CN114950423A - 室内低浓度甲醛净化催化剂产品及其制备方法 - Google Patents
室内低浓度甲醛净化催化剂产品及其制备方法 Download PDFInfo
- Publication number
- CN114950423A CN114950423A CN202210647024.0A CN202210647024A CN114950423A CN 114950423 A CN114950423 A CN 114950423A CN 202210647024 A CN202210647024 A CN 202210647024A CN 114950423 A CN114950423 A CN 114950423A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- formaldehyde
- solution
- active component
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- -1 oxygen ions Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 21
- 239000011572 manganese Substances 0.000 description 19
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000012876 carrier material Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920003081 Povidone K 30 Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 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
- 238000005034 decoration Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- 208000014085 Chronic respiratory disease Diseases 0.000 description 1
- 206010067477 Cytogenetic abnormality Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- JWGKHOVOXDSJJF-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Zr+4].O(Cl)Cl.[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Zr+4].O(Cl)Cl.[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] JWGKHOVOXDSJJF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 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 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/10—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering
- F24F8/15—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means
- F24F8/167—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means using catalytic reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
室内低浓度甲醛净化催化剂产品及其制备方法。该催化剂产品由基体和涂覆在基体上的催化剂涂层构成。本发明的催化剂涂层包含两种混合或分层涂覆的催化剂，第一种催化剂比表面积大，对室内低浓度甲醛具有优良的吸附作用，第二种催化剂则可以为活性组分提供更多的氧离子，从而提高催化剂的催化氧化反应，达到高效催化净化室内低浓度甲醛的目的。
Description
技术领域
本发明总体涉及一种甲醛净化催化剂。
背景技术
室内装修的胶合板、人造板、胶水等排放的甲醛、甲苯、苯等VOCs物种可引起慢性呼吸道疾病，新生儿染色体异常、白血病、智力下降等，甲醛、甲苯和苯已经被世界卫生组织确定为高度致癌物质。通常情况下，装潢和家具材料中的甲醛在室温条件下会缓慢释放出来，持续时间长达两年以上，导致室内环境中长期存在低浓度但处于超标状态的甲醛物质。因此，室内颗粒物和甲醛及其他VOCs污染物严重危害居民的身体健康，亟需得到治理。
活性炭吸附是用于室内甲醛净化最常用的技术手段，但由于活性炭对低浓度甲醛吸附强度和吸附容量都较低，在实际使用过程中去除甲醛的效率低，且达到饱和就失去净化效率，不能高效去除室内甲醛和长期使用，甚至存在二次释放的问题。另外，工业VOCs净化技术主要针对高浓度甲醛(甲醛浓度10-100ppm)，无法适用于净化低浓度的室内甲醛(实际浓度约为0.01-0.6ppm)。
发明内容
本发明的目的是提供一种适于净化室内低浓度甲醛的产品。
根据本发明的第一方面，提供了一种甲醛净化催化剂产品，其包括基体和涂覆在基体上的催化剂涂层，催化剂涂层包含第一催化剂和第二催化剂，其中
第一催化剂由第一活性组分和第一载体构成，第一活性组分选自Pt、Pd和Co中的至少一种，第一载体为由CeO2，ZrO2和MnO2组成的CexZryMnzO(2z+2x+2y)复合材料，其中x,y,z＝0.1～0.9，第一活性组分为第一催化剂总质量的0.1wt％～1.5wt％；
第二催化剂由第二活性组分和第二载体构成，第二活性组分选自Pt、Pd、Co和Mn中的至少一种，第二载体选自由Ce、La和/或SiO2所改性的Al2O3复合材料中的至少一种，第二活性组分为第二催化剂总质量的0.1wt％～1.5wt％。
在根据本发明的催化剂涂层中，第一催化剂与第二催化剂的重量比例优选为9:1～1:9，更优选为5:1～1:5。
根据本发明的甲醛净化催化剂产品，其中基体由多孔材料制成，优选为堇青石蜂窝陶瓷。
在根据本发明的第一催化剂中，第一载体优选为例如通过共沉淀法+沉积沉淀法制成。第一活性组分则可以由例如可溶性金属盐溶液通过原位还原或沉积沉淀的方法负载在第一载体表面；这可以提高活性组分的分散性和稳定性。第一活性组分优选为Pt。
在根据本发明的第二催化剂中，第二载体优选为由La所改性的Al2O3复合材料，可以例如通过共沉淀法制成。第二活性组分则可以由例如可溶性金属盐溶液通过原位还原或沉积沉淀的方法负载在第二载体表面；这可以提高活性组分的分散性和稳定性。第二活性组分优选为Mn。
根据本发明的第二方面，提供了一种上述甲醛净化催化剂产品的制备方法，包括：将第一催化剂和第二催化剂与粘结剂混合后涂敷在基体上，干燥后经焙烧即制得。
第一催化剂和第二催化剂可以与粘结剂分别单独混合后分层涂敷，也可以一起混合后进行涂敷。干燥温度优选为80℃～100℃。焙烧温度优选为450℃～600℃，时间优选为1～3h。
本发明的第一催化剂比表面积大，对室内低浓度甲醛具有优异的吸附作用，第二催化剂则可以为活性组分提供更多的氧离子，提高催化剂的催化氧化反应。二者协同作用，从而可以达到高效催化净化室内低浓度甲醛的目的。
附图说明
图1为根据本发明制备的Ce0.25Zr0.75O2固溶体的XRD图；
图2为本发明实施例1制备的催化剂产品的甲醛降解率时间曲线图。
图3为本发明实施例1制备的低浓度甲醛净化催化剂产品的照片。
具体实施方式
下面结合实施例和附图对本发明做进一步说明，本领域技术人员应该理解，实施例和附图只是为了更好地理解本发明，并不用于任何限制目的。
实施例1
制备第一催化剂
按照Ce:Zr:Mn摩尔比＝0.25:0.75:0.5称取14.33g六水硝酸铈、17.49g碳酸氧锆、11.99g硝酸锰备用以下步骤1)和2)。
1)共沉淀法准备CeO2-ZrO2载体材料
用浓硝酸溶解上述备用的碳酸氧锆形成碳酸氧锆硝解溶液，其中浓硝酸质量：碳酸氧锆质量＝1:10。将碳酸氧锆硝解溶液和上述备用的硝酸铈混合后采用去离子水稀释至1000倍溶液，形成CeO2-ZrO2前驱体稀释溶液。将氨水和碳铵混合(摩尔量均为3mol)后形成1000ml的缓冲溶液作为沉淀剂，将前驱体稀释溶液和缓冲溶液共同滴入沉淀罐中，所得沉淀物经过滤、洗涤，在100℃干燥12h，再在600℃焙烧3h后得到具有Ce0.25Zr0.75O2固溶体晶相CeO2-ZrO2复合载体材料，其XRD图如图1所示。
2)沉积沉淀法准备Ce0.25Zr0.75Mn0.5O3复合载体材料
将尿素和上述备用的硝酸锰混合在去离子水中准备硝酸锰前驱体溶液，其中尿素与Mn的摩尔比为5:1(尿素质量为20.12g)，并将步骤1)所制得的CeO2-ZrO2载体材料搅拌分散其中。之后在100℃水浴中连续沉积沉淀12h，所得悬浮溶液在100℃下干燥，600℃焙烧3h后得到20g Ce0.25Zr0.75Mn0.5O3复合载体材料。
3)原位还原法准备单金属Pt纳米催化剂(第一催化剂：其中Pt含量为0.5wt％)
按照上述Ce0.25Zr0.75Mn0.5O3复合载体材料与单金属Pt的质量比为99.5:0.5称取0.56gPt(NO3)2溶液(Pt含量为18wt％)，并采用2ml去离子水进行稀释，超声混合均匀后得到Pt金属稀释溶液。再按照PVP质量:单金属Pt质量＝20:1称取聚乙烯吡咯烷酮(PVP-K30)2g，并将PVP粉末超声震荡溶解在去离子水中形成PVP溶液，其中PVP质量:去离子水质量＝15:1。将Pt金属稀释溶液滴加到PVP溶液中，超声震荡1h使其混合均匀，并添加去离子水对Pt2 +—PVP混合溶液进行稀释，其中去离子水体积：Pt2+—PVP溶液＝20:1，之后超声震荡+搅拌1h后获得混合均匀的Pt2+—PVP稀释溶液。再将步骤2)制得的Ce0.25Zr0.75Mn0 . 5O3复合载体材 料加入Pt2+—PVP稀释溶液，并搅拌均匀。之后按照Pt金属摩尔量:还原剂摩尔量＝1:10的量添加0.90g还原剂抗坏血酸，并在100℃反应3h，冷却至室温(25℃)，100℃干燥12h，500℃焙烧3h，即获得第一催化剂。
制备第二催化剂
1)共沉淀法准备La-Al2O3复合载体材料
按照待制备的复合载体材料中La的质量百分含量为5wt％称取99.04g九水硝酸铝和0.32g的六水硝酸镧，并将二者采用去离子水稀释至1000倍溶液形成前驱体稀释溶液。再采用上述制备的氨水和碳铵混合的缓冲溶液作为沉淀剂，将前驱体稀释溶液和缓冲溶液共同滴入沉淀罐中，所得沉淀物经过滤、洗涤，在100℃干燥12h，再在600℃焙烧3h，得到5wt％La-Al2O3载体材料10g。
2)原位还原法准备单金属Mn纳米催化剂(第二催化剂：其中Mn含量为0.5wt％)
按照上述La-Al2O3载体材料与单金属Mn的质量比为99.5:0.5称取0.16g的Mn(NO3)4溶液，采用20ml去离子水进行稀释，超声混合均匀后形成Mn金属前驱体稀释溶液。按照PVP质量:单金属Mn质量＝20:1称取1g聚乙烯吡咯烷酮(PVP-K30)。将PVP粉末超声震荡溶解在去离子水中形成PVP溶液，其中PVP质量:去离子水质量＝15:1。再将Mn金属稀释溶液滴加到PVP溶液中，超声1h使其混合均匀后形成Mn4+—PVP混合溶液。然后添加去离子水对Mn4 +—PVP混合溶液进行稀释，其中去离子水体积:Mn4+—PVP溶液＝20:1，之后超声震荡+搅拌1h后获得混合均匀的Mn4+—PVP稀释溶液。接下来将上述La-Al2O3载体材料加入Mn4+—PVP稀释溶液(活性组分前驱体溶液)，并搅拌均匀。之后按照Mn金属摩尔量:还原剂摩尔量＝10:1添加0.0034g还原剂硼氢化钠，并在100℃反应3h；再冷却至室温(25℃)，过滤、洗涤，100℃干燥12h，500℃焙烧3h后即制得第二催化剂。
制备甲醛净化催化剂产品
将第一催化剂、第二催化剂(二者质量比3:2)与铝溶胶(Al2O3·nH2O，含量为催化剂总质量的3wt％)混合，然后将所得混合浆料涂覆在孔目数为400cell/in2，体积为80ml的蜂窝陶瓷基体上，涂覆量为150g/L，完成12g催化材料涂覆后，100℃干燥12h，550℃焙烧3h，即得到本发明的甲醛催化剂产品，见图3。
对实施例1的催化剂产品进行活性评价实验，实验条件如下：
模拟密闭室为3立方米，内空气组成：甲醛：3500ppm，氧气：21％，氮气：平衡气，舱内湿度65±5RH、温度23±1℃。采用轴流风机实现室内空气循环并确保循环风通过催化剂。
如图2所示：在60min内，甲醛降解率达到90％以上。
实施例2
第一催化剂和第二催化剂的制备同实施例1。
将第一催化剂和第二催化剂分别与铝溶胶(含量为催化剂总质量的3wt％)混合，分别球磨30min后得到第一和第二催化剂浆料。先将第二催化剂浆料涂覆在孔目数为400cell/in2，体积为80ml的蜂窝陶瓷基体上，涂覆量为60g/L；完成4.8g第二催化剂涂覆后，100℃干燥12h，550℃焙烧3h，得到第二催化剂涂覆的蜂窝陶瓷基体材料。再将第一催化剂浆料涂覆在涂覆有第二催化剂的蜂窝陶瓷基体材料上，涂覆量为90g/L；完成7.2g第一催化剂涂覆后，100℃干燥12h，550℃焙烧3h，即得到分层涂覆的催化剂产品。
Claims (5)
1.一种甲醛净化催化剂产品，包括基体和涂覆在基体上的催化剂涂层，催化剂涂层包含第一催化剂和第二催化剂，其中
第一催化剂由第一活性组分和第一载体构成，第一活性组分选自Pt、Pd和Co中的至少一种，第一载体为由CeO2，ZrO2和MnO2组成的CexZryMnzO(2z+2x+2y)复合材料，其中x,y,z＝0.1～0.9，第一活性组分为第一催化剂总质量的0.1wt％～1.5wt％；
第二催化剂由第二活性组分和第二载体构成，第二活性组分选自Pt、Pd、Co和Mn中的至少一种，第二载体选自由Ce、La和/或SiO2所改性的Al2O3复合材料中的至少一种，第二活性组分为第二催化剂总质量的0.1wt％～1.5wt％。
2.根据权利要求1所述的甲醛净化催化剂产品，其中催化剂涂层中的第一催化剂与第二催化剂的重量比例为9:1～1:9。
3.根据权利要求1所述的甲醛净化催化剂产品，其中基体材料为堇青石蜂窝陶瓷。
4.根据权利要求1所述的甲醛净化催化剂产品，其中第二载体为由La所改性的Al2O3复合材料。
5.一种根据权利要求1所述的甲醛净化催化剂产品的制备方法，包括：将第一催化剂和第二催化剂与粘结剂混合后涂敷在基体上，干燥后经焙烧即制得。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210647024.0A CN114950423B (zh) | 2022-06-08 | 2022-06-08 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210647024.0A CN114950423B (zh) | 2022-06-08 | 2022-06-08 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114950423A true CN114950423A (zh) | 2022-08-30 |
| CN114950423B CN114950423B (zh) | 2023-06-09 |
Family
ID=82961171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210647024.0A Active CN114950423B (zh) | 2022-06-08 | 2022-06-08 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114950423B (zh) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904633A (en) * | 1986-12-18 | 1990-02-27 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalyst for purifying exhaust gas and method for production thereof |
| EP1138382A1 (en) * | 2000-03-28 | 2001-10-04 | dmc2 Degussa Metals Catalysts Cerdec AG | Single layer high perfomance catalyst |
| CN101601999A (zh) * | 2008-06-14 | 2009-12-16 | 比亚迪股份有限公司 | 一种汽车尾气净化催化剂及其制备方法 |
| CN104226306A (zh) * | 2014-10-14 | 2014-12-24 | 北京恒泰实达科技股份有限公司 | 一种用于室温氧化消除甲醛的催化剂及其制备方法 |
| CN104549531A (zh) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | 一种蜂窝陶瓷载体及其制备方法 |
| CN104667947A (zh) * | 2015-02-13 | 2015-06-03 | 刘耀军 | 一种区块分布式贵金属复合氧化物VOCs催化剂及制备方法 |
| CN106890642A (zh) * | 2017-02-13 | 2017-06-27 | 无锡威孚环保催化剂有限公司 | 用于处理工业废气中苯类物质的催化剂及其制备方法 |
| CN107398272A (zh) * | 2017-08-09 | 2017-11-28 | 西安凯立新材料股份有限公司 | 一种甲醛室温催化用复合载体催化剂及其制备方法 |
| CN108246312A (zh) * | 2018-01-25 | 2018-07-06 | 无锡威孚环保催化剂有限公司 | 具有低温活性挥发性有机污染物净化的催化剂及制备方法 |
| US20180333699A1 (en) * | 2015-12-18 | 2018-11-22 | Basf Corporation | A catalyst device for treatment of formaldehyde and volatile organic compounds |
| CN111939898A (zh) * | 2020-09-08 | 2020-11-17 | 中自环保科技股份有限公司 | 一种甲醇燃料汽车尾气净化催化剂及其制备方法 |
| AU2021100281A4 (en) * | 2021-01-16 | 2021-04-15 | Huazhong University Of Science & Technology | A Mn doped cerium-zirconium solid solution used for flue gas mercury and toluene removal and a preparation method thereof |
| CN113019360A (zh) * | 2021-03-17 | 2021-06-25 | 南京工业大学 | 一种负载型复合氧化物催化剂及其制备方法和应用 |
| CN113304745A (zh) * | 2021-06-04 | 2021-08-27 | 中自环保科技股份有限公司 | 一种Pt-Pd-Rh三元催化剂及其制备方法 |
| WO2022047132A1 (en) * | 2020-08-28 | 2022-03-03 | Basf Corporation | Oxidation catalyst comprising a platinum group metal and a base metal oxide |
-
2022
- 2022-06-08 CN CN202210647024.0A patent/CN114950423B/zh active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904633A (en) * | 1986-12-18 | 1990-02-27 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalyst for purifying exhaust gas and method for production thereof |
| EP1138382A1 (en) * | 2000-03-28 | 2001-10-04 | dmc2 Degussa Metals Catalysts Cerdec AG | Single layer high perfomance catalyst |
| CN101601999A (zh) * | 2008-06-14 | 2009-12-16 | 比亚迪股份有限公司 | 一种汽车尾气净化催化剂及其制备方法 |
| CN104549531A (zh) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | 一种蜂窝陶瓷载体及其制备方法 |
| CN104226306A (zh) * | 2014-10-14 | 2014-12-24 | 北京恒泰实达科技股份有限公司 | 一种用于室温氧化消除甲醛的催化剂及其制备方法 |
| CN104667947A (zh) * | 2015-02-13 | 2015-06-03 | 刘耀军 | 一种区块分布式贵金属复合氧化物VOCs催化剂及制备方法 |
| US20180333699A1 (en) * | 2015-12-18 | 2018-11-22 | Basf Corporation | A catalyst device for treatment of formaldehyde and volatile organic compounds |
| CN106890642A (zh) * | 2017-02-13 | 2017-06-27 | 无锡威孚环保催化剂有限公司 | 用于处理工业废气中苯类物质的催化剂及其制备方法 |
| CN107398272A (zh) * | 2017-08-09 | 2017-11-28 | 西安凯立新材料股份有限公司 | 一种甲醛室温催化用复合载体催化剂及其制备方法 |
| CN108246312A (zh) * | 2018-01-25 | 2018-07-06 | 无锡威孚环保催化剂有限公司 | 具有低温活性挥发性有机污染物净化的催化剂及制备方法 |
| WO2022047132A1 (en) * | 2020-08-28 | 2022-03-03 | Basf Corporation | Oxidation catalyst comprising a platinum group metal and a base metal oxide |
| CN111939898A (zh) * | 2020-09-08 | 2020-11-17 | 中自环保科技股份有限公司 | 一种甲醇燃料汽车尾气净化催化剂及其制备方法 |
| AU2021100281A4 (en) * | 2021-01-16 | 2021-04-15 | Huazhong University Of Science & Technology | A Mn doped cerium-zirconium solid solution used for flue gas mercury and toluene removal and a preparation method thereof |
| CN113019360A (zh) * | 2021-03-17 | 2021-06-25 | 南京工业大学 | 一种负载型复合氧化物催化剂及其制备方法和应用 |
| CN113304745A (zh) * | 2021-06-04 | 2021-08-27 | 中自环保科技股份有限公司 | 一种Pt-Pd-Rh三元催化剂及其制备方法 |
Non-Patent Citations (6)
| Title |
|---|
| HENGCHENG LIAO ET AL: ""Preparation of Pd/(Ce1−xYx)O2/γ-Al2O3/cordierite catalysts and its catalytic combustion activity for methane"", 《CATALYSIS COMMUNICATIONS》, vol. 76 * |
| S. AZALIM ET AL: ""Washcoating of cordierite honeycomb with Ce–Zr–Mn mixed oxides for VOC catalytic oxidation"", 《CHEMICAL ENGINEERING JOURNAL》, vol. 223 * |
| XIAOXIAO LAI ET AL: ""Catalytic Oxidation of Toluene Over Potassium Modified Mn/Ce0.65Zr0.35O2 Catalyst"", 《ACTA PHYSICO-CHIMICA SINICA》, vol. 36 * |
| 唐幸福: ""锰—铈固溶体催化剂上甲醛完全氧化反应的研究"", 《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》, no. 4 * |
| 江玉洁等: ""Pd/CeZrOx-Al2O3/Cordierite整体式催化剂的制备及其丙烷催化燃烧性能"", 《华东理工大学学报(自然科学版)》, vol. 46 * |
| 陈莹等: ""涂覆在堇青石上的负载贵金属催化剂催化氧化甲醛的性能研究"", 《化学通报》, vol. 78 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114950423B (zh) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11713705B2 (en) | Nitrous oxide removal catalysts for exhaust systems | |
| CN107921416B (zh) | 用于排气系统的一氧化二氮去除催化剂 | |
| EP3257815B1 (en) | Micron-scale cerium oxide particle having multi-core single-shell structure and preparation method therefor | |
| KR101990156B1 (ko) | 세륨 산화물 및 니오븀 산화물을 포함하는 조성물을 촉매로 사용하는, 질소 산화물(NOx)-함유 가스를 처리하는 방법 | |
| WO2008150462A2 (en) | Catalyst for selective reduction of nitrogen oxides, method for making same and use thereof | |
| JPH0353968B2 (zh) | ||
| CN105358249B (zh) | 氮氧化物去除用催化剂 | |
| KR20140117361A (ko) | 황산 바륨을 함유하는 알루미나 재료, 및 그것을 이용한 배기가스 정화용 촉매 | |
| CN109876856B (zh) | 一种低温烟气脱硝催化剂及其制备方法 | |
| JP2020528348A (ja) | リーン／リッチシステムのための自動車排気からのｎ２ｏ除去 | |
| CN109590021B (zh) | 一种夹心结构的氨泄漏催化剂及其制备方法和应用 | |
| CN106890642B (zh) | 用于处理工业废气中苯类物质的催化剂及其制备方法 | |
| CN111375423B (zh) | 一种高温催化燃烧催化剂及其制备方法 | |
| JP2015174023A (ja) | 排ガス浄化用触媒 | |
| JP2024501748A (ja) | 貴金属が単独原子状態で担持された三元触媒、その調製方法及び使用 | |
| EP3581268A1 (en) | Exhaust gas purifying catalyst composition, method for producing same and exhaust gas purifying catalyst for automobiles | |
| CN114950423A (zh) | 室内低浓度甲醛净化催化剂产品及其制备方法 | |
| WO2013108756A1 (ja) | 排ガス浄化用卑金属触媒の製造方法 | |
| WO2021043267A1 (en) | Low-temperature denitration catalyst | |
| JPH1076159A (ja) | 排気ガス浄化触媒及びその製造方法 | |
| CN113680383A (zh) | 一种空气中醛类和苯系物净化复合材料及其制备方法和应用 | |
| EP3138622B1 (en) | Carrier for exhaust gas purification catalyst and exhaust gas purification catalyst | |
| CN1935361A (zh) | 废气净化催化剂及其制造方法 | |
| CN115041191B (zh) | 一种耐硫耐氯催化氧化催化剂及其制备方法 | |
| WO2022142836A1 (zh) | 一种催化组合物、催化剂层、催化装置和气体处理系统 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |