CN112191267A - 一种催化氧化脱除烟气中二噁英的蜂窝式催化剂及其制备方法 - Google Patents
一种催化氧化脱除烟气中二噁英的蜂窝式催化剂及其制备方法 Download PDFInfo
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- CN112191267A CN112191267A CN202011060005.5A CN202011060005A CN112191267A CN 112191267 A CN112191267 A CN 112191267A CN 202011060005 A CN202011060005 A CN 202011060005A CN 112191267 A CN112191267 A CN 112191267A
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- Prior art keywords
- honeycomb catalyst
- flue gas
- catalyst
- catalytic oxidation
- pug
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
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- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 239000010955 niobium Substances 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical group CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 47
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 41
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 239000012744 reinforcing agent Substances 0.000 claims description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 4
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- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 abstract description 12
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
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- 235000011150 stannous chloride Nutrition 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
本发明公开了一种用于催化氧化脱除烟气中二噁英的蜂窝式催化剂及其制备方法。该蜂窝式催化剂的活性组分包括钒、钨和IVA族元素,以及轻稀土、铌、钼、铜、锑元素中的一种或几种,活性组分在有机胺和氨水络合作用下均匀分散于钛白粉和ZSM‑5复合载体表面,所制备的催化剂比表面积高,机械强度好;对二噁英具有消除效率高,起活温度低,反应活性和稳定性高的特点;在180℃时蜂窝式催化剂对邻二氯苯的脱除率高于80%,200℃时高于90%,250℃时高达99.7%。本发明中的蜂窝式催化剂中不含贵金属,原料廉价易得,蜂窝式催化剂一次剂压成型,成品率高,制备方法简单,成本较低,有利于在工业上大规模应用。
Description
技术领域
本发明涉及一种催化氧化脱除烟气中二噁英的催化剂,尤其涉及一种脱除烟气中二噁英的蜂窝式催化剂及其制备方法,属于环保催化剂开发及大气污染物控制领域。
背景技术
二噁英是一种持久性有机污染物,自上世纪50年代被发现以来,越来越受到人们的关注,并在2001年被列入《关于持久性有机污染物的斯德哥尔摩公约》清单,该公约2004年在我国生效。针对愈发严峻的二噁英治理形势,多种方式被用于烟气中二噁英的脱除,包括冷凝法、吸附法、直接燃烧法、生物法、光催化法和催化降解法。催化降解法由于具有能耗低、脱除效率高、能够降解低浓度二噁英、运行成本低、易于工业化等特点被广泛研究。CN103657638A公开了一种利用涂覆方法制备的整体式二噁英脱除钒基催化剂,该催化剂活性组分为V2O5-WO3-TiO2。CN1623632A公开了一种Ag-V-W(Mo或Cr)/TiO2为活性组分的催化剂,该催化剂可同时脱除二噁英、一氧化碳和氮氧化物的钒基催化剂。这些方法尽管可以降低烟气中二噁英的含量,但是这些催化剂存在制备成本高,难以成型和工业化的问题,而且某些催化剂主要以脱硝或脱一氧化碳为主,对二噁英的降解效率低,处理后的烟气仍然达不到国家排放标准。
发明内容
本发明针对烟气中二噁英的催化降解和现有催化剂技术存在的不足,提供一种催化氧化脱除烟气中二噁英的蜂窝式催化剂及其制备方法。
一、蜂窝式催化剂的活性组分及制备
1、蜂窝式催化剂的组分
本发明的蜂窝式催化剂,由活性组分、载体和玻璃纤维组成;其中,活性组分包括钒,钨,IVA族元素,以及轻稀土、铌、钼、铜、锑元素中的一种或几种。活性组分中,各元素以氧化物计,钒和钨的量分别为1.0~11.5%,IVA族元素的量分别为0.1~8.0%,轻稀土元素的量为0.1~6.0%,铌、钼、铜、锑的量分别为0.1~4.5%。载体为钛白粉和ZSM-5复合材料,钛白粉的含量为53.0~90.0%,ZSM-5的含量为0~15.0%。强度增强剂为玻璃纤维,玻璃纤维的含量为0.5~10.0%。
2、蜂窝式催化剂的制备
(1)将乙醇胺加入到去离子水中,形成乙醇胺溶液,乙醇胺的加入量为催化剂质量的0.5~10.0%;乙醇胺为单乙醇胺、二乙醇胺或三乙醇胺中的一种或几种。
(2)在乙醇胺和水溶液中将活性组分的前驱体溶解后,与载体、辅料按照设计比例进行混合,混合后的泥料在混炼机中进行混炼,同时用氨水调节泥料pH至7.0~8.5,控制泥料水分在28.0~31.0%,充分搅拌混炼均匀后,对泥料进行过滤、真空捏合和预挤出;
活性组分的前驱体物质中,钒的前驱体为草酸氧钒、硫酸氧钒或偏钒酸铵的一种或几种;钨的前驱体为偏钨酸铵、仲钨酸铵或磷钨酸铵的一种或几种;铌的前驱体为氯化铌、草酸铌或氧化铌中的一种或几种;钼的前驱体为钼酸铵、七钼酸铵或钼酸钠中的一种或几种;IVA族元素的前驱体为其氧化物、硫酸盐、草酸盐、氯盐或有机化合物中的一种或几种;轻稀土元素、铜和锑的前驱体为各自的硝酸盐、氯盐或硫酸盐的一种或几种。各活性组分前驱体溶解后加入到混炼机中的次序可根据具体情况调整;
辅料包括玻璃纤维(强度增强剂)、木浆(造孔剂)、硬脂酸(润滑剂)、乳酸(吸附剂)、CMC(粘结剂、保水剂和增塑剂)、PEO(粘结剂、增塑剂和造孔剂);各辅料的加入量分别为催化剂质量的0.5~10%;各辅料的加入次序可根据具体情况调整。
(3)将预挤出的泥料密封后,在温度20~30℃,湿度60~70%的环境中陈腐24~48小时。为了获得塑性较好的泥料,将陈腐完后的泥料可进行再次真空捏合、预挤出和二次陈腐,陈腐条件和一次陈腐时一致。
(4)将陈腐后的泥料在强力挤出机上进行挤出成型,干燥,然后在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。其中,挤出催化剂孔数为15~60。干燥条件:温度为20~60℃,湿度为90~20%,时间为8~9天。焙烧条件:最高温度为400~550℃,产品出窑温度为60~80℃,焙烧时间控制在25~45小时。
二、蜂窝式催化剂的性质及性能
1. 蜂窝式催化剂物理化学性质
本发明制备的蜂窝式催化剂具有比表面积高(90~150 m2/g),机械强度好(轴向抗压强度≥2.5 Mpa,径向抗压强度≥0.6 Mpa,磨损指数≤1.0 %),催化剂制备成品率高的优势。
2. 蜂窝式催化剂二噁英类污染物脱除性能测试
测试过程中使用的探针污染物为与二噁英结构相似的邻二氯苯,测试条件为:邻二氯苯浓度:1000 ppm,空速:5000h-1,O2体积含量:20%,N2为平衡气。
测试结果表明,本发明制备的蜂窝式催化剂对二噁英类似物—邻二氯苯具有较高的脱除效率,而且在180℃时蜂窝式催化剂对邻二氯苯的脱除率高于80%,200℃时对邻二氯苯脱除率高于90%,250℃时高达99.7%,说明本发明二噁英脱除蜂窝式催化剂具有低的起活温度和高的反应活性。
综上所述,本发明相对现有技术具有以下优点:
1. 本发明催化剂中加入了二噁英催化降解活性组分,活性组分在有机胺和氨水络合作用下均匀分散于载体表面,所制备的催化剂比表面积高,机械强度好;对二噁英消除效率高,具有起活温度低,反应活性和稳定性高的特点;
2.本发明中的蜂窝式催化剂主要成分为过渡金属氧化物,催化剂中不含贵金属,原料廉价易得,蜂窝式催化剂一次剂压成型,成品率高,制备方法简单,成本较低,有利于在工业上大规模应用;
3. 通过调节催化剂成型孔数,本发明中的蜂窝式催化剂可直接用于生活垃圾焚烧、危废焚烧、发电供热和钢铁烧结烟气中二噁英的脱除。
附图说明
图1为本发明脱除烟气中二噁英的蜂窝式催化剂制备流程图。
图2为本发明脱除烟气中二噁英的蜂窝式催化剂实物图。
具体实施方式
下面通过具体实施例对本发明蜂窝式催化剂制备及脱除烟气中二噁英的性能作进一步说明。
实施例1
(1)将1.5 kg乙醇胺加入到35.0 kg去离子水中,形成乙醇胺水溶液A;
(2)在溶解罐中,将溶液A加热到70℃,然后将7.0 kg 四氯化锡,11.6 kg草酸氧钒,9.1kg 仲钨酸铵,3.9 kg 硝酸镧,0.8 kg硝酸镨加入溶液A中,形成溶液B;
(3)将271.4 kg钛白粉,10.1 kg ZSM-5分子筛,1.5 kg玻璃纤维,1.5 kg木浆、2.0 kg硬脂酸,2.0 kg乳酸,16.0 kg CMC和10 kg PEO加入到混料机中,加入少量水和氨水溶液,搅拌10分钟;然后加入溶液B,继续搅拌40分钟,用氨水调节pH至7.0,控制水分在29.0%,继续搅拌40分钟后,进行过滤和真空捏合;
(4)将捏合好的泥料密封后放在温度为25℃,湿度为60%的环境中进行陈腐,陈腐时间为24小时;
(5)将陈腐完后的泥料进行再次捏合、过滤和预挤出,然后将预挤出的泥料进行二次陈腐,陈腐条件和一次陈腐时一致;
(6)陈腐完后,将泥料在强力挤出机上进行挤出成型,干燥;挤出催化剂孔数为35孔;干燥条件为:随着干燥时间的进行,环境温度从20℃逐渐升到60℃,湿度从90%逐渐降到20%,干燥时间为8天;
(7)干燥好的催化剂在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。焙烧最高温度为400℃,产品出窑温度为60℃,焙烧时间控制在25小时。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
实施例2
(1)将9.0 kg乙醇胺加入到46.0 kg去离子水中,形成乙醇胺水溶液A;
(2)在溶解罐中,将溶液A加热到70℃,然后将27.0 kg偏钒酸铵,6.4 kg偏钨酸铵加入溶液A中,形成溶液B;
(3)在溶解罐中将6.2 kg硫酸亚锡,3.2 kg醋酸锑加入15.0 kg去离子水中,形成溶液C;
(4)将138.0 kg钛白粉,12.0 kg玻璃纤维,3.5 kg CMC和6.0 kg PEO加入到混料机中干混均匀,加入少量水和氨水溶液,搅拌40分钟;将溶液B加入混料机中,搅拌30分钟;将75.0 kg钛白粉和水加入到混料机中,高速搅拌60分钟;将溶液C和6.0 kg硬脂酸加入混料机中,搅拌50分钟;将4.5 kg木浆和3.5 kg乳酸加入混料机中,搅拌60分钟;将45.0 kg钛白粉和水加入到混料机中搅拌30分钟,同时用氨水调节pH至7.5,控制总水分在29.0%,继续搅拌40分钟后,经过滤、真空捏合、预挤出后得到塑性较好的泥料;
(5)将预挤出的泥料密封后放在温度为30℃,湿度为65%的环境中进行陈腐,陈腐时间为48小时;
(6)将陈腐完后的泥料在强力挤出机上进行挤出成型,干燥;挤出催化剂孔数为15孔;干燥条件为:随着干燥时间的进行,环境温度从20℃逐渐升到50℃,湿度从80%逐渐降到20%,干燥时间为8天;
(7)干燥好的催化剂在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。焙烧最高温度为450℃,产品出窑温度为80℃,焙烧时间控制在25小时。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
实施例3
(1)将12.0 kg乙醇胺加入到45.0 kg去离子水中,形成乙醇胺水溶液A;
(2)在溶解罐中,将溶液A加热到70℃,再将19.3 kg偏钒酸铵,12.8 kg偏钨酸铵的加入溶液A中,形成溶液B;
(3)在溶解罐中将18.0 kg草酸铌,2.6 kg硫酸铈和1.7 kg硅胶加入20.0 kg去离子水中,形成溶液C;
(4)将139.5 kg钛白粉,8.5 kg ZSM-5分子筛,9.0 kg玻璃纤维,12.0 kg CMC和6.0 kgPEO加入到混料机中干混均匀,然后加入少量水和氨水溶液,搅拌30分钟;将溶液B加入混料机中,搅拌60分钟;将65.0 kg钛白粉和水加入到混料机中,高速搅拌40分钟;将溶液C和15.5 kg硬脂酸加入混料机中,搅拌60分钟;将10.0 kg木浆和2.0 kg乳酸加入混料机中,搅拌30分钟;将40.0 kg钛白粉,5.0 kg ZSM-5分子筛和水加入到混料机中搅拌30分钟,同时用氨水调节pH至8.0,控制总水分在30.0%,继续搅拌40分钟后,充分混炼均匀,经过滤、真空捏合、预挤出后得到塑性较好的泥料;
(5)将预挤出的泥料密封后放在温度为30℃,湿度为70%的环境中进行陈腐,陈腐时间为48小时;
(6)将陈腐完后的泥料在强力挤出机上进行挤出成型,干燥;挤出催化剂孔数为40孔;干燥条件为:随着干燥时间的进行,环境温度从30℃逐渐升高到60℃,湿度从80%逐渐降低到30%,干燥时间为7天;
(7)干燥好的催化剂在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。焙烧最高温度为500℃,产品出窑温度为60℃,焙烧时间控制在45小时。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
实施例4
(1)将18.0 kg乙醇胺加入到50.0 kg去离子水中,形成乙醇胺水溶液A;
(2)在溶解罐中,将溶液A加热到80℃,再将18.3 kg硫酸氧钒,25.7 kg仲钨酸铵加入溶液A中,形成溶液B;
(3)在溶解罐中,将3.9 kg 硝酸镧,1.5 kg五氧化二铌加入15.0 kg去离子水中,形成溶液C;将1.3 kg氧化锗加入10.0 kg去离子水中,形成溶液D;
(4)将125.0 kg钛白粉,18.0 kg玻璃纤维,3.0 kg CMC和9.0 kg PEO加入到混料机中干混均匀,然后加入水和少量氨水溶液,搅拌40分钟;将溶液B加入混料机中,搅拌30分钟;将80.0 kg钛白粉、溶液C和水加入到混料机中,高速搅拌30分钟;将4.5 kg木浆、6.0 kg乳酸和10.5 kg硬脂酸加入混料机中,搅拌30分钟;将60.0 kg钛白粉、溶液D和水加入到混料机中搅拌60分钟,同时用氨水调节pH至8.5,控制总水分在30.0%。继续搅拌40分钟后,经过滤、真空捏合、预挤出后得到塑性较好的泥料;
(5)将预挤出的泥料密封后放在温度为30℃,湿度为60%的环境中进行陈腐,陈腐时间为48小时;
(6)将陈腐完后的泥料在强力挤出机上进行挤出成型,干燥;挤出催化剂孔数为50孔;干燥条件为:随着干燥时间的进行,环境温度从40℃逐渐升高到60℃,湿度从70%逐渐降低到20%,干燥时间为7天;
(7)干燥好的催化剂在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。焙烧最高温度为550℃,产品出窑温度为80℃,焙烧时间控制在25小时。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
实施例5
(1)将25.0 kg乙醇胺加入到55.0 kg去离子水中,形成乙醇胺水溶液A;
(2)在溶解罐中,将溶液A加热到90℃,然后将30.9 kg偏钒酸铵,9.1 kg 仲钨酸铵,3.4kg正硅酸乙酯加入溶液A中,形成溶液B;
(3)在溶解罐中将3.9 kg硝酸镨加入15.0 kg去离子水中,形成溶液C;在溶解罐中将1.8 kg七钼酸铵,0.9 kg乙酸铜加入8.0 kg去离子水中,形成溶液D;
(4)将100.0 kg钛白粉,9.0 kg玻璃纤维、12.0 kg CMC和6.0 kg PEO加入到混料机中干混均匀,然后加入溶液B、水和少量氨水溶液,搅拌50分钟;将70.0 kg钛白粉、溶液C和水加入到混料机中,高速搅拌40分钟;将15 kg木浆、1.5 kg乳酸和1.5 kg硬脂酸加入混料机中,搅拌30分钟;将85.0 kg钛白粉、5.0 kg ZSM-5分子筛、溶液D和水加入到混料机中搅拌30分钟,同时用氨水调节pH至8.0,控制总水分在28.0~31.0%,然后继续搅拌60分钟后,充分混炼均匀,经真空捏合、过滤、预挤出后得到塑性较好的泥料;
(5)将预挤出的泥料密封后放在温度为25℃,湿度为65%的环境中进行陈腐,陈腐时间为36小时;
(6)将陈腐完后的泥料在强力挤出机上进行挤出成型,干燥;挤出催化剂孔数为60孔;干燥条件为:随着干燥时间的进行,环境温度从20℃逐渐升高到60℃,湿度从90%逐渐降低到30%,干燥时间为9天;
(7)干燥好的催化剂在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。焙烧最高温度为450℃,产品出窑温度为80℃,焙烧时间控制在45小时。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
对比例1
将7.5 kg乙醇胺加入75.0 kg去离子水中,形成乙醇胺水溶液A;在溶解罐中,将溶液A加热到80℃,然后将18.3 kg硫酸氧钒,19.1 kg磷钨酸加入溶液A中,形成溶液B;将264.0kg钛白粉,9.0 kg玻璃纤维,2.5 kg木浆,5.0 kg硬脂酸,3.5 kg CMC和6.0 kg PEO加入到混料机中,加入水和少量氨水溶液,搅拌15分钟;然后加入溶液B,继续搅拌40分钟,用氨水调节pH至8.0,控制水分在30.0%,然后经过滤、真空捏合、陈腐、干燥、焙烧得到二噁英脱除蜂窝式催化剂,陈腐、干燥和焙烧条件与实施例1相同。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
对比例2
将15.0 kg乙醇胺加入81.0 kg去离子水中,形成乙醇胺水溶液A;在溶解罐中,将溶液A加热到80℃,然后将25.5 kg仲钨酸铵,24.0 kg硝酸铈,32.6 kg氯化亚锡加入溶液A中,形成溶液B;将261.0 kg钛白粉,15.0 kg玻璃纤维,5.0 kg木浆,10.0 kg乳酸,12.5 kg CMC和3.0 kg PEO加入混料机中,加入水和少量氨水溶液,搅拌10分钟;然后加入溶液B,继续搅拌40分钟,用氨水调节pH至8.0,控制水分在30.0%,然后经过滤、真空捏合、陈腐、干燥、焙烧得到二噁英脱除蜂窝式催化剂,陈腐、干燥和焙烧条件与实施例5相同。蜂窝式催化剂的物理性质见表1。蜂窝式催化剂二噁英类污染物脱除性能见表2。
Claims (10)
1.一种催化氧化脱除烟气中二噁英的蜂窝式催化剂,由活性组分、载体和强度增强剂组成;其特征在于:活性组分包括钒,钨,IVA族元素,以及轻稀土、铌、钼、铜、锑元素中的一种或几种。
2.如权利要求1所述一种催化氧化脱除烟气中二噁英的蜂窝式催化剂,其特征在于:所述活性组分中,各元素以氧化物计,钒和钨的含量分别为1.0~11.5%,IVA族元素的量分别为0.1~8.0%,轻稀土元素的量分别为0.1~6.0%,铌、钼、铜、锑的量分别为0.1~4.5%。
3.如权利要求1所述一种用于催化氧化脱除烟气中二噁英的蜂窝式催化剂,其特征在于:载体为钛白粉和ZSM-5复合材料,钛白粉的含量为53.0~90.0%,ZSM-5的含量为0~15.0%。
4.如权利要求1所述一种催化氧化脱除烟气中二噁英的蜂窝式催化剂,其特征在于:强度增强剂为玻璃纤维,玻璃纤维的含量为0.5~10.0%。
5.如权利要求1所述一种催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,包括以下步骤:
(1)将乙醇胺加入到去离子水中,形成乙醇胺溶液,乙醇胺的加入量为催化剂质量的0.5~10.0%;
(2)在乙醇胺和水溶液中将活性组分前驱体溶解后,与载体、辅料按照设计比例进行混合,混合后的料在混炼机中进行混炼,同时用氨水调节泥料pH至7.0~8.5,控制泥料水分在28.0~31.0%,充分搅拌混炼均匀后,对泥料进行过滤、真空捏合和预挤出;
(3)将预挤出的泥料密封后,在温度20~30℃,湿度60~70%的环境中陈腐24~48小时;
(4)将陈腐后的泥料在强力挤出机上进行挤出成型,干燥,然后在连续式网带窑炉中进行焙烧,得到蜂窝式催化剂。
6.如权利要求5所述催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,其特征在于:步骤(1)中,乙醇胺为单乙醇胺、二乙醇胺或三乙醇胺中的一种或几种。
7.如权利要求5所述催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,其特征在于:步骤(2)活性组分的前驱体物质中,钒的前驱体为草酸氧钒、硫酸氧钒或偏钒酸铵的一种或几种;钨的前驱体为偏钨酸铵、仲钨酸铵或磷钨酸铵的一种或几种;铌的前驱体为氯化铌、草酸铌或氧化铌中的一种或几种;钼的前驱体为钼酸铵、七钼酸铵或钼酸钠中的一种或几种;IVA族元素的前驱体为其氧化物、硫酸盐、草酸盐、氯盐或有机化合物中的一种或几种;轻稀土元素、铜和锑的前驱体为各自的硝酸盐、氯盐或硫酸盐的一种或几种;各活性组分前驱体溶解后加入到混炼机中的次序可根据具体情况调整。
8.如权利要求5所述催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,其特征在于:步骤(2)中的辅料包括强度增强剂玻璃纤维、木浆、硬脂酸、乳酸、羧甲基纤维素、聚氧化乙烯;各辅料的加入量分别为催化剂质量的0.5~10%;各辅料的加入次序可根据具体情况调整。
9.如权利要求5所述催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,其特征在于:步骤(3)中,为了获得塑性更好的泥料,陈腐完后的泥料可再次进行真空捏合、预挤出和二次陈腐,陈腐条件和一次陈腐时一致。
10.如权利要求5所述催化氧化脱除烟气中二噁英的蜂窝式催化剂的制备方法,其特征在于:步骤(4)中,挤出催化剂孔数为15~60;干燥条件:温度为20~60℃,湿度为90~20%,时间为8~9天;焙烧条件为:最高温度为400~550℃,产品出窑温度为60~80℃,焙烧时间控制在25~45小时。
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