.6 parts of Ammonias and 36.8-44.4 parts of cetrimonium chloride solutions, five water tetramethylammonium hydroxide of 3.0-6.9 part, 35.5-41.0 parts of silicic acid tetramethyl-ammonium solution, 4.0-9.8 parts of fumed silica are generated reaction gel；It is then placed in hydrothermal reaction kettle, the concentrated sulfuric acid is added, then adjust pH and continue hydro-thermal reaction 1-4 times, sulfur dioxide adsorbent is made after carrying out powder calcination in the product after air-drying.The present invention has the advantages that removal rate of sulfur dioxide is high, sulphur adsorption capacity is big, is suitble to use under 250-800 DEG C of high temperature, the improvement particularly suitable for coal-fired flue-gas under the hot environments such as metallurgy, electric power.
Description
Technical field
The invention belongs to sulfur dioxide adsorbent preparation technical fields, more particularly, to a kind of absorption sulfur dioxide in flue gas
Adsorbent material preparation method, the improvement particularly suitable for coal-fired flue-gas under the hot environments such as metallurgy, electric power.
Background technique
It is well known that because fossil fuel burning and exhausting in atmosphere SOx to atmospheric environment caused by seriously pollute, to people
The existence of class, animal and plant constitutes a serious threat.It is counted according to national environmental statistics bulletin in 2015, SO in national exhaust gas2Row
1859.1 ten thousand tons are high-volume up to, causes strong influence to the production and life of the people.How SOx row is cost-effectively controlled
High-volume have become the important topic that vast desulfurization person faces.It is further endangered caused by sulphur emissions to reduce or eliminate, country
It is required that every profession and trade minimum discharge.
Gas absorption desulfurization technology has that treating capacity is big, sulphur concentration is low in outlet and various sulfide adaptability after desulfurization
High advantage has broad application prospects in terms of the removing of abjection sulfur dioxide in flue gas.Therefore, a kind of engineering throwing is developed
The environmentally friendly sulfur dioxide adsorption technology for providing subsequent processing lower, that the by-product after desulfurization is not present again is extremely urgent.
CN103769043A discloses adsorbent, preparation and its application method of sulfurous gas in a kind of gas, adsorbent
By zinc oxide (preferably 40-65%), metallic promoter agent (preferably 5-15%), M41S series mesoporous material (preferably 12-25%), calcium
Oxysalt (preferably 14-30%), VB or vib metal oxide (preferably 3-10%).The absorption object of institute's publicity is removing
Sulfurous gas in natural gas, the adsorbent are not mentioned to the removing situation to sulfur dioxide in flue gas gas.
CN105344336A discloses a kind of preparation method of sulfur dioxide adsorbent, and adsorbent is by triblock copolymer
P1235 parts, 2 parts of tetraethyl orthosilicate, 1 part of aluminium chloride, 3 parts of 3- aminopropyl triethoxysilane add in 20 parts of deionized water,
The materials compositions such as 4 parts of sodium hydroxide solution are added dropwise while stirring.The concentration for removing sulfur dioxide in gas is 20ppm, gas stream
Fast 200mL/min, 10-30 DEG C of room temperature.The adsorbent does not refer to its ability for adsorbing sulfur dioxide at high temperature, and industry is raw
The temperature of the coal-fired flue-gas of flue gas emission is higher in production, and urgent need will develop one kind and be suitble to adsorb dioxy in flue gas in the case of a high temperature
Change the adsorbent material of sulphur.
Summary of the invention
The purpose of the present invention is to the above-mentioned problems in the prior art, and provide a kind of removal rate of sulfur dioxide
It is high, sulphur adsorption capacity is big, is suitble to the preparation of the sulfur dioxide adsorbent for smoke gas treatment used under 250-800 DEG C of high temperature
Method.
Above-mentioned purpose to realize the present invention, preparation method of the present invention for the sulfur dioxide adsorbent of smoke gas treatment are logical
Following technical scheme is crossed to realize.
The technique that the present invention is used for the preparation method of the sulfur dioxide adsorbent of smoke gas treatment are as follows:
(1) mass fraction according to 100 parts count, respectively by the Ammonia of 4.6-5.6 part 25.0-30.0% with
The cetrimonium chloride solution of 36.8-44.4 parts of 20-25%, five water tetramethylammonium hydroxide of 3.0-6.9 part, 35.5-41.0 parts of 5-
15% silicic acid tetramethyl-ammonium solution, 4.0-9.8 parts of fumed silica are put into container and are stirred, are mixed to form reaction
Gel；It is then placed in hydrothermal reaction kettle, carries out natural cooling after 80-100 DEG C, soaking time 12-48 hours of heat preservation；
(2) after step (1) natural cooling, hot water reaction kettle is taken out and opened, the concentrated sulfuric acid is added and adjusts pH value to 7-
10.0；Then again into 80-100 DEG C, 12-48 hours hydrothermal reaction process；PH and continuation hydro-thermal reaction 1-4 times are adjusted, every time
Hydrothermal reaction condition be 80-100 DEG C and 12-48 hours；After adjusting pH by preamble and hydro-thermal reaction 2-5 times, utilize
Distilled water is cleaned, and excessive surfactant is washed, and is then air-dried 12-48 hours at room temperature；
(3) product after air-drying step (3) at room temperature carries out powder calcination, powder calcination program are as follows: greenhouse to 450-
550 DEG C, heating rate is 1-5 DEG C/min, obtains sulfur dioxide absorption after 450-550 DEG C of soaking time is 5-20 hours
Agent.
Preparation method preferred technique of the present invention for the sulfur dioxide adsorbent of smoke gas treatment are as follows:
(1) mass fraction according to 100 parts count, respectively by the Ammonia of 4.7-5.1 part 27.0-30.0% with
The cetrimonium chloride solution of 39.2-44.0 parts of 23-25%, five water tetramethylammonium hydroxide of 5.2-6.8 part, 36.5-40.6 parts of 9-
11% silicic acid tetramethyl-ammonium solution, 7.5-9.0 parts of fumed silica are put into container and are stirred, are mixed to form reaction
Gel；It is then placed in hydrothermal reaction kettle, carries out natural cooling after 80-90 DEG C, soaking time 18-30 hours of heat preservation；
(2) after step (1) natural cooling, hot water reaction kettle is taken out and opened, the concentrated sulfuric acid is added and adjusts pH value to 7.6-
8.5；Then again into 80-90 DEG C, 18-30 hours hydrothermal reaction process；It adjusts pH and continues hydro-thermal reaction 2-3 times, each
Hydrothermal reaction condition is 80-90 DEG C and 18-30 hours；After adjusting pH by preamble and hydro-thermal reaction 3-4 times, distillation is utilized
Water is cleaned, and excessive surfactant is washed, and is then air-dried 36-48 hours at room temperature；
(3) product after air-drying step (3) at room temperature carries out powder calcination, powder calcination program are as follows: greenhouse to 500-
550 DEG C, heating rate is 1-3 DEG C/min, obtains sulfur dioxide absorption after 500-550 DEG C of soaking time is 8-16 hours
Agent.
Wherein step (1) more preferably raw material proportioning are as follows:
Ammonia: 4.8-4.9 parts；
Cetrimonium chloride solution: 41.0-43.5 parts；
Five water tetramethylammonium hydroxide: 5.4-6.3 parts；
Silicic acid tetramethyl-ammonium solution: 36.5-39.6 parts；
Fumed silica: 8.0-9.0 parts.
The present invention is by ammonium hydroxide, cetrimonium chloride, tetramethylammonium hydroxide, silicic acid tetramethyl-ammonium and fumed silica etc.
The MCM-41 with hexagonal phase of material hydro-thermal reaction synthesis.Results of laboratory shows compared with prior art, of the invention
The preparation method of sulfur dioxide adsorbent for smoke gas treatment is had using the sulfur dioxide adsorbent of above technical scheme preparation
Have it is following the utility model has the advantages that
(1) the sulfur dioxide adsorbent prepared is used for smoke gas treatment, and sulfur dioxide selective absorption is high, and adsorption capacity is big,
The use of adsorbent material can be reduced；
(2) the sulfur dioxide adsorbent prepared has the characteristics that be resistant to higher temperatures, has a wide range of application, material under high temperature loss
It is few, reduce cost；
(3) requirement of the sulfur dioxide adsorbent prepared is simple, reduces requirement, reduces condition guarantee and disappear
Consumption, saves entreprise cost；
(4) the sulfur dioxide adsorbent recycling prepared is simple, and utilization rate is higher after recycling, reduces cost recovery, improves
Use the economic benefit of enterprise；
(5) sulfur dioxide sorbent material has the activity and compression strength of good scrubbing CO_2, can be efficient
The sulfur dioxide in flue gas is removed, and is less likely to occur to be poisoned, there is longer service life.
Detailed description of the invention
Fig. 1 is that preparation method of the present invention for the sulfur dioxide adsorbent of smoke gas treatment synthesizes sulfur dioxide adsorbent
Schematic diagram.
Specific embodiment
For the description present invention, the sulfur dioxide adsorbent of smoke gas treatment is used for the present invention with reference to the accompanying drawings and examples
Preparation method be described in further details.
Raw material are counted according to 100g, are mixed into the Ammonia and 36.8- of 4.6-5.6g25-30% respectively in beaker
The cetrimonium chloride solution of 44.4g20-25%, five water tetramethylammonium hydroxide of 3.0-6.9g, 35.5-41.0g5-15% silicic acid
Tetramethyl-ammonium solution, 4.0-9.8g fumed silica form reaction gel, using magnetic stirring apparatus, stir gel 30 minutes,
It is then placed in hydrothermal reaction kettle, it is natural after 80-100 DEG C, soaking time 12-48 hours, 12-48 hours of heat preservation in reaction baking oven
It is cooling to take out.After taking-up, hot water reaction kettle is opened, pH value is adjusted to 7-10.0 by the concentrated sulfuric acid.Then again into 80-100 DEG C,
12-48 hours hydrothermal reaction process.The process for adjusting pH and continuation hydro-thermal reaction has altogether 1-4 times.Each hydro-thermal reaction item
Part is 80-100 DEG C and 12-48 hours, after 3-5 times, is cleaned using distilled water, and excessive surface-active is washed
Then agent air-dries 12-48 hours at room temperature again.Powder calcination program be greenhouse arrive 450-550 DEG C, heating rate for 1-5 DEG C/
min.450-550 DEG C of soaking time is 5-20 hours.
Specific embodiment: it is mixed into ammonium hydroxide (the NH of 2.4g29% respectively in beaker4OH) solution and 21.2g25%
Cetrimonium chloride solution (CH3(CH2)15N(Cl)(CH3)3), five water tetramethylammonium hydroxide ((CH of 3.0g3)4N(OH)·5H2O)、
Silicic acid the tetramethyl-ammonium ((CH of 18.9g10%3)4N(OH)·2SiO2) solution, there are also 4.5g fumed silica (SiO2) formed
Reaction gel stirs gel 30 minutes using magnetic stirring apparatus, is then placed in hydrothermal reaction kettle, keeps the temperature 80 in reaction baking oven
DEG C, natural cooling is taken out after soaking time 24 hours, 24 hours.After taking-up, hot water reaction kettle is opened, pH is adjusted by the concentrated sulfuric acid
It is worth 8.0.Then the hydrothermal reaction process of 80 DEG C, 24 hours is carried out again.The process for adjusting pH and continuation hydro-thermal reaction has 3 altogether
Secondary, each hydrothermal reaction condition is 80 DEG C and 24 hours, after 3 times, is cleaned using distilled water, is washed excessive
Surfactant, then again at room temperature air-dry 48 hours.Powder calcination program is greenhouse to 540 DEG C, heating rate is 1 DEG C/
min.540 DEG C of soaking times are 10 hours.The material according to synthesized by above-mentioned steps belongs to one kind of M41S series, specially has
There is the MCM-41 of hexagonal phase.
Sulfur dioxide adsorbent of the present invention by ammonium hydroxide, cetrimonium chloride, tetramethylammonium hydroxide, silicic acid tetramethyl-ammonium and
The MCM-41 with hexagonal phase of the materials hydro-thermal reaction such as fumed silica synthesis.Fig. 1 is the present invention for smoke gas treatment
The schematic diagram of the preparation method synthesis sulfur dioxide adsorbent of sulfur dioxide adsorbent.The present invention as shown in Figure 1 is used for flue gas
The sulfur dioxide adsorbent of improvement preparation method synthesis sulfur dioxide adsorbent schematic diagram find out, surfactant molecule
(CH3(CH2)15N(Cl)(CH3)3With CH3)4N(OH)·5H2O it) plays template action and forms surfactant micellar, by surface-active
Agent micella gradually forms rod-shaped micelle, and rod-shaped micelle is self-assembly of hexagonal phase arrangement architecture, then by (CH3)4N(OH)·
2SiO2) and SiO2The surface of silicate grafting and hexagonal phase structure that combination is formed, calcines the gel for containing hexagonal phase structure,
Form the MCM-41 with hexagonal phase.
The method for the sulfur dioxide adsorbent absorption sulfur dioxide in flue gas that the present invention develops: keep flue gas abundant with adsorbent
Contact, sulfur dioxide in flue gas concentration 100-800ppm, adsorption temp can be 250-800 DEG C.Present invention may apply to appoint
What suitable pressure, the pressure of the raw material processed influence not big for sweetening process, generally from easy to operate and Cheng Benfang
Face considers that contact pressure is preferably 0.1-0.3MPa.It is carried out in fluidized bed, fixed bed or moving bed, reaction is in normal pressure, non-oxygen
It is carried out under the property changed atmosphere.
Desulfurization case study on implementation 1:
The method of adsorbent absorption sulfur dioxide in flue gas: carrying out in a fluidized bed, come into full contact with flue gas with adsorbent,
Flue gas flow 2.0L/min, sulfur dioxide in flue gas concentration 500ppm, adsorption temp can be 350 DEG C.Contact pressure is
0.15MPa, adsorption cycle 24 hours, removal rate of sulfur dioxide 88.7%, sulphur adsorption capacity 5.5%.
Desulfurization case study on implementation 2:
The method of adsorbent absorption sulfur dioxide in flue gas: carrying out in fixed bed, come into full contact with flue gas with adsorbent,
Flue gas flow 5.0L/min, sulfur dioxide in flue gas concentration 350ppm, adsorption temp can be 400 DEG C.Contact pressure is
0.18MPa, adsorption cycle 12 hours, removal rate of sulfur dioxide 91.7%, sulphur adsorption capacity 5.2%.
Desulfurization case study on implementation 3:
The method of adsorbent absorption sulfur dioxide in flue gas: carrying out in moving bed, come into full contact with flue gas with adsorbent,
Flue gas flow 8.0L/min, sulfur dioxide in flue gas concentration 280ppm, adsorption temp can be 330 DEG C.Contact pressure is
0.1MPa, adsorption cycle 18 hours, removal rate of sulfur dioxide 92.3%, sulphur adsorption capacity 7.8%.
The sulfur dioxide adsorbent and acticarbon that 1 present invention of table develops are to sulfur dioxide in flue gas adsorption test pair
Compare result.
The adsorbent of the present invention of table 1 and activated carbon adsorption sulfurous acid gas test comparing result
Test result shows high-efficient 4-8.4 percentage points of adsorbent specific activity charcoal absorption sulfur dioxide of the present invention, takes off
Sulphur effect is obvious.
Claims (5)
1. a kind of preparation method of the sulfur dioxide adsorbent for smoke gas treatment, it is characterised in that the technique of use are as follows:
(1) mass fraction is counted according to 100 parts, respectively by the Ammonia and 36.8- of 4.6-5.6 parts of 25.0-30.0%
The cetrimonium chloride solution of 44.4 parts of 20-25%, five water tetramethylammonium hydroxide of 3.0-6.9 part, 35.5-41.0 parts of 5-15% silicon
Sour tetramethyl-ammonium solution, 4.0-9.8 parts of fumed silica, which are put into container, to be stirred, is mixed to form reaction gel；So
After be put into hydrothermal reaction kettle, carry out natural cooling after 80-100 DEG C, soaking time 12-48 hours of heat preservation；
(2) after step (1) natural cooling, hot water reaction kettle is taken out and opened, the concentrated sulfuric acid is added and adjusts pH value to 7-10.0；So
Afterwards again into 80-100 DEG C, 12-48 hours hydrothermal reaction process；It adjusts pH and continues hydro-thermal reaction 1-4 times, each hydro-thermal is anti-
Answering condition is 80-100 DEG C and 12-48 hours；After adjusting pH by preamble and hydro-thermal reaction 2-5 times, using distilled water into
Row cleaning, washes excessive surfactant, then air-dries 12-48 hours at room temperature；
(3) product after air-drying step (2) at room temperature carries out powder calcination, powder calcination program are as follows: greenhouse to 450-550
DEG C, heating rate is 1-5 DEG C/min, obtains sulfur dioxide adsorbent after 450-550 DEG C of soaking time is 5-20 hours.
2. a kind of preparation method of the sulfur dioxide adsorbent for smoke gas treatment, it is characterised in that the technique of use are as follows:
(1) mass fraction is counted according to 100 parts, respectively by the Ammonia and 39.2- of 4.7-5.1 parts of 27.0-30.0%
The cetrimonium chloride solution of 44.0 parts of 23-25%, five water tetramethylammonium hydroxide of 5.2-6.8 part, 36.5-40.6 parts of 9-11% silicon
Sour tetramethyl-ammonium solution, 7.5-9.0 parts of fumed silica, which are put into container, to be stirred, is mixed to form reaction gel；So
After be put into hydrothermal reaction kettle, carry out natural cooling after 80-90 DEG C, soaking time 18-30 hours of heat preservation；
(2) after step (1) natural cooling, hot water reaction kettle is taken out and opened, the concentrated sulfuric acid is added and adjusts pH value to 7.6-8.5；
Then again into 80-90 DEG C, 18-30 hours hydrothermal reaction process；It adjusts pH and continues hydro-thermal reaction 2-3 times, each hydro-thermal
Reaction condition is 80-90 DEG C and 18-30 hours；After adjusting pH by preamble and hydro-thermal reaction 3-4 times, using distilled water into
Row cleaning, washes excessive surfactant, then air-dries 36-48 hours at room temperature；
(3) product after air-drying step (2) at room temperature carries out powder calcination, powder calcination program are as follows: greenhouse to 500-550
DEG C, heating rate is 1-3 DEG C/min, obtains sulfur dioxide adsorbent after 500-550 DEG C of soaking time is 8-16 hours.
3. the preparation method for the sulfur dioxide adsorbent of smoke gas treatment as claimed in claim 1 or 2, it is characterised in that step
Suddenly the raw material proportioning used in (1) are as follows: Ammonia: 4.8-4.9 parts；Cetrimonium chloride solution: 41.0-43.5 parts；Five water
Tetramethylammonium hydroxide: 5.4-6.3 parts；Silicic acid tetramethyl-ammonium solution: 36.5-39.6 parts；Fumed silica: 8.0-9.0 parts.
4. the preparation method for the sulfur dioxide adsorbent of smoke gas treatment as claimed in claim 3, it is characterised in that step
(1) raw material proportioning used in are as follows: 4.8 parts of Ammonia；42.4 parts of cetrimonium chloride solution；Five water tetramethylammonium hydroxide
6.0 part；37.8 parts of silicic acid tetramethyl-ammonium solution；9.0 parts of fumed silica；In step (2), the concentrated sulfuric acid is added and adjusts pH value
To 8.0.
5. the preparation method for the sulfur dioxide adsorbent of smoke gas treatment as claimed in claim 4, it is characterised in that in step
Suddenly powder calcination program in (3) are as follows: to 540 DEG C, heating rate is 1 DEG C/min in greenhouse, after 540 DEG C of soaking times are 10 hours
Obtain sulfur dioxide adsorbent.
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| Title |
|---|
| 李刚 等: "硅基介孔材料吸附烟气中二氧化硫的效能研究", 《工业安全与环保》 * |
| 汪杰 等: "MCM-41中孔分子筛研究进展", 《石油大学学报（自然科学版）》 * |
| 秦庆东著: "《东南土木青年教师科研论丛 介孔硅材料吸附水中污染物技术与原理》", 30 September 2015, 东南大学出版社 * |
| 靳昕: "MCM-41中孔分子筛吸附重金属离子及SO2、NO2气体的实验研究", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 * |
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