WO2020135202A1 - 具有三维多级孔道结构的蜂窝式scr脱硝催化剂及制备方法 - Google Patents
具有三维多级孔道结构的蜂窝式scr脱硝催化剂及制备方法 Download PDFInfo
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- WO2020135202A1 WO2020135202A1 PCT/CN2019/126497 CN2019126497W WO2020135202A1 WO 2020135202 A1 WO2020135202 A1 WO 2020135202A1 CN 2019126497 W CN2019126497 W CN 2019126497W WO 2020135202 A1 WO2020135202 A1 WO 2020135202A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title description 7
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 10
- 239000004310 lactic acid Substances 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000011152 fibreglass Substances 0.000 abstract 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Definitions
- the invention belongs to the technical field of industrial denitration, and particularly relates to a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure and a preparation method.
- the denitration layout of coal-fired power plants mainly uses high-dust layout.
- the flue gas dust passing through is easy to cause the catalyst bed to be blocked and generate high pressure.
- the catalyst will pass through loading, impact, and particulate matter in the flue gas during use. Wear and other consumption, therefore, in practical applications, in addition to ensuring the activity of the catalyst, it is more important to consider its practicability, such as mechanical strength, porosity and other properties.
- the denitration efficiency increases with the increase of the specific surface area, and the increase of the porosity of the catalyst will increase its specific surface area to a certain extent.
- honeycomb denitration catalyst The forming process of the honeycomb denitration catalyst and the use of pore-forming agents directly affect its mechanical strength and porosity, so the forming process needs to be optimized.
- some researchers can prepare a honeycomb denitration catalyst with high porosity and multi-stage pore structure by adjusting the extrusion pressure and the amount and type of pore-forming agent, which not only improves the mechanical strength, but also reduces the amount of catalyst. Therefore, it is a very effective method to adjust the mechanical strength and denitration efficiency of the catalyst by adjusting the pore structure.
- Adsorption capacity of the catalyst has a huge impact on the efficiency of removal of NO x adsorption capacity is the most direct correlation factors of the microstructure of the catalyst.
- a good microstructure means that the catalyst has a larger specific surface area, more microporous structure, proper pore size distribution and fast mass transfer rate, which increases its adsorption capacity of gas molecules, thereby improving denitrification performance.
- the specific surface area increases, the number of micropores in the catalyst increases and the average pore diameter decreases, which is detrimental to the diffusion of gas in the catalyst. Therefore, the effect of the pore structure of the catalyst on the denitrification process depends on the degree of influence on the gas diffusion and chemical reaction process when the pore structure changes.
- the three-dimensional multi-level channel structure can greatly increase the specific surface area of the material and the utilization rate of the pores, so as to increase the diffusion rate of the gas in the pores and enhance the denitration effect.
- the multi-level channel structure material can also reduce the channel blockage caused by macromolecules and improve the diffusion efficiency.
- Mesoporous or microporous channels are used as the reaction space for the reactants. The reactants can be quickly accessed in the large pore system with a small pressure drop Active site, at the same time, the product can be detached in time to stop the reaction.
- the technical problem to be solved by the present invention is how to modify the micropore structure and pore characteristics of the honeycomb denitration catalyst to adjust its macroscopic performance, thereby preparing a honeycomb denitration catalyst with high porosity and a certain mechanical strength.
- a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure including the following parts by weight of raw materials: titanium dioxide 80-100, pulp cotton 1-2, multi-walled carbon nanotubes 0.1-0.5, carbon black 0.5-2.5, silica 1 ⁇ 3, glass fiber 5 ⁇ 10, ammonium metavanadate 1-3, ammonium metatungstate 5 ⁇ 10, cerium nitrate hexahydrate 5 ⁇ 10, monoethanolamine 5 ⁇ 15, carboxymethyl cellulose 1-2, epoxy Ethane is 1-2, lactic acid 5-15, stearic acid 1-2, ammonia water 15-25, deionized water 30-50.
- a method for preparing a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure includes the following steps:
- step (1) Add the acidified multi-walled carbon nanotubes and carbon black mixture powder obtained in step (1) to ammonia water, and disperse them uniformly by ultrasound to obtain a mixed solution 1;
- step (4) The mixed sludge obtained in step (4) is extruded, dried, and calcined to obtain the target product.
- the diameter of the multi-wall carbon nanotubes in the step (1) is 10-20 nm, and the length is 5-15 ⁇ m; the particle size of the carbon black is about 15-20 nm.
- the mass ratio of the multi-walled carbon nanotubes and carbon black in step (1) is 1: (1 to 5); the mass ratio of the total mass of the multi-walled carbon nanotubes and carbon black to the mixed acid solution is 1: (5 ⁇ 10).
- the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1.
- the concentration of ammonia in the step (2) is 15%
- the ultrasonic dispersion power is 400-800W
- the time is 0.5-2h.
- the heating dissolution temperature in the step (3) is 60-90°C.
- the mixture in step (4) is stirred for 0.5 to 1 h before being added to the mixed liquid 1 and the mixed liquid 2.
- the mixed liquid 1 and the mixed liquid 2 are added to the mixture containing titanium dioxide, silica, glass fiber, stearic acid and pulp cotton with stirring at a rotating speed of 200-400 rpm, at a rotating speed Carry out kneading at 600-800 rpm. After kneading evenly, add carboxymethyl cellulose, ethylene oxide and lactic acid at 70-90°C, and knead again at a speed of 600-800 rpm to obtain mixed mud. Aging, the aging time is 12 ⁇ 48h.
- the number of pores of the honeycomb catalyst extruded in the step (5) is 20 ⁇ 20 pores; the drying temperature is 20-60° C.; a mixed gas with an oxygen content of 30-50% is introduced during the calcination process, Keep the entire calcination in oxygen-rich conditions.
- the present invention discloses a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure and a preparation method thereof.
- the catalyst uses titanium dioxide as a carrier, and vanadium pentoxide, tungsten trioxide, and cerium dioxide are
- the active component uses pulp cotton, multi-walled carbon nanotubes and carbon black as composite pore-forming agents, as well as the balance of other additives.
- the prepared material has a three-dimensionally ordered pore network and mesoporous structure interconnected with each other, which improves the pressure resistance At the same time of strength, it maintains its characteristics of large specific surface area.
- the three-dimensional channel structure has a rich spatial network of nano-scale micropores-mesopores and elongated mass transfer channels, which can not only improve the porosity and specific surface area of the catalyst, but also maintain a high crushing strength; in addition, the channels are mutually
- the connected feature can resist the uneven deposition of vanadium oxide and dust in the flue gas on its surface, and slow down the active site coverage caused by the clogging of micropores by particles such as calcium sulfate.
- the prepared catalyst has high porosity, and has certain mechanical strength, so it has great industrial application prospects.
- a preparation method of a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure includes the following steps:
- the catalyst mixed sludge obtained in the above step (4) is extruded and shaped with a 20 ⁇ 20 abrasive, dried at 20°C until the water content is less than 3%, and calcined at 550°C for 5 hours in an atmosphere of 35% oxygen content To get the target product;
- the obtained catalyst monomer was cut into test blocks of 150mm ⁇ 150mm ⁇ 150mm, the mechanical strength was tested using an electronic universal testing machine, and the specific surface area was tested using a static nitrogen adsorption method; according to the specific implementation steps of Example 1, the crushed product was prepared strength radial / axial direction, respectively 1.5Mpa and 4.9Mpa, the specific surface area reaches 68m 2 / g.
- a preparation method of a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure includes the following steps:
- the catalyst mixed sludge obtained in the above step (4) is extruded and shaped with a 20 ⁇ 20 grinding tool, dried at 40°C until the moisture is less than 3%, and calcined at 550°C for 5 hours in an atmosphere of 40% oxygen content. Get the target product;
- the obtained catalyst monomer was cut into test blocks of 150 mm ⁇ 150 mm ⁇ 150 mm, the mechanical strength was tested using an electronic universal testing machine, and the specific surface area was tested using a static nitrogen adsorption method. According to the specific implementation steps of this Example 2, the crushed strength diameter/axial direction of the prepared product reached 1.1 Mpa and 4.1 Mpa, respectively, and the specific surface area reached 72 m 2 /g.
- a preparation method of a honeycomb SCR denitration catalyst with a three-dimensional multi-stage channel structure includes the following steps:
- the catalyst mixed sludge obtained in the above step (4) is extruded and shaped with a 20 ⁇ 20 abrasive, dried at 60°C until the moisture is less than 3%, and calcined at 550°C for 5 hours in an atmosphere of 30% oxygen content. Get the target product;
- the obtained catalyst monomer was cut into test blocks of 150 mm ⁇ 150 mm ⁇ 150 mm, the mechanical strength was tested using an electronic universal testing machine, and the specific surface area was tested using a static nitrogen adsorption method. According to the specific implementation steps of Example 3, the crushing strength diameter/axial direction of the prepared product reaches 1.7 MPa and 5.3 MPa, respectively, and the specific surface area reaches 51 m 2 /g.
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Abstract
具有三维多级孔道结构的蜂窝式SCR脱硝催化剂,包括下列重量份的原料制备而成:二氧化钛80~100、纸浆棉1~2、多壁碳纳米管0.1~0.5、炭黑0.5~2.5、二氧化硅1~3、玻璃纤维5~10、偏钒酸铵1~3、偏钨酸铵5~10、六水合硝酸铈5~10、单乙醇胺5~15、羧甲基纤维素1~2、环氧乙烷为1~2、乳酸5~15、硬脂酸1~2、氨水15~25、去离子水30~50。制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,所制备的催化剂具有三维有序彼此连通的孔网络和介孔结构,提高了耐压强度的同时,维持了其大比表面积的特性。
Description
本发明属于工业脱硝技术领域,具体涉及具有三维多级孔道结构的蜂窝式SCR脱硝催化剂及制备方法。
作为去除燃煤烟气中氮氧化物的干式脱硝技术,选择性催化还原脱硝法被广泛采用,它使用氨作还原剂,使烟气中的NO及NO
2通过催化剂层后还原生成N
2和H
2O,达到脱除烟气中NO
x的目的。催化剂多数采用以TiO
2为载体、V
2O
5、WO
3为活性组分的多孔介质,具有高脱硝率、选择性好、运行稳定、温度适中等诸多优点,故一直备受国内外研究人员的青睐。其核心问题在于催化剂的研制、开发及改进。
目前,燃煤电厂脱硝布置方式主要使用高尘布置式,通过的烟气粉尘大,容易使得催化剂床层堵塞而产生高压;另外,催化剂在使用过程中会经过装车、撞击、烟气中颗粒物的磨损等消耗,因此,在实际应用中,除了要保证催化剂的活性以外,更重要的是考虑它的实用性,如机械强度、孔隙率等性能。在催化剂的活性温度范围内,脱硝效率随着比表面积的增大而增大,催化剂孔隙率的提高会在一定程度上提升其比表面积。但是,在高孔隙率条件下,很难制备出高强度的催化剂。因此,如何制备高孔隙率,且有一定机械强度的蜂窝式脱硝催化剂仍然是目前亟待解决的问题。
蜂窝式脱硝催化剂的成型工艺和造孔剂的使用直接影响其机械强度和孔隙率,所以需对成型工艺进行优化。目前,一些研究人员通过调节挤出压力和造孔剂的加入量及种类,可以制备出高孔隙率和多级孔结构的蜂窝式脱硝催化剂,既 提升了机械强度,又能减少催化剂用量。因此,通过调节孔结构来调控催化剂的机械强度和脱硝效率是很有效的一种方法。
催化剂的吸附能力对脱除NO
x的效率有着巨大的影响,吸附能力最直接的关联因素是催化剂的微观结构。一个良好的微观结构意味着催化剂有更大比表面积,更多的微孔结构,合适的孔径分布和快速的传质速率,增加其对气体分子的吸附量,进而提高脱硝性能。然而,当比表面积增大时,催化剂内的微孔数增多,平均孔径下降,对气体在催化剂中的扩散不利。因此,催化剂的孔结构对脱硝过程的影响取决于当孔结构变化时,分别对气体扩散及化学反应过程的影响程度。三维多级孔道结构能大大增加材料的比表面积、孔的利用率,达到提高气体在孔隙中的扩散速率而增强脱硝效果。多级孔道结构的材料也能减少大分子造成的孔道堵塞和提高扩散效率,介孔或者微孔孔道作为反应物的反应空间,反应物在大孔体系以很小的压力降就可快捷的接近活性位,同时使产物可及时脱离而中止反应。目前,将三维多级孔道结构引入蜂窝式脱硝催化剂研究还未见文献和专利报道。
发明内容
本发明所要解决的技术问题在于:如何通过改造蜂窝式脱硝催化剂的微观孔结构、孔特性,调控其宏观性能,从而制备出高孔隙率,且有一定机械强度的蜂窝式脱硝催化剂。
本发明采用以下技术方案解决上述技术问题:
具有三维多级孔道结构的蜂窝式SCR脱硝催化剂,包括下列重量份的原料:二氧化钛80~100、纸浆棉1~2、多壁碳纳米管0.1~0.5、炭黑0.5~2.5、二氧化硅1~3、玻璃纤维5~10、偏钒酸铵1~3、偏钨酸铵5~10、六水合硝酸铈5~ 10、单乙醇胺5~15、羧甲基纤维素1~2、环氧乙烷为1~2、乳酸5~15、硬脂酸1~2、氨水15~25、去离子水30~50。
优选的,一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,包括以下步骤:
(1)将多壁碳纳米管和炭黑分散于混酸中酸化处理3~6h,冷却至室温后用蒸馏水稀释,过滤洗涤至中性,产物于75~80℃下真空干燥10~12h,研成粉末,得到酸化的多壁碳纳米管和炭黑混合物粉末;
(2)将步骤(1)所得酸化的多壁碳纳米管和炭黑混合物粉末添加到氨水中,超声分散均匀,得到混合液①;
(3)将偏钒酸铵、偏钨酸铵、六水合硝酸铈加入至单乙醇胺和去离子水的混合溶液中,加热溶解,得到混合液②;
(4)将混合液①和混合液②在搅拌下加入含有二氧化钛、二氧化硅、玻璃纤维、硬脂酸和纸浆棉的混合料中,混炼,加入羧甲基纤维素、环氧乙烷和乳酸,再次混练,得到混合泥料,进行老化;
(5)将步骤(4)获得的混合泥料挤出成型、干燥、煅烧,得到目标产品。
优选的,所述步骤(1)中所述的多壁碳纳米管直径为10~20nm,长度为5~15μm;所述的炭黑的粒径约为15~20nm。
优选的,步骤(1)中所述多壁碳纳米管和炭黑的质量比为1∶(1~5);所述多壁碳纳米管和炭黑的总质量与混酸溶液的质量比为1∶(5~10)。
优选的,所述混酸由浓硫酸和浓硝酸按体积比3∶1混合而成。
优选的,所述步骤(2)中氨水的浓度为15%,超声分散功率为400~800W,时间0.5~2h。
优选的,所述步骤(3)中加热溶解温度为60~90℃。
优选的,所述步骤(4)中混合料在添加到混合液①和混合液②中之前先搅拌0.5~1h。
优选的,所述步骤(4)中将混合液①和混合液②在转速为200~400rpm搅拌下加入含有二氧化钛、二氧化硅、玻璃纤维、硬脂酸和纸浆棉的混合料中,以转速为600~800rpm进行混炼,混炼均匀后,在70~90℃下加入羧甲基纤维素、环氧乙烷和乳酸,再次以转速为600~800rpm进行混练,得到混合泥料,进行老化,老化时间为12~48h。
优选的,所述步骤(5)中挤出成型的蜂窝式催化剂孔数为20×20孔;干燥温度为20~60℃;煅烧过程中通入含氧量为30~50%的混合气体,保持整个煅烧为富氧条件。
本发明技术有益效果:本发明公开了一种具有三维多级孔道结构的蜂窝式SCR脱硝催化剂及其制备方法,所述催化剂以二氧化钛为载体,五氧化二钒、三氧化钨和二氧化铈为活性组分,以纸浆棉、多壁碳纳米管和炭黑为复合造孔剂,以及余量其他助剂,所制备材料具有三维有序彼此连通的孔网络和介孔结构,提高了耐压强度的同时,维持了其大比表面积的特性。
在制备过程中,将多壁碳纳米管和炭黑酸化后提高了水溶性,使得其在泥料中均匀分散,一维碳纳米管形成网状交织结构,在富氧条件下充分煅烧氧化分解,将各微孔-介孔连接形成一种快速传质的三维多级通道。该三维孔道结构拥有丰富的空间网络状纳米级微孔-介孔以及细长的传质通道,既可以提高催化剂的孔隙率和比表面积,又保持了较高的压碎强度;此外,孔道相互连通的特性,可以抵抗烟道气中钒氧化物及粉尘在其表面不均匀沉积,减缓硫酸钙等微粒对微孔的 堵塞造成的活性位点覆盖。所制备的催化剂,孔隙率高,且有一定机械强度,很具工业应用前景。
为便于本领域技术人员理解本发明技术方案,现结合实施例对本发明技术方案做进一步的说明。所描述的实施例是本发明的一部分实施例,而不是全部的实施例。
实施例1
一种具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的制备方法,包括以下步骤:
(1)将0.2kg多壁碳纳米管和1.0kg炭黑分散于总质量为8kg浓硫酸和浓硝酸的混酸溶液中,40℃下搅拌处理3h,冷却至室温后用蒸馏水稀释,过滤洗涤至中性,产物于75℃下真空干燥10h,研成粉末,得到酸化的多壁碳纳米管和炭黑混合物粉末;其中所述混酸溶液中V(浓硫酸)∶V(浓硝酸)体积比为3∶1;
(2)将上述得到的酸化的多壁碳纳米管和炭黑混合物粉末添加到20kg浓度为15%的氨水中,在功率为400W下超声分散0.5h,得到混合液①;
(3)依次将1.5kg偏钒酸铵、6kg偏钨酸铵和6kg六水合硝酸铈加入至含有5kg单乙醇胺水溶液中,加热至60℃充分溶解,得到混合液②;
(4)将上述混合液①和混合液②在转速为200rpm搅拌下加入含有90kg二氧化钛、2kg二氧化硅、6kg玻璃纤维、2kg硬脂酸和1.5kg纸浆棉的混合料中,以转速为600rpm进行混炼,混炼均匀后,在70℃下加入8kg乳酸、1.5kg羧甲基纤维素和1.5kg环氧乙烷,再次以转速为600rpm进行混练,得到混合泥料, 老化12h;
(5)将所述步骤(4)获得的催化剂混合泥料用20×20的磨具挤出成型,20℃下干燥至水分低于3%、于35%含氧量气氛下550℃煅烧5h,得到目标产品;
将得到的催化剂单体切割成150mm×150mm×150mm的测试块,使用电子式万能试验机测试机械强度,使用静态氮气吸附法测试其比表面积;根据实施例1具体实施步骤,制备产品的压碎强度径/轴向分别达到1.5Mpa和4.9Mpa,比表面积达到68m
2/g。
实施例2
一种具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的制备方法,包括以下步骤:
(1)将0.3kg多壁碳纳米管和1.5kg炭黑分散于总质量为10kg浓硫酸和浓硝酸的混酸溶液中,40℃下搅拌处理4h,冷却至室温后用蒸馏水稀释,过滤洗涤至中性,产物于80℃下真空干燥12h,研成粉末,得到酸化的多壁碳纳米管和炭黑混合物粉末;其中所述混酸溶液中V(浓硫酸)∶V(浓硝酸)体积比为3∶1;
(2)将上述得到的酸化的多壁碳纳米管和炭黑混合物粉末添加到20kg浓度为15%的氨水中,在功率为600W下超声分散1h,得到混合液①;
(3)依次将1.5kg偏钒酸铵、6kg偏钨酸铵和6kg六水合硝酸铈加入至含有5kg单乙醇胺水溶液中,加热至80℃充分溶解,得到混合液②;
(4)将上述混合液①和混合液②在转速为300rpm搅拌下加入含有90kg二氧化钛、2kg二氧化硅、6kg玻璃纤维、2kg硬脂酸和1.8kg纸浆棉的混合料中,以转速为700rpm进行混炼,混炼均匀后,在80℃下加入8kg乳酸、1.5kg羧甲 基纤维素和1.5kg环氧乙烷,再次以转速为700rpm进行混练,得到混合泥料,老化24h;
(5)将所述步骤(4)获得的催化剂混合泥料用20×20的磨具挤出成型,40℃干燥至水分低于3%、于40%含氧量气氛下550℃煅烧5h,得到目标产品;
将得到的催化剂单体切割成150mm×150mm×150mm的测试块,使用电子式万能试验机测试机械强度,使用静态氮气吸附法测试其比表面积。根据本实施例2具体实施步骤,制备产品的压碎强度径/轴向分别达到1.1Mpa和4.1Mpa,比表面积达到72m
2/g。
实施例3
一种具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的制备方法,包括以下步骤:
(1)将0.1kg多壁碳纳米管和0.5kg炭黑分散于总质量为6kg浓硫酸和浓硝酸的混酸溶液中,40℃下搅拌处理6h,冷却至室温后用蒸馏水稀释,过滤洗涤至中性,产物于80℃下真空干燥12h,研成粉末,得到酸化的多壁碳纳米管和炭黑混合物粉末;其中所述混酸溶液中V(浓硫酸)∶V(浓硝酸)体积比为3∶1;
(2)将上述得到的酸化的多壁碳纳米管和炭黑混合物粉末添加到20kg浓度为15%的氨水中,在功率为800W超声分散2h,得到混合液①;
(3)依次将1.5kg偏钒酸铵、6kg偏钨酸铵和6kg六水合硝酸铈加入至含有5kg单乙醇胺水溶液中,加热至90℃充分溶解,得到混合液②;
(4)将上述混合液①和混合液②在转速为400rpm搅拌下加入含有90kg二氧化钛、2kg二氧化硅、6kg玻璃纤维、2kg硬脂酸和1.0kg纸浆棉的混合料中, 以转速为800rpm进行混炼,混炼均匀后,在90℃下加入8kg乳酸、1.5kg羧甲基纤维素和1.5kg环氧乙烷,再次以转速为800rpm进行混练,得到混合泥料,老化24h;
(5)将所述步骤(4)获得的催化剂混合泥料用20×20的磨具挤出成型,60℃干燥至水分低于3%、于30%含氧量气氛下550℃煅烧5h,得到目标产品;
将得到的催化剂单体切割成150mm×150mm×150mm的测试块,使用电子式万能试验机测试机械强度,使用静态氮气吸附法测试其比表面积。根据本实施例3具体实施步骤,制备产品的压碎强度径/轴向分别达到1.7Mpa和5.3Mpa,比表面积达到51m
2/g。
尽管本发明已经通过上述优选实施例做了详细的介绍,但应当认识到上述的描述不应当被认为是对本发明的限值。对于本发明所属技术领域的技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明保护的范围。
Claims (10)
- 具有三维多级孔道结构的蜂窝式SCR脱硝催化剂,其特征在于,包括下列重量份的原料制备而成:二氧化钛80~100、纸浆棉1~2、多壁碳纳米管0.1~0.5、炭黑0.5~2.5、二氧化硅1~3、玻璃纤维5~10、偏钒酸铵1~3、偏钨酸铵5~10、六水合硝酸铈5~10、单乙醇胺5~15、羧甲基纤维素1~2、环氧乙烷为1~2、乳酸5~15、硬脂酸1~2、氨水15~25、去离子水30~50。
- 一种制备如权利要求1所述的具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,包括以下步骤:(1)将多壁碳纳米管和炭黑分散于混酸中酸化处理3~6h,冷却至室温后用蒸馏水稀释,过滤洗涤至中性,产物于75~80℃下真空干燥10~12h,研成粉末,得到酸化的多壁碳纳米管和炭黑混合物粉末;(2)将步骤(1)所得酸化的多壁碳纳米管和炭黑混合物粉末添加到氨水中,超声分散均匀,得到混合液①;(3)将偏钒酸铵、偏钨酸铵、六水合硝酸铈加入至单乙醇胺和去离子水的混合溶液中,加热溶解,得到混合液②;(4)将混合液①和混合液②在搅拌下加入含有二氧化钛、二氧化硅、玻璃纤维、硬脂酸和纸浆棉的混合料中,混炼,加入羧甲基纤维素、环氧乙烷和乳酸,再次混练,得到混合泥料,进行老化;(5)将步骤(4)获得的混合泥料挤出成型、干燥、煅烧,得到目标产品。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(1)中所述的多壁碳纳米管直径为10~20nm,长度为5~15μm;所述的炭黑的粒径约为15~20nm。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝 催化剂的方法,其特征在于,步骤(1)中所述多壁碳纳米管和炭黑的质量比为1∶(1~5);所述多壁碳纳米管和炭黑的总质量与混酸溶液的质量比为1∶(5~10)。
- 根据权利要求4所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述混酸由浓硫酸和浓硝酸按体积比3∶1混合而成。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(2)中氨水的浓度为15%,超声分散功率为400~800W,时间0.5~2h。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(3)中加热溶解温度为60~90℃。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(4)中混合料在添加到混合液①和混合液②中之前先搅拌0.5~1h。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(4)中将混合液①和混合液②在转速为200~400rpm搅拌下加入含有二氧化钛、二氧化硅、玻璃纤维、硬脂酸和纸浆棉的混合料中,以转速为600~800rpm进行混炼,混炼均匀后,在70~90℃下加入羧甲基纤维素、环氧乙烷和乳酸,再次以转速为600~800rpm进行混练,得到混合泥料,进行老化,老化时间为12~48h。
- 根据权利要求2所述一种制备具有三维多级孔道结构的蜂窝式SCR脱硝催化剂的方法,其特征在于,所述步骤(5)中挤出成型的蜂窝式催化剂孔数 为20×20孔;干燥温度为20~60℃;煅烧过程中通入含氧量为30~50%的混合气体,保持整个煅烧为富氧条件。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0970534A (ja) * | 1995-09-05 | 1997-03-18 | Babcock Hitachi Kk | 脱硝触媒の製造方法 |
US20060040823A1 (en) * | 2004-08-18 | 2006-02-23 | Stockwell David M | Catalyst for NOx and/or SOx control |
CN103769239A (zh) * | 2014-01-27 | 2014-05-07 | 济南大学 | 具有多级孔结构的蜂窝型脱硝催化剂及其制备方法 |
CN105013473A (zh) * | 2015-07-20 | 2015-11-04 | 福建紫荆环境工程技术有限公司 | 一种同时脱除二噁英和nox的催化剂及其制备方法 |
CN105148948A (zh) * | 2015-07-21 | 2015-12-16 | 安徽省元琛环保科技有限公司 | 一种可脱除二噁英的脱硝催化剂及其制备方法 |
CN105413677A (zh) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | 一种电厂除尘后用低温脱硝催化剂及其制备方法 |
CN107876042A (zh) * | 2017-11-10 | 2018-04-06 | 西南化工研究设计院有限公司 | 一种高几何比表面积低温烟气脱硝催化剂及其制备方法 |
US10022671B2 (en) * | 2016-03-24 | 2018-07-17 | Cataler Corporation | Exhaust gas purification device |
CN108404902A (zh) * | 2018-02-09 | 2018-08-17 | 华电青岛环保技术有限公司 | 一种scr蜂窝型脱硝催化剂及其制备方法 |
CN109731569A (zh) * | 2018-12-27 | 2019-05-10 | 安徽元琛环保科技股份有限公司 | 具有三维多级孔道结构的蜂窝式scr脱硝催化剂及制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5299647B2 (ja) * | 2010-04-09 | 2013-09-25 | Jfeエンジニアリング株式会社 | 排ガスの処理装置 |
CN105521777A (zh) * | 2015-12-31 | 2016-04-27 | 安徽省元琛环保科技有限公司 | 一种低温脱硝催化剂的制备方法 |
CN108067296B (zh) * | 2016-11-15 | 2019-11-15 | 中国石油化工股份有限公司 | 一种蜂窝状Mn基低温脱硝催化剂的制备方法 |
CN108273494A (zh) * | 2017-12-29 | 2018-07-13 | 浙江德创环保科技股份有限公司 | 一种用于宽温度窗口的脱硝催化剂及其制备方法 |
CN108636417A (zh) * | 2018-04-25 | 2018-10-12 | 清华大学 | 一种脱除no的金属氧化物催化剂及其制备方法 |
-
2018
- 2018-12-27 CN CN201811611515.XA patent/CN109731569B/zh active Active
-
2019
- 2019-12-19 WO PCT/CN2019/126497 patent/WO2020135202A1/zh active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0970534A (ja) * | 1995-09-05 | 1997-03-18 | Babcock Hitachi Kk | 脱硝触媒の製造方法 |
US20060040823A1 (en) * | 2004-08-18 | 2006-02-23 | Stockwell David M | Catalyst for NOx and/or SOx control |
CN103769239A (zh) * | 2014-01-27 | 2014-05-07 | 济南大学 | 具有多级孔结构的蜂窝型脱硝催化剂及其制备方法 |
CN105013473A (zh) * | 2015-07-20 | 2015-11-04 | 福建紫荆环境工程技术有限公司 | 一种同时脱除二噁英和nox的催化剂及其制备方法 |
CN105148948A (zh) * | 2015-07-21 | 2015-12-16 | 安徽省元琛环保科技有限公司 | 一种可脱除二噁英的脱硝催化剂及其制备方法 |
CN105413677A (zh) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | 一种电厂除尘后用低温脱硝催化剂及其制备方法 |
US10022671B2 (en) * | 2016-03-24 | 2018-07-17 | Cataler Corporation | Exhaust gas purification device |
CN107876042A (zh) * | 2017-11-10 | 2018-04-06 | 西南化工研究设计院有限公司 | 一种高几何比表面积低温烟气脱硝催化剂及其制备方法 |
CN108404902A (zh) * | 2018-02-09 | 2018-08-17 | 华电青岛环保技术有限公司 | 一种scr蜂窝型脱硝催化剂及其制备方法 |
CN109731569A (zh) * | 2018-12-27 | 2019-05-10 | 安徽元琛环保科技股份有限公司 | 具有三维多级孔道结构的蜂窝式scr脱硝催化剂及制备方法 |
Cited By (13)
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CN111686716A (zh) * | 2020-07-29 | 2020-09-22 | 江西省环境保护科学研究院 | WOx改性碳纳米管负载金属氧化物的低温SCR烟气脱硝催化剂及制备方法与应用 |
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CN114797837A (zh) * | 2022-03-20 | 2022-07-29 | 浙江大学 | 能在低温条件下协同催化脱除烟气中二次污染物的催化剂 |
WO2024103671A1 (zh) * | 2022-11-14 | 2024-05-23 | 国能龙源环保有限公司 | 利用废旧风电叶片制备脱硝催化剂的方法和应用 |
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