WO2024027077A1 - Method for using ammonia water to accelerate catalytic decomposition of formaldehyde by means of manganese-based catalyst - Google Patents
Method for using ammonia water to accelerate catalytic decomposition of formaldehyde by means of manganese-based catalyst Download PDFInfo
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- WO2024027077A1 WO2024027077A1 PCT/CN2022/139574 CN2022139574W WO2024027077A1 WO 2024027077 A1 WO2024027077 A1 WO 2024027077A1 CN 2022139574 W CN2022139574 W CN 2022139574W WO 2024027077 A1 WO2024027077 A1 WO 2024027077A1
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- formaldehyde
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- based catalyst
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 41
- 239000011572 manganese Substances 0.000 title claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000003421 catalytic decomposition reaction Methods 0.000 title abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 15
- 239000002156 adsorbate Substances 0.000 claims description 10
- 238000004817 gas chromatography Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 231100000462 teratogen Toxicity 0.000 description 1
- 239000003439 teratogenic agent Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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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
- B01D53/74—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
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- 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
Definitions
- the invention belongs to the field of environmental cleanliness and relates to a method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst, and a method of using ammonia water to accelerate the catalytic removal of formaldehyde under the catalysis of metal nanoparticles.
- the chemical substance formaldehyde is recognized as the most representative cause of indoor air pollution.
- Indoor formaldehyde mainly comes from building materials, furniture, artificial panels, various adhesive coatings, synthetic textiles, etc.
- Formaldehyde is a highly toxic substance. Formaldehyde ranks second on my country's priority control list of toxic chemicals. It has been identified as a carcinogen and teratogen by the World Health Organization. It is a recognized source of allergic reactions and a potential strong mutagenic agent.
- formaldehyde removal is particularly important.
- Indoor formaldehyde removal methods mainly include ventilation method, biological method, adsorption method, photodegradation method, catalytic oxidation method, etc.
- Manganese dioxide (MnO 2 ) has high catalytic oxidation properties, stability, and low cost, making it a widely studied catalyst. At the same time, by doping transition metals, the cost of manganese dioxide can be effectively reduced and the surface area can be increased. , increase active oxygen and improve redox performance.
- the purpose of the present invention is to provide a method for accelerating the catalytic decomposition and degradation of formaldehyde using ammonia water.
- the present invention uses MnO 2 and modified MnO 2 as catalyst research objects, and adds a small amount of ammonia water to the surface of the catalyst in the formaldehyde atmosphere to improve the conversion efficiency of formaldehyde.
- the method involved in the invention not only has the characteristics of simple process operation, green safety and low cost, but also can realize large-scale continuous production and has obvious economic and environmental benefits.
- the technical solution is:
- a method of using ammonia water to accelerate the catalytic degradation of formaldehyde by a manganese-based catalyst is as follows: weigh an appropriate amount of manganese-based catalyst and put it into a specific reactor, and the reactor is connected to a gas chromatograph. First, the manganese-based catalyst is subjected to adsorbate removal treatment under high vacuum conditions; then, the vacuum pressure difference is used to introduce dried formaldehyde gas into the reactor and let it stand for half an hour; then a small amount is dripped into the catalyst surface.
- Ammonia water so that the mass ratio range of the input amount of ammonia water and the manganese-based catalyst is 1:10; use gas chromatography to detect the concentration change of formaldehyde online and calculate the formaldehyde removal rate of the sample, and the removal rate can reach 100%.
- the reactor refers to a hard glass tube or quartz tube with one end closed and one end open;
- the manganese-based catalyst is a MnO 2 catalyst, or a transition metal-doped MnO 2 catalyst such as Cr, Cu or Zn, and the transition metal component accounts for 10wt% of the catalyst;
- the reaction input amount of the manganese-based catalyst ranges from 0.01 to 0.05g;
- the initial concentration range of the formaldehyde reactant is 1.0 to 5.0 mg/m 3 .
- the invention provides a method for accelerating the decomposition and removal of formaldehyde using ammonia water under the catalysis of a nanometer manganese oxide catalyst.
- MnO 2 or MnO 2 doped with transition metals Cr, Cu, Zn, etc. is used as the catalyst in the study, and ammonia water is used to accelerate the decomposition and removal of formaldehyde.
- ammonia is used to change the formaldehyde usage environment to a weak alkaline one, the weak alkalinity on the catalyst surface will be conducive to the response and decomposition of formaldehyde, which can increase the reaction efficiency by more than 4 times.
- the method of the present invention is simple to operate. It only uses ammonia water as alkali liquid for operation. Based on the weak alkaline change of the unique nano-manganese-based catalyst surface, it can effectively improve the conversion and decomposition rate of formaldehyde.
- Figure 1 is a comparison chart of the reaction effects of the Cr/MnO 2 catalyst in catalytically decomposing formaldehyde with or without the addition of ammonia.
- a method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst as follows:
- Reaction steps perform adsorbate removal treatment on the manganese-based catalyst under high vacuum conditions for half an hour; then, use a formaldehyde release instrument to introduce dried formaldehyde gas into the reactor according to the vacuum pressure difference, and let it stand for half an hour. , so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0mg/m 3 ; then, 1.0ml of ammonia water is dripped into the catalyst surface; the reaction is for 4 hours, and the concentration change of formaldehyde is detected online using gas chromatography, and the formaldehyde removal rate of the sample is calculated .
- Figure 1 shows the reaction effect of the Cr/MnO 2 catalyst catalytically decomposing formaldehyde with or without the addition of ammonia. It can be seen from the gas chromatography detection results: after adding ammonia, the activity of the Cr/MnO 2 catalyst has been significantly improved. , after 4 hours of reaction, the formaldehyde conversion rate can reach 100%, while the formaldehyde conversion rate of the catalyst without adding ammonia water only reaches about 18%. It can be seen that after the ammonia water is added, the activity of the catalyst increases by more than 4 times. This is mainly because the addition of ammonia water changes the surface of the catalyst to form a weak alkalinity, resulting in a greater improvement in activity.
- a method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst as follows:
- the measurement results show that after adding a small amount of alkaline ammonia water, the 10% Cu/MnO 2 catalyst can significantly improve the catalytic decomposition effect of formaldehyde.
- a method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst as follows:
- the measurement results show that after adding a small amount of alkaline ammonia water, the 10% Zn/MnO 2 catalyst can significantly improve the catalytic decomposition effect of formaldehyde.
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- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
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Abstract
A method for using ammonia water to accelerate the catalytic decomposition of formaldehyde by means of a manganese-based catalyst: an MnO2 or transition metal Cr, Cu, or Zn-doped MnO2 catalyst is used, and at an initial formaldehyde concentration of 1.0 mg/m3, the complete decomposition of formaldehyde can be achieved by adding a small amount of ammonia water.
Description
本发明属于环境洁净领域，涉及到一种使用氨水加速锰基催化剂催化降解甲醛的方法，使用氨水在金属纳米颗粒的催化下加速甲醛催化去除的方法。The invention belongs to the field of environmental cleanliness and relates to a method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst, and a method of using ammonia water to accelerate the catalytic removal of formaldehyde under the catalysis of metal nanoparticles.
造成室内空气污染公认具有代表性的是化学物质甲醛，室内甲醛主要来源于建筑材料、家具、人造板材、各种黏合剂涂料和合成纺织品等等。甲醛为较高毒性的物质，在我国有毒化学品优先控制名单上甲醛高居第二位，它已经被世界卫生组织确定为致癌和致畸形物质，是公认的***反应源，也是潜在的强致突变物之一。鉴于室内甲醛污染的问题，进行甲醛的去除尤为重要。室内甲醛的去除方法主要有通风法、生物法、吸附法、光降解法、催化氧化法等等。二氧化锰(MnO
2)具有较高的催化氧化性、稳定性，且成本较低而成为广泛研究的催化剂，同时通过掺杂过渡金属，能够有效降低二氧化锰的使用成本，还能够提高表面积，增加活性氧、改善氧化还原性能。
The chemical substance formaldehyde is recognized as the most representative cause of indoor air pollution. Indoor formaldehyde mainly comes from building materials, furniture, artificial panels, various adhesive coatings, synthetic textiles, etc. Formaldehyde is a highly toxic substance. Formaldehyde ranks second on my country's priority control list of toxic chemicals. It has been identified as a carcinogen and teratogen by the World Health Organization. It is a recognized source of allergic reactions and a potential strong mutagenic agent. One of the things. In view of the problem of indoor formaldehyde pollution, formaldehyde removal is particularly important. Indoor formaldehyde removal methods mainly include ventilation method, biological method, adsorption method, photodegradation method, catalytic oxidation method, etc. Manganese dioxide (MnO 2 ) has high catalytic oxidation properties, stability, and low cost, making it a widely studied catalyst. At the same time, by doping transition metals, the cost of manganese dioxide can be effectively reduced and the surface area can be increased. , increase active oxygen and improve redox performance.
研究表明，在氧化锰晶体中掺杂Cu,Zn,Cr，Co等组分，能够显著提高催化降解甲醛的性能。Liu等人在Applied Clay Science(2018,161,265-273)报道，在锰氧化物中掺入Cu离子后，在250℃温度下甲醛的转化率高达90％，可以有效氧化为CO
2、H
2O等成分。尽管研究取得了一些进展，但是仍然存在一定的问题，主要表现在室温下甲醛的分解率仍旧较低，应用场景容易受到工艺因素的影响，等等。因此，如何将甲醛分子高效地催化氧化分解无疑是对研究者们的一大挑战，同时在室温下将甲醛分解去除，将对环境自洁领域产生非常重要的影响。
Studies have shown that doping Cu, Zn, Cr, Co and other components into manganese oxide crystals can significantly improve the performance of catalytic degradation of formaldehyde. Liu et al. reported in Applied Clay Science (2018, 161, 265-273) that after incorporating Cu ions into manganese oxide, the conversion rate of formaldehyde is as high as 90% at 250°C, and it can be effectively oxidized into CO 2 and H 2 O and other ingredients. Although research has made some progress, there are still certain problems, mainly manifested in the fact that the decomposition rate of formaldehyde at room temperature is still low, the application scenario is easily affected by process factors, and so on. Therefore, how to efficiently catalyze, oxidize and decompose formaldehyde molecules is undoubtedly a major challenge for researchers. At the same time, decomposing and removing formaldehyde at room temperature will have a very important impact on the field of environmental self-cleaning.
发明内容Contents of the invention
为克服室温下MnO
2催化剂分解甲醛效率低下的问题，本发明目的在于：提供一种使用氨水加速甲醛催化分解降解的方法。
In order to overcome the problem of low efficiency of decomposing formaldehyde by MnO 2 catalyst at room temperature, the purpose of the present invention is to provide a method for accelerating the catalytic decomposition and degradation of formaldehyde using ammonia water.
本发明使用MnO
2以及改性的MnO
2为催化剂研究对象，在甲醛氛围里加入少许的氨水至催化剂的表面，以提高甲醛的转化效率。本发明涉及的方法不仅具有工艺操作简单、绿色安全且成本低的特点，可以实现规模连续化生 产，具有明显的经济效益和环境效益。该技术方案为：
The present invention uses MnO 2 and modified MnO 2 as catalyst research objects, and adds a small amount of ammonia water to the surface of the catalyst in the formaldehyde atmosphere to improve the conversion efficiency of formaldehyde. The method involved in the invention not only has the characteristics of simple process operation, green safety and low cost, but also can realize large-scale continuous production and has obvious economic and environmental benefits. The technical solution is:
1、一种使用氨水加速锰基催化剂催化降解甲醛的方法，其反应过程为：称取适量的锰基催化剂放入特定的反应器中，反应器与气相色谱相连。首先，在高真空条件下对锰基催化剂进行吸附物脱除处理；接着，利用真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时；随后向催化剂表面中滴入少量氨水，使所述的氨水投入量与锰基催化剂的质量比范围为1:10；利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率，去除率可达100％。1. A method of using ammonia water to accelerate the catalytic degradation of formaldehyde by a manganese-based catalyst. The reaction process is as follows: weigh an appropriate amount of manganese-based catalyst and put it into a specific reactor, and the reactor is connected to a gas chromatograph. First, the manganese-based catalyst is subjected to adsorbate removal treatment under high vacuum conditions; then, the vacuum pressure difference is used to introduce dried formaldehyde gas into the reactor and let it stand for half an hour; then a small amount is dripped into the catalyst surface. Ammonia water, so that the mass ratio range of the input amount of ammonia water and the manganese-based catalyst is 1:10; use gas chromatography to detect the concentration change of formaldehyde online and calculate the formaldehyde removal rate of the sample, and the removal rate can reach 100%.
所述的反应器是指一端密闭一端开口的硬质玻璃管或者石英管；The reactor refers to a hard glass tube or quartz tube with one end closed and one end open;
所述的锰基催化剂为MnO
2催化剂，或者Cr、Cu或Zn等过渡金属掺杂的MnO
2催化剂，过渡金属成分占催化剂的含量为10wt％；
The manganese-based catalyst is a MnO 2 catalyst, or a transition metal-doped MnO 2 catalyst such as Cr, Cu or Zn, and the transition metal component accounts for 10wt% of the catalyst;
所述的锰基催化剂的反应投入量范围为0.01～0.05g；The reaction input amount of the manganese-based catalyst ranges from 0.01 to 0.05g;
所述的甲醛反应物初始浓度范围为1.0～5.0mg/m
3。
The initial concentration range of the formaldehyde reactant is 1.0 to 5.0 mg/m 3 .
本发明提供了一种使用氨水在纳米氧化锰催化剂的催化下加速甲醛分解去除的方法。使用MnO
2或者过渡金属Cr，Cu，Zn等掺杂的MnO
2作为研究的催化剂，使用氨水加速进行甲醛的分解去除。当使用氨水改变甲醛的使用环境为弱碱性后，催化剂表面的弱碱度将有利于甲醛的响应和分解，能够使反应效率提高4倍以上。本发明方法操作简单，仅仅使用氨水充当碱液进行操作，基于独特的纳米锰基催化剂表面进行弱碱性改变，能够有效提高甲醛的转化分解率。
The invention provides a method for accelerating the decomposition and removal of formaldehyde using ammonia water under the catalysis of a nanometer manganese oxide catalyst. MnO 2 or MnO 2 doped with transition metals Cr, Cu, Zn, etc. is used as the catalyst in the study, and ammonia water is used to accelerate the decomposition and removal of formaldehyde. When ammonia is used to change the formaldehyde usage environment to a weak alkaline one, the weak alkalinity on the catalyst surface will be conducive to the response and decomposition of formaldehyde, which can increase the reaction efficiency by more than 4 times. The method of the present invention is simple to operate. It only uses ammonia water as alkali liquid for operation. Based on the weak alkaline change of the unique nano-manganese-based catalyst surface, it can effectively improve the conversion and decomposition rate of formaldehyde.
图1为Cr/MnO
2催化剂在有无添加氨水情况下催化分解甲醛的反应效果对比图。
Figure 1 is a comparison chart of the reaction effects of the Cr/MnO 2 catalyst in catalytically decomposing formaldehyde with or without the addition of ammonia.
下面结合具体的实施例对本发明作进一步说明：The present invention will be further described below in conjunction with specific examples:
实施例1Example 1
一种使用氨水加速锰基催化剂催化降解甲醛的方法，按下述步骤：A method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst, as follows:
1)称取锰基催化剂0.01g的10％Cr/MnO
2催化剂放入反应器中，反应器与气相色谱相连；
1) Weigh 0.01g of manganese-based catalyst 10% Cr/MnO 2 catalyst and put it into the reactor, and the reactor is connected to the gas chromatograph;
2)反应步骤：在高真空条件下对锰基催化剂进行吸附物脱除处理半小时；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m
3；随后，向催化剂表面中滴入1.0ml氨水；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。
2) Reaction steps: perform adsorbate removal treatment on the manganese-based catalyst under high vacuum conditions for half an hour; then, use a formaldehyde release instrument to introduce dried formaldehyde gas into the reactor according to the vacuum pressure difference, and let it stand for half an hour. , so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0mg/m 3 ; then, 1.0ml of ammonia water is dripped into the catalyst surface; the reaction is for 4 hours, and the concentration change of formaldehyde is detected online using gas chromatography, and the formaldehyde removal rate of the sample is calculated .
图1为Cr/MnO
2催化剂在有无添加氨水情况下催化分解甲醛的反应效果图，从气相色谱的检测结果可以看出：在投入了氨水后，Cr/MnO
2催化剂的活性有了显著提高，反应4小时后，甲醛的转化率可达到100％，而未加氨水的催化剂的甲醛转化率仅仅达到18％左右。可见，氨水投入后，催化剂的活性增加了4倍以上，这主要是由于氨水的添加改变了催化剂的表面形成弱碱性，致使活性有了较大的提高。
Figure 1 shows the reaction effect of the Cr/MnO 2 catalyst catalytically decomposing formaldehyde with or without the addition of ammonia. It can be seen from the gas chromatography detection results: after adding ammonia, the activity of the Cr/MnO 2 catalyst has been significantly improved. , after 4 hours of reaction, the formaldehyde conversion rate can reach 100%, while the formaldehyde conversion rate of the catalyst without adding ammonia water only reaches about 18%. It can be seen that after the ammonia water is added, the activity of the catalyst increases by more than 4 times. This is mainly because the addition of ammonia water changes the surface of the catalyst to form a weak alkalinity, resulting in a greater improvement in activity.
实施例2Example 2
一种使用氨水加速锰基催化剂催化降解甲醛的方法，按下述步骤：A method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst, as follows:
1)称取锰基催化剂商业化的10％Cu/MnO
2催化剂0.01g放入反应器中，反应器与气相色谱相连；
1) Weigh 0.01g of the commercial 10% Cu/MnO 2 catalyst for manganese-based catalysts and put it into the reactor, and the reactor is connected to the gas chromatograph;
2)先在高真空条件下对锰基催化剂进行吸附物脱除处理半小时，将该Cu/MnO
2表面的吸附物进行脱除处理；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m
3；随后，向催化剂表面中滴入1.0ml氨水，所述的氨水投入量与锰基催化剂的质量比范围为1:10；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。
2) First, perform adsorbate removal treatment on the manganese-based catalyst under high vacuum conditions for half an hour to remove the adsorbate on the surface of Cu/ MnO2 ; then, use a formaldehyde release instrument to discharge the adsorbates into the reactor according to the vacuum pressure difference. Pour in the dried formaldehyde gas and let it stand for half an hour so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0 mg/m 3 ; then, drop 1.0 ml of ammonia water into the catalyst surface, and the ammonia water input amount is equal to The mass ratio range of the manganese-based catalyst is 1:10; react for 4 hours, use gas chromatography to detect the concentration changes of formaldehyde online, and calculate the formaldehyde removal rate of the sample.
测量结果表明，少许的碱性氨水投入后，10％Cu/MnO
2催化剂能够显著提高甲醛的催化分解效果。
The measurement results show that after adding a small amount of alkaline ammonia water, the 10% Cu/MnO 2 catalyst can significantly improve the catalytic decomposition effect of formaldehyde.
实施例3Example 3
一种使用氨水加速锰基催化剂催化降解甲醛的方法，按下述步骤：A method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst, as follows:
1)称取商业化的锰基催化剂10％Zn/MnO
2催化剂0.01g放入反应器中，反应器与气相色谱相连；
1) Weigh 0.01g of the commercial manganese-based catalyst 10% Zn/MnO 2 catalyst into the reactor, and the reactor is connected to the gas chromatograph;
2)在高真空条件下对锰基催化剂脱除半小时，将Zn/MnO
2表面的吸附物进行脱除处理；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经 干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m
3；随后，向该催化剂表面中滴入1.0ml氨水；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。
2) Remove the manganese-based catalyst under high vacuum conditions for half an hour to remove the adsorbed matter on the surface of Zn/ MnO2 ; then, use a formaldehyde release instrument to pass the dried formaldehyde into the reactor according to the vacuum pressure difference. Formaldehyde gas is allowed to stand for half an hour, so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0 mg/m 3 ; then, 1.0 ml of ammonia water is dripped into the surface of the catalyst; react for 4 hours, and use gas chromatography to detect the concentration of formaldehyde online. Change, calculate the formaldehyde removal rate of the sample.
测量结果表明，少许的碱性氨水投入后，10％Zn/MnO
2催化剂能够显著提高甲醛的催化分解效果。
The measurement results show that after adding a small amount of alkaline ammonia water, the 10% Zn/MnO 2 catalyst can significantly improve the catalytic decomposition effect of formaldehyde.
Claims (8)
- 一种使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，称取适量的锰基催化剂放入反应器中，反应器与气相色谱相连，首先，在真空条件下对锰基催化剂进行吸附物脱除处理；接着，利用真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时；随后，向催化剂表面中滴入少量氨水，所述的氨水投入量与锰基催化剂的质量比范围为1:10；利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。A method of using ammonia water to accelerate the catalytic degradation of formaldehyde over a manganese-based catalyst. It is characterized by weighing an appropriate amount of manganese-based catalyst and putting it into a reactor. The reactor is connected to a gas chromatograph. First, the manganese-based catalyst is adsorbed under vacuum conditions. material removal treatment; then, use the vacuum pressure difference to pass the dried formaldehyde gas into the reactor, and let it stand for half an hour; then, drop a small amount of ammonia water into the catalyst surface, the amount of ammonia water input is the same as the manganese-based catalyst The mass ratio range is 1:10; use gas chromatography to detect formaldehyde concentration changes online and calculate the formaldehyde removal rate of the sample.
- 根据权利要求1所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，所述的反应器是指一端密闭一端开口的硬质玻璃管或者石英管。The method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst according to claim 1, characterized in that the reactor refers to a hard glass tube or quartz tube with one end closed and one end open.
- 根据权利要求1所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，所述的锰基催化剂为MnO 2催化剂，或者包括Cr、Cu或Zn过渡金属掺杂的MnO 2催化剂，过渡金属成分占锰基催化剂的含量为10wt％。 The method of using ammonia water to accelerate the catalytic degradation of formaldehyde using a manganese-based catalyst according to claim 1, characterized in that the manganese-based catalyst is a MnO 2 catalyst, or a MnO 2 catalyst doped with Cr, Cu or Zn transition metals. The metal component accounts for 10wt% of the manganese-based catalyst.
- 根据权利要求1所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，所述的锰基催化剂的反应投入量范围为0.01～0.05g。The method of using ammonia water to accelerate the catalytic degradation of formaldehyde by a manganese-based catalyst according to claim 1, characterized in that the reaction input amount of the manganese-based catalyst ranges from 0.01 to 0.05g.
- 根据权利要求1所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，所述的甲醛反应物初始浓度范围为1.0～5.0mg/m 3。 The method of using ammonia water to accelerate the catalytic degradation of formaldehyde over a manganese-based catalyst according to claim 1, wherein the initial concentration range of the formaldehyde reactant is 1.0 to 5.0 mg/m 3 .
- 根据权利要求1至5任一项所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，按下述步骤：The method for using ammonia water to accelerate the catalytic degradation of formaldehyde over a manganese-based catalyst according to any one of claims 1 to 5, characterized in that the following steps are followed:1)称取锰基催化剂0.01g的10％Cr/MnO 2催化剂放入反应器中，反应器与气相色谱相连； 1) Weigh 0.01g of manganese-based catalyst 10% Cr/MnO 2 catalyst and put it into the reactor, and the reactor is connected to the gas chromatograph;2)反应步骤：在高真空条件下对锰基催化剂进行吸附物脱除处理半小时；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m 3；随后，向催化剂表面中滴入1.0ml氨水；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。 2) Reaction steps: perform adsorbate removal treatment on the manganese-based catalyst under high vacuum conditions for half an hour; then, use a formaldehyde release instrument to introduce dried formaldehyde gas into the reactor according to the vacuum pressure difference, and let it stand for half an hour. , so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0mg/m 3 ; then, 1.0ml of ammonia water is dripped into the catalyst surface; the reaction is for 4 hours, and the concentration change of formaldehyde is detected online using gas chromatography, and the formaldehyde removal rate of the sample is calculated .
- 根据权利要求1至5任一项所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，按下述步骤：The method for using ammonia water to accelerate the catalytic degradation of formaldehyde over a manganese-based catalyst according to any one of claims 1 to 5, characterized in that the following steps are followed:1)称取锰基催化剂商业化的10％Cu/MnO 2催化剂0.01g放入反应器中，反应器与气相色谱相连； 1) Weigh 0.01g of the commercial 10% Cu/MnO 2 catalyst for manganese-based catalysts and put it into the reactor, and the reactor is connected to the gas chromatograph;2)先在高真空条件下对锰基催化剂进行吸附物脱除处理半小时，将该Cu/MnO 2表面的吸附物进行脱除处理；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m 3；随后，向催化剂表面中滴入1.0ml氨水，所述的氨水投入量与锰基催化剂的质量比范围为1:10；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。 2) First, perform adsorbate removal treatment on the manganese-based catalyst under high vacuum conditions for half an hour to remove the adsorbate on the surface of Cu/ MnO2 ; then, use a formaldehyde release instrument to discharge the adsorbates into the reactor according to the vacuum pressure difference. Pour in the dried formaldehyde gas and let it stand for half an hour so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0 mg/m 3 ; then, drop 1.0 ml of ammonia water into the catalyst surface, and the ammonia water input amount is equal to The mass ratio range of the manganese-based catalyst is 1:10; react for 4 hours, use gas chromatography to detect the concentration changes of formaldehyde online, and calculate the formaldehyde removal rate of the sample.
- 根据权利要求1至5任一项所述使用氨水加速锰基催化剂催化降解甲醛的方法，其特征在于，按下述步骤：The method for using ammonia water to accelerate the catalytic degradation of formaldehyde over a manganese-based catalyst according to any one of claims 1 to 5, characterized in that the following steps are followed:1)称取商业化的锰基催化剂10％Zn/MnO 2催化剂0.01g放入反应器中，反应器与气相色谱相连； 1) Weigh 0.01g of the commercial manganese-based catalyst 10% Zn/MnO 2 catalyst into the reactor, and the reactor is connected to the gas chromatograph;2)在高真空条件下对锰基催化剂脱除半小时，将Zn/MnO 2表面的吸附物进行脱除处理；接着，利用甲醛释放仪根据真空压力差向反应器中通入已经干燥过的甲醛气体，静置半小时，使反应器中甲醛反应物初始浓度范围为1.0mg/m 3；随后，向该催化剂表面中滴入1.0ml氨水；反应4小时，利用气相色谱在线检测甲醛的浓度变化，计算样品的甲醛去除率。 2) Remove the manganese-based catalyst under high vacuum conditions for half an hour to remove the adsorbates on the surface of Zn/ MnO2 ; then, use a formaldehyde release instrument to pass the dried formaldehyde into the reactor according to the vacuum pressure difference. Formaldehyde gas is allowed to stand for half an hour, so that the initial concentration range of the formaldehyde reactant in the reactor is 1.0 mg/m 3 ; then, 1.0 ml of ammonia water is dropped into the catalyst surface; the reaction is carried out for 4 hours, and the concentration of formaldehyde is detected online using gas chromatography Change, calculate the formaldehyde removal rate of the sample.
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