CN103143361A - Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof - Google Patents

Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof Download PDF

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CN103143361A
CN103143361A CN2013101065704A CN201310106570A CN103143361A CN 103143361 A CN103143361 A CN 103143361A CN 2013101065704 A CN2013101065704 A CN 2013101065704A CN 201310106570 A CN201310106570 A CN 201310106570A CN 103143361 A CN103143361 A CN 103143361A
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张慧
窦立广
段雪
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Beijing University of Chemical Technology
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Abstract

一种石墨烯促进型水滑石基脱硝催化剂及其制备方法,属于环境保护催化剂技术领域。催化剂的化学式为M2+ 2Mg2+Al3+(O);其中,M2+为Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合,M2+:Mg2+:Al3+的摩尔比为2:1:1;催化剂比表面积为80~110 m2/g,孔体积为0.3~0.4 cc/g,孔径分布为介孔分布。该催化剂通过共沉淀法将水滑石(LDHs)纳米片负载于石墨烯表面,焙烧后得到M2+ 2Mg2+Al3+(O)。优点在于,该催化剂对NOx的储存量具有很高的催化活性和较好的稳定性,大大优于无石墨烯促进型水滑石基催化剂,同时还具有增强的NO直接分解能力。

Figure 201310106570

A graphene-promoted hydrotalcite-based denitration catalyst and a preparation method thereof belong to the technical field of environmental protection catalysts. The chemical formula of the catalyst is M 2+ 2 Mg 2+ Al 3+ (O); wherein, M 2+ is one or a combination of Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ , and M 2+ The molar ratio of + : Mg 2+ : Al 3+ is 2:1:1; the specific surface area of the catalyst is 80-110 m 2 /g, the pore volume is 0.3-0.4 cc/g, and the pore size distribution is mesopore distribution. The catalyst supports hydrotalcite (LDHs) nanosheets on the surface of graphene by co-precipitation method, and M 2+ 2 Mg 2+ Al 3+ (O) is obtained after calcination. The advantage is that the catalyst has high catalytic activity and good stability for the storage of NOx , which is much better than the non-graphene-promoted hydrotalcite-based catalyst, and it also has enhanced NO direct decomposition ability.

Figure 201310106570

Description

一种石墨烯促进型水滑石基脱硝催化剂及其制备方法A kind of graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof

技术领域 technical field

本发明属于环境保护催化剂技术领域,特别是提供了一种石墨烯促进型水滑石基脱硝催化剂及其制备方法。The invention belongs to the technical field of environmental protection catalysts, and in particular provides a graphene-promoted hydrotalcite-based denitration catalyst and a preparation method thereof.

技术背景 technical background

进入二十一世纪以来,随着国民经济和交通运输业的不断发展,直接带动了机动车行业不断向前推进,使得机动车的生产量和保有量迅速增加,这在给我们的生活带来便利的同时,也给我们赖以生存的环境造成了严重的污染。其中,机动车尾气中NOx的排放(主要是NO)已经成为主要的大气污染源之一,由此形成的光化学烟雾和酸雨对城市环境和公众健康造成了严重威胁。考虑到对化石燃料的高效利用,贫燃发动机将是未来机动车的发展趋势,因此,贫燃条件下对NOx的脱除成为环保领域的一个研究热点和难点。在众多脱硝技术中,氮氧化物储存还原技术(NOStorage-Reduction, NSR)是移动源脱除NOx最具前景的发展技术。储存性能是NSR催化剂所具有的一个非常重要的特征,它直接影响NOx在适当条件下的完全脱除,因此其氮氧化物储存量(NOx Storage Capacity,NSC)是考察催化剂活性高低的一个重要方面。Since the beginning of the 21st century, with the continuous development of the national economy and the transportation industry, it has directly driven the motor vehicle industry forward, resulting in a rapid increase in the production and ownership of motor vehicles, which has brought great benefits to our lives. While convenient, it has also caused serious pollution to the environment on which we live. Among them, the emission of NOx (mainly NO) from motor vehicle exhaust has become one of the main sources of air pollution, and the resulting photochemical smog and acid rain pose a serious threat to the urban environment and public health. Considering the efficient use of fossil fuels, lean-burn engines will be the development trend of future motor vehicles. Therefore, the removal of NO x under lean-burn conditions has become a research hotspot and difficulty in the field of environmental protection. Among many denitrification technologies, NO x Storage-Reduction (NSR) technology is the most promising development technology for mobile source NO x removal. Storage performance is a very important characteristic of NSR catalysts, which directly affects the complete removal of NO x under appropriate conditions, so its nitrogen oxide storage capacity (NO x Storage Capacity, NSC) is an indicator of the activity of the catalyst. important aspect.

水滑石(LDHs)是由带正电荷层板和层间阴离子有序组装而形成的层状化合物,其化学组成可以用通式表示为:[M2+ 1-xM3+ x(OH)2]x+(An-)x/n·mH2O,其中M2+和M3+分别为主体层板上的二价和三价金属阳离子,An-为层间阴离子,x (=M3+/(M2++M3+))为摩尔比值。以LDHs为前驱体焙烧得到的复合金属氧化物兼具金属元素分布均一和本征碱性,在脱硝反应中具有直接分解、储存和还原多功能性,因而在NSR技术研究中受到了广泛关注。然而,由传统共沉淀法制备的LDHs粒径通常较大,且高温焙烧中容易烧结。因此由LDHs前体焙烧得到的复合金属氧化物通常存在比表面积小、粒子分散性差的缺点,从而使催化剂催化活性降低。同时又有研究表明焙烧温度越高此缺点表现越明显。如2009年,Li等在Applied Catalysis B: Environmental 第91卷406-415页中报道,由共沉淀法制备的LDHs基Co2.5Mg0.5AlO复合金属氧化物催化剂随焙烧温度提高催化剂的氮氧化物储存量迅速降低,这主要是由于催化剂烧结造成的比表面积降低及表面活性中心数量减少所致。Hydrotalcites (LDHs) are layered compounds formed by the orderly assembly of positively charged laminates and interlayer anions. Its chemical composition can be expressed by the general formula: [M 2+ 1-x M 3+ x (OH) 2 ] x+ (A n- ) x/n mH 2 O, where M 2+ and M 3+ are divalent and trivalent metal cations on the main laminate, A n- is an interlayer anion, x (= M 3+ /(M 2+ +M 3+ )) is a molar ratio. The composite metal oxides obtained by roasting LDHs as precursors have both uniform distribution of metal elements and intrinsic alkalinity, and have direct decomposition, storage and reduction functions in the denitrification reaction, so they have received extensive attention in the research of NSR technology. However, the particle size of LDHs prepared by traditional co-precipitation method is usually large, and it is easy to sinter during high-temperature calcination. Therefore, the composite metal oxides obtained by calcination of LDHs precursors usually have the disadvantages of small specific surface area and poor particle dispersion, thus reducing the catalytic activity of the catalyst. At the same time, some studies have shown that the higher the calcination temperature, the more obvious this shortcoming will be. For example, in 2009, Li et al. reported in Applied Catalysis B: Environmental, Vol. 91, pages 406-415, that the LDHs-based Co 2.5 Mg 0.5 AlO composite metal oxide catalyst prepared by the co-precipitation method increased the nitrogen oxide storage of the catalyst with the increase of the calcination temperature. The amount decreased rapidly, which was mainly due to the reduction of the specific surface area and the reduction of the number of surface active centers caused by catalyst sintering.

目前,通过选择一些合适的载体,提高纳米催化剂粒子的分散度进而提高催化活性的研究激起了广泛兴趣。例如,近年来关于新型碳载体如碳纤维(CF)、活性炭(AC)和碳纳米管(CNT)等负载金属单质/金属氧化物的报道有很多。2011年,Li等人在Journal of Hazardous Materials第192卷915-921页报道了碳纳米管(CNT)负载V2O5/TiO2催化剂,碳纳米管的促进作用表现在提高了催化剂的比表面积和孔体积,从而为催化反应提供了更多活性位。2012年,Xu等人在The Journal of Physical Chemistry C第112卷19841-19845页中报道的石墨烯(Graphene)负载Au、Pt、Pd纳米粒子催化剂在催化领域显示出巨大的应用潜力,其中很重要的原因就是石墨烯载体对活性组分的分散作用。以上事例说明选择合适的碳载体能够提高金属单质或金属氧化物的分散度,从而提高催化活性。At present, the study of improving the dispersion of nano-catalyst particles and improving the catalytic activity by selecting some suitable supports has aroused widespread interest. For example, in recent years, there have been many reports on novel carbon supports such as carbon fibers (CF), activated carbon (AC), and carbon nanotubes (CNTs) to support simple metals/metal oxides. In 2011, Li et al. reported carbon nanotube (CNT) supported V 2 O 5 /TiO 2 catalysts on pages 915-921 of Volume 192 of Journal of Hazardous Materials. The promotion effect of carbon nanotubes is reflected in the increase of the specific surface area of the catalyst. and pore volume, thus providing more active sites for catalytic reactions. In 2012, the graphene (Graphene) supported Au, Pt, Pd nanoparticle catalyst reported by Xu et al. in The Journal of Physical Chemistry C, Volume 112, 19841-19845, showed great application potential in the field of catalysis, among which it is very important The reason is the dispersion effect of the graphene carrier on the active component. The above examples show that choosing a suitable carbon support can increase the dispersion of metal element or metal oxide, thereby improving the catalytic activity.

发明内容 Contents of the invention

本发明的目的在于提供一种石墨烯促进型水滑石基脱硝催化剂及其制备方法。制备过程简便且条件温和,不需要任何有机试剂,所得的石墨烯负载水滑石复合材料中水滑石纳米片尺寸均一且高分散。焙烧后所得到的石墨烯促进型水滑石基催化剂在脱硝反应中显示出优异的NOx储存能力及分解性能,归因于石墨烯对活性组分的高分散促进作用。The object of the present invention is to provide a graphene-promoted hydrotalcite-based denitration catalyst and a preparation method thereof. The preparation process is simple and the conditions are mild, and no organic reagent is required, and the hydrotalcite nanosheets in the obtained graphene-loaded hydrotalcite composite material are uniform in size and highly dispersed. The obtained graphene-promoted hydrotalcite-based catalysts after calcination showed excellent NO x storage capacity and decomposition performance in the denitration reaction, which was attributed to the high dispersion promotion effect of graphene on the active components.

氧化石墨烯在初始制备首先以静电作用力吸附盐溶液中金属阳离子,成核过程中抑制了水滑石晶核的生长和团聚,从而得到高分散、尺寸均一的水滑石基催化剂,进而克服现有技术中水滑石基催化剂普遍氮氧化物储存量不高的缺点。该催化剂在贫燃条件下对NOx的脱除呈现了很高的储存能力和较好的直接分解性能,大大优于无石墨烯促进型水滑石基催化剂,同时制备过程简便、条件温和。催化剂循环利用4次,储存量、分解率基本保持不变,表明催化剂具有较高的稳定性。In the initial preparation, graphene oxide first adsorbs metal cations in the salt solution by electrostatic force, and inhibits the growth and agglomeration of hydrotalcite nuclei during the nucleation process, thereby obtaining a highly dispersed and uniformly sized hydrotalcite-based catalyst, thereby overcoming the existing Hydrotalcite-based catalysts generally have a shortcoming of low storage capacity of nitrogen oxides in the technology. The catalyst exhibits high storage capacity and good direct decomposition performance for NOx removal under lean-burn conditions, which is much better than graphene-free promoted hydrotalcite-based catalysts, and the preparation process is simple and the conditions are mild. The catalyst was recycled 4 times, and the storage capacity and decomposition rate remained basically unchanged, indicating that the catalyst had high stability.

本发明的石墨烯促进型水滑石基脱硝催化剂的化学式为M2+ 2Mg2+Al3+(O);其中,M2+为Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合,M2+:Mg2+:Al3+的摩尔比为2:1:1;催化剂比表面积为80~110 m2/g,孔体积为0.3~0.4 cc/g,孔径分布为介孔分布。The chemical formula of the graphene-promoted hydrotalcite-based denitration catalyst of the present invention is M 2+ 2 Mg 2+ Al 3+ (O); wherein, M 2+ is Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ One or several combinations of them, the molar ratio of M 2+ : Mg 2+ : Al 3+ is 2:1:1; the specific surface area of the catalyst is 80-110 m 2 /g, and the pore volume is 0.3-0.4 cc/ g, The pore size distribution is mesopore distribution.

该催化剂通过共沉淀法将水滑石(LDHs)纳米片负载于石墨烯(Graphene)表面,焙烧后得到M2+ 2Mg2+Al3+(O)。The catalyst loads hydrotalcite (LDHs) nanosheets on the surface of graphene (Graphene) by co-precipitation method, and obtains M 2+ 2 Mg 2+ Al 3+ (O) after calcination.

本发明的石墨烯促进水滑石基催化剂的制备方法是首先将一定比例的M2+(Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合)、Mg2+、Al3+的盐溶液与氧化石墨烯胶体溶液混合,金属阳离子静电吸附于氧化石墨烯表面,再在碱性环境下原位生成小粒径、高分散的水滑石纳米片,焙烧后获得相应的催化剂。具体包括下述步骤:The preparation method of the graphene-promoted hydrotalcite-based catalyst of the present invention is to firstly mix a certain proportion of M 2+ (one or more combinations of Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ ), Mg 2 + , Al 3+ salt solution is mixed with graphene oxide colloidal solution, metal cations are electrostatically adsorbed on the surface of graphene oxide, and then small-sized, highly dispersed hydrotalcite nanosheets are generated in situ in an alkaline environment, and obtained after roasting corresponding catalyst. Specifically include the following steps:

(1)石墨的预氧化:依次将浓H2SO4、K2S2O4和P2O5加入到烧瓶中,搅拌下加入石墨粉,最后在60~80oC水浴锅中反应6~8小时,洗涤至中性,干燥、备用;其中石墨:浓H2SO4: K2S2O4: P2O5的质量比为1:4~8:0.5:0.5。(1) Pre-oxidation of graphite: Add concentrated H 2 SO 4 , K 2 S 2 O 4 and P 2 O 5 into the flask in sequence, add graphite powder under stirring, and finally react in a 60-80 o C water bath for 6 ~8 hours, washed to neutral, dried, and set aside; wherein the mass ratio of graphite:concentrated H 2 SO 4 :K 2 S 2 O 4 :P 2 O 5 is 1:4~8:0.5:0.5.

(2)氧化石墨烯的制备:于四口烧瓶中量取浓H2SO4,在0~10oC搅拌条件下依次将预氧化石墨粉和NaNO3 加入到浓 H2SO4 中,并慢慢加入KMnO4,搅拌反应60~90分钟;然后将烧瓶转移至35oC的恒温水浴中,继续搅拌 30~60分钟;最后在搅拌中加入去离子水,控制反应温度于95~98oC之间,继续搅拌30~60分钟;用3% H2O2 30~50ml处理反应液至呈现金黄色,然后趁热过滤,再用 5% HCl 和去离子水充分洗涤至滤液中无 SO42-;其中石墨:浓H2SO4: NaNO3:KMnO4的质量比为1:42:0.5:3,浓H2SO4: H2O的体积比为1:2。(2) Preparation of graphene oxide: measure concentrated H 2 SO 4 in a four-neck flask, add pre-oxidized graphite powder and NaNO 3 to the concentrated H 2 SO 4 in sequence under stirring at 0-10 o C, and Slowly add KMnO 4 , stir and react for 60-90 minutes; then transfer the flask to a constant temperature water bath at 35 o C, and continue stirring for 30-60 minutes; finally add deionized water while stirring, and control the reaction temperature at 95-98 o C, continue to stir for 30-60 minutes; treat the reaction solution with 30-50ml of 3% H 2 O 2 until golden yellow, then filter while hot, and then fully wash with 5% HCl and deionized water until there is no SO4 in the filtrate 2- ; wherein the mass ratio of graphite: concentrated H 2 SO 4 : NaNO 3 : KMnO 4 is 1:42:0.5:3, and the volume ratio of concentrated H 2 SO 4 : H 2 O is 1:2.

(3)M2+ 2Mg2+Al3+(O)催化剂的制备:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌条件下以100W~1000W频率超声0.5~2小时即得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 ~0.021 mol M2+ (NO32·xH2O,M2+是Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合,0.0035~0.0105 mol Mg (NO32·6H2O,0.0035~0.0105 mol Al(NO33·9H2O溶解于100 ml去离子水中并倒入500 ml 氧化石墨烯胶体溶液中,搅拌30~60分钟并辅助超声;再将摩尔比 [Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持30~50分钟,碱液滴加结束时溶液pH稳定在10±0.5;最后65oC晶化4小时,离心、洗涤、60~80oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂表示为M2+ 2Mg2+Al3+(O)。(3) Preparation of M 2+ 2 Mg 2+ Al 3+ (O) catalyst: Transfer 1 g of graphite oxide to a 1L four-neck flask, dilute it with deionized water to 500 ml, and stir at 100W ~1000W frequency ultrasound for 0.5~2 hours to obtain a uniformly dispersed graphene oxide colloidal solution with a mass concentration of 2mg/ml; weigh 0.007~0.021 mol M 2+ (NO 3 ) 2 xH 2 O, M 2+ is One or more combinations of Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ , 0.0035~0.0105 mol Mg (NO 3 ) 2 ·6H 2 O, 0.0035~0.0105 mol Al(NO 3 ) 3 · 9H 2 O was dissolved in 100 ml deionized water and poured into 500 ml graphene oxide colloidal solution, stirred for 30-60 minutes and assisted by ultrasound; then the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 · 9H 2 O]=2, [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye is dropped into the flask and kept for 30-50 minutes, the pH of the solution is stable at 10±0.5 when the lye is added; o C was crystallized for 4 hours, centrifuged, washed, and dried at 60-80 o C, and the product was calcined in a muffle furnace in an air atmosphere at 500 o C for 4 hours to obtain a catalyst expressed as M 2+ 2 Mg 2+ Al 3+ (O).

本发明与现有技术相比具有以下优点和特点:Compared with the prior art, the present invention has the following advantages and characteristics:

(1)以一种简单的合成路线制备了水滑石/石墨烯(LDH/Graphene)复合材料,所得载体稳定性高、易于水滑石纳米片分散、尺寸均一。(1) The hydrotalcite/graphene (LDH/Graphene) composite material was prepared by a simple synthetic route. The obtained carrier has high stability, easy dispersion of hydrotalcite nanosheets and uniform size.

(2)本发明所制得的水滑石基脱硝催化剂尖晶石粒子高度分散、粒径小,且多次循环利用仍然具有很高的NOx储存量(NSC),具有很好的商业应用前景,提供了一种高储存量的水滑石基脱硝催化剂及其制备方法。(2) The spinel particles of the hydrotalcite-based denitration catalyst prepared by the present invention are highly dispersed and small in particle size, and they still have a high NO x storage capacity (NSC) after repeated recycling, and have good commercial application prospects , provide a high-storage hydrotalcite-based denitration catalyst and a preparation method thereof.

附图说明 Description of drawings

图1为实施例1前躯体的SEM谱图。Fig. 1 is the SEM spectrogram of embodiment 1 precursor.

图2为实施例1前躯体的TEM谱图。Fig. 2 is the TEM spectrogram of embodiment 1 precursor.

图3为实施例1前躯体焙烧后所得催化剂Co2+ 2Mg2+Al3+(O)的SEM谱图。Fig. 3 is the SEM spectrogram of the catalyst Co 2+ 2 Mg 2+ Al 3+ (O) obtained after the precursor of Example 1 was roasted.

具体实施方式 Detailed ways

下面结合实施例对本发明做进一步的详细描述,但本发明的实施方式不限于此。The present invention will be further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

实施例1:Example 1:

(1)石墨的预氧化:依次将24 ml浓H2SO4、5 g K2S2O4和5 gP2O5加入到烧瓶中, 搅拌下加入10 g石墨粉,最后在 80oC水浴锅中反应6小时,洗涤至中性,干燥、备用。(1) Pre-oxidation of graphite: add 24 ml of concentrated H 2 SO 4 , 5 g of K 2 S 2 O 4 and 5 g of P 2 O 5 into the flask in turn, add 10 g of graphite powder under stirring, and finally React in a water bath for 6 hours, wash until neutral, dry, and set aside.

(2)氧化石墨烯的制备:于500 ml烧瓶中量取115 ml 浓 H2SO4,在冰水浴中搅拌条件下依次将5 g预氧化石墨粉和2.5 g NaNO3加入到浓 H2SO4 中,并慢慢加入15 g KMnO4,搅拌反应90分钟;然后将烧瓶转移至 35±3oC的恒温水浴中,继续搅拌 30分钟;最后在搅拌中加入230 ml去离子水,控制反应温度低于 98oC,继续搅拌30分钟;用3% H2O2 30ml处理反应液至呈现金黄色,然后趁热过滤,用 5% HCl 和去离子水充分洗涤至滤液中无 SO42-(2) Preparation of graphene oxide: Measure 115 ml of concentrated H 2 SO 4 in a 500 ml flask, add 5 g of pre-oxidized graphite powder and 2.5 g of NaNO 3 to the concentrated H 2 SO 4 under stirring in an ice-water bath 4 , and slowly added 15 g KMnO 4 , stirred for 90 minutes; then transferred the flask to a constant temperature water bath at 35±3 o C, and continued to stir for 30 minutes; finally, added 230 ml of deionized water to control the reaction When the temperature is lower than 98 o C, continue to stir for 30 minutes; treat the reaction solution with 30ml of 3% H 2 O 2 until golden yellow, then filter while hot, and wash thoroughly with 5% HCl and deionized water until there is no SO4 2- in the filtrate .

(3)Co2+ 2Mg2+Al3+(O)催化剂的制备:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 molCo(NO32·6H2O,0.0035mol Mg (NO32·6H2O,0.0035molAl(NO33·9H2O溶解于100 ml去离子水中并倒入氧化石墨烯胶体溶液中,搅拌30分钟并辅以超声;最后将摩尔比 [Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持滴加时间为40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Co2+ 2Mg2+Al3+(O)。(3) Preparation of Co 2+ 2 Mg 2+ Al 3+ (O) catalyst: transfer 1 g of graphite oxide to a 1L four-neck flask, dilute it with deionized water to 500 ml, and ultrasonicate for 1 hour under stirring Obtain a uniformly dispersed graphene oxide colloidal solution with a mass concentration of 2 mg/ml; weigh 0.007 molCo(NO 3 ) 2 6H 2 O, 0.0035 mol Mg (NO 3 ) 2 6H 2 O, 0.0035 molAl(NO 3 ) 3 ·9H 2 O was dissolved in 100 ml deionized water and poured into the graphene oxide colloidal solution, stirred for 30 minutes and assisted by ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 · 9H 2 O]=2, [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye is dropped into the flask, and the time for adding the lye is about 40 minutes. When the lye is added, the pH of the solution is stable at 10; Crystallize at 65 o C for 4 hours, centrifuge, wash, and dry at 60 o C, and roast the product in a muffle furnace in an air atmosphere at 500 o C for 4 hours to obtain the catalyst Co 2+ 2 Mg 2+ Al 3+ (O) .

实施例2:Example 2:

本实施例除下述特征外同实施例1:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.014 molCo(NO32·6H2O,0.007mol Mg (NO32·6H2O,0.007mol Al(NO33·9H2O溶解于100ml去离子水中并倒入氧化石墨烯胶体溶液中,搅拌30分钟并辅以超声;最后将摩尔比[Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持滴加时间为40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Co2+ 2Mg2+Al3+(O)。This embodiment is the same as embodiment 1 except the following features: 1 g of graphite oxide is transferred to a 1L four-necked flask, diluted with deionized water to 500 ml, and ultrasonically stirred for 1 hour to obtain uniformly dispersed graphene oxide Colloidal solution, the mass concentration is 2mg/ml; weigh 0.014 mol Co(NO 3 ) 2 6H 2 O, 0.007 mol Mg (NO 3 ) 2 6H 2 O, 0.007 mol Al(NO 3 ) 3 9H 2 O Dissolved in 100ml deionized water and poured into the graphene oxide colloidal solution, stirred for 30 minutes and supplemented with ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 9H 2 O]=2, [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye is dropped into the flask, and the dropping time is kept for about 40 minutes. When the lye is added, the pH of the solution is stable at 10; finally, it is crystallized at 65 o C for 4 hours , centrifuged, washed, and dried at 60 o C. The product was calcined in a muffle furnace at 500 o C in an air atmosphere for 4 hours to obtain the catalyst Co 2+ 2 Mg 2+ Al 3+ (O).

实施例3:Example 3:

本实施例除下述特征外同实施例1:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.021 molCo(NO32·6H2O,0.0105 mol Mg (NO32·6H2O,0.0105 mol Al(NO33·9H2O溶解于100ml去离子水中并倒入500 ml 氧化石墨烯溶液中,搅拌30分钟并辅以超声;最后将摩尔比[Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持滴加时间为40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Co2+ 2Mg2+Al3+(O)。This embodiment is the same as embodiment 1 except the following features: 1 g of graphite oxide is transferred to a 1L four-necked flask, diluted with deionized water to 500 ml, and ultrasonically stirred for 1 hour to obtain uniformly dispersed graphene oxide Colloidal solution, the mass concentration of which is 2 mg/ml; weigh 0.021 mol Co(NO 3 ) 2 ·6H 2 O, 0.0105 mol Mg (NO 3 ) 2 ·6H 2 O, 0.0105 mol Al(NO 3 ) 3 ·9H 2 O Dissolved in 100ml deionized water and poured into 500 ml graphene oxide solution, stirred for 30 minutes and assisted by ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 9H 2 O]=2 , [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye was dropped into the flask, and the dropping time was kept for about 40 minutes. When the lye was added, the pH of the solution was stable at 10; finally, 65 o C crystallized 4 hours, centrifuged, washed, and dried at 60 o C, and the product was calcined in a muffle furnace at 500 o C in an air atmosphere for 4 hours to obtain the catalyst Co 2+ 2 Mg 2+ Al 3+ (O).

实施例4:Example 4:

本实施例除下述特征外同实施例1:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 molCu(NO32·3H2O,0.0035 mol Mg (NO32·6H2O,0.0035 mol Al(NO33·9H2O溶解于100 ml去离子水中并倒入氧化石墨烯胶体溶液中,搅拌30分钟并辅以超声;最后将摩尔比[Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持滴加时间为40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4 小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Cu2+ 2Mg2+Al3+(O)。This embodiment is the same as embodiment 1 except the following features: 1 g of graphite oxide is transferred to a 1L four-necked flask, diluted with deionized water to 500 ml, and ultrasonically stirred for 1 hour to obtain uniformly dispersed graphene oxide Colloidal solution, the mass concentration is 2 mg/ml; weigh 0.007 mol Cu(NO 3 ) 2 ·3H 2 O, 0.0035 mol Mg (NO 3 ) 2 ·6H 2 O, 0.0035 mol Al(NO 3 ) 3 ·9H 2 O Dissolved in 100 ml deionized water and poured into the graphene oxide colloidal solution, stirred for 30 minutes and assisted by ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 9H 2 O]=2 , [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye was dropped into the flask, and the dropping time was kept for about 40 minutes. When the lye was added, the pH of the solution was stable at 10; finally, 65 o C crystallized 4 hours, centrifuged, washed, and dried at 60 o C, and the product was calcined in a muffle furnace in an air atmosphere at 500 o C for 4 hours to obtain the catalyst Cu 2+ 2 Mg 2+ Al 3+ (O).

实施例5:Example 5:

本实施例除下述特征外同实施例1:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 molNi(NO32·6H2O,0.0035 mol Mg (NO32·6H2O,0.0035 mol Al(NO33·9H2O溶解于100 ml去离子水中并倒入氧化石墨烯胶体溶液中,搅拌30分钟并辅以超声;最后将摩尔比[Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持滴加时间为40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4 小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Ni2+ 2Mg2+Al3+(O)。This embodiment is the same as embodiment 1 except the following features: 1 g of graphite oxide is transferred to a 1L four-necked flask, diluted with deionized water to 500 ml, and ultrasonically stirred for 1 hour to obtain uniformly dispersed graphene oxide Colloidal solution, the mass concentration is 2mg/ml; Weigh 0.007 mol Ni(NO 3 ) 2 ·6H 2 O, 0.0035 mol Mg (NO 3 ) 2 ·6H 2 O, 0.0035 mol Al(NO 3 ) 3 ·9H 2 O Dissolved in 100 ml deionized water and poured into the graphene oxide colloidal solution, stirred for 30 minutes and assisted by ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 9H 2 O]=2 , [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye was dropped into the flask, and the dropping time was kept for about 40 minutes. When the lye was added, the pH of the solution was stable at 10; finally, 65 o C crystallized 4 hours, centrifuged, washed, and dried at 60 o C, and the product was roasted in a muffle furnace at 500 o C in an air atmosphere for 4 hours to obtain the catalyst Ni 2+ 2 Mg 2+ Al 3+ (O).

实施例6:Embodiment 6:

本实施例除下述特征外同实施例1:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌下超声1小时得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 molMn(NO3)2,0.0035mol Mg (NO32·6H2O,0.0035 mol Al(NO33·9H2O溶解于100 ml去离子水中并倒入氧化石墨烯胶体溶液中,搅拌30分钟并辅以超声;最后将摩尔比 [Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持40分钟左右,碱液滴加结束时溶液pH稳定在10;最后65oC晶化4小时,离心、洗涤、60oC烘干,将产物在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂Mn2+ 2Mg2+Al3+(O)。This embodiment is the same as embodiment 1 except the following features: 1 g of graphite oxide is transferred to a 1L four-necked flask, diluted with deionized water to 500 ml, and ultrasonically stirred for 1 hour to obtain uniformly dispersed graphene oxide Colloidal solution, the mass concentration is 2 mg/ml; weigh 0.007 molMn(NO 3 ) 2 , 0.0035 mol Mg (NO 3 ) 2 ·6H 2 O, 0.0035 mol Al(NO 3 ) 3 ·9H 2 O and dissolve in 100 ml Deionized water and poured into the graphene oxide colloidal solution, stirred for 30 minutes and assisted by ultrasound; finally the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 9H 2 O]=2, [NaOH] /[Na 2 CO 3 ]=3.2 The mixed lye was dropped into the flask and kept for about 40 minutes. The pH of the solution was stable at 10 at the end of the lye addition; finally, it was crystallized at 65 o C for 4 hours, centrifuged, washed, and 60 o C drying, the product was calcined in a muffle furnace at 500 o C in an air atmosphere for 4 hours to obtain the catalyst Mn 2+ 2 Mg 2+ Al 3+ (O).

Claims (2)

1.一种石墨烯促进型水滑石基脱硝催化剂,其特征在于,该催化剂的化学式为M2+ 2Mg2+Al3+(O);其中,M2+为Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合,M2+:Mg2+:Al3+的摩尔比为2:1:1;催化剂比表面积为80~110m2/g,孔体积为0.3~0.4 cc/g,孔径分布为介孔分布;1. A graphene-promoted hydrotalcite-based denitration catalyst, characterized in that the chemical formula of the catalyst is M 2+ 2 Mg 2+ Al 3+ (O); wherein, M 2+ is Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ or a combination of several, the molar ratio of M 2+ : Mg 2+ : Al 3+ is 2:1:1; the specific surface area of the catalyst is 80-110m 2 /g, and the pores The volume is 0.3-0.4 cc/g, and the pore size distribution is mesopore distribution; 该催化剂通过共沉淀法将水滑石纳米片负载于石墨烯表面,焙烧后得到。The catalyst is obtained by loading hydrotalcite nanosheets on the surface of graphene through a co-precipitation method and roasting. 2.一种权利要求1所述的石墨烯促进型水滑石基脱硝催化剂的制备方法,其特征在于,包括以下步骤:2. a kind of preparation method of graphene-promoted hydrotalcite-based denitration catalyst according to claim 1, is characterized in that, comprises the following steps: (1)石墨的预氧化:依次将浓H2SO4、K2S2O4和P2O5加入到烧瓶中,搅拌下加入石墨粉,最后在60~80oC水浴锅中反应6~8小时,洗涤至中性,干燥、备用;其中石墨:浓H2SO4: K2S2O4: P2O5的质量比为1:4~8:0.5:0.5;(1) Pre-oxidation of graphite: Add concentrated H 2 SO 4 , K 2 S 2 O 4 and P 2 O 5 into the flask in sequence, add graphite powder under stirring, and finally react in a 60-80 o C water bath for 6 ~8 hours, washed to neutral, dried, and set aside; the mass ratio of graphite:concentrated H 2 SO 4 :K 2 S 2 O 4 :P 2 O 5 is 1:4~8:0.5:0.5; (2)氧化石墨烯的制备:于四口烧瓶中量取浓H2SO4,在0~10oC搅拌条件下依次将预氧化石墨粉和NaNO3 加入到浓 H2SO4 中,并加入KMnO4,搅拌反应60~90分钟;然后将烧瓶转移至35oC的恒温水浴中,继续搅拌 30~60分钟;最后在搅拌中加入去离子水,控制反应温度于95~98oC之间,继续搅拌30~60分钟;用3% H2O2 30~50 ml处理反应液至呈现金黄色,然后趁热过滤,再用 5% HCl 和去离子水充分洗涤至滤液中无 SO42-;其中石墨:浓H2SO4: NaNO3: KMnO4的质量比为1:42:0.5:3,浓H2SO4: H2O的体积比为1:2。(2) Preparation of graphene oxide: measure concentrated H 2 SO 4 in a four-neck flask, add pre-oxidized graphite powder and NaNO 3 to the concentrated H 2 SO 4 in sequence under stirring at 0-10 o C, and Add KMnO 4 , stir and react for 60-90 minutes; then transfer the flask to a constant temperature water bath at 35 o C, and continue stirring for 30-60 minutes; finally add deionized water during stirring, and control the reaction temperature between 95-98 o C Continue stirring for 30-60 minutes; treat the reaction liquid with 30-50 ml of 3% H 2 O 2 until golden yellow, then filter it while it is hot, and wash thoroughly with 5% HCl and deionized water until there is no SO4 2 in the filtrate - ; wherein the mass ratio of graphite: concentrated H 2 SO 4 : NaNO 3 : KMnO 4 is 1:42:0.5:3, and the volume ratio of concentrated H 2 SO 4 : H 2 O is 1:2. (3)M2+ 2Mg2+Al3+(O)催化剂的制备:将1 g氧化石墨转移到到1L四口烧瓶中,用去离子水将其稀释500 ml,在搅拌条件下以100W~1000W频率超声0.5~2小时即得到分散均匀的氧化石墨烯胶体溶液,其质量浓度为2mg/ml;称取0.007 ~0.021 mol M2+ (NO32·xH2O,M2+是Cu2+、Co2+、Ni2+、Mn2+中的一种或几种组合, 0.0035~0.0105 molMg (NO32·6H2O,0.0035~0.0105 mol Al(NO33·9H2O溶解于100 ml去离子水中并倒入500 ml 氧化石墨烯胶体溶液中,搅拌30~60分钟并辅助超声;再将摩尔比 [Na2CO3]/[Al(NO3)3·9H2O]=2,[NaOH]/[Na2CO3]=3.2的混合碱液滴到烧瓶中,保持30~50分钟,碱液滴加结束时溶液pH稳定在10±0.5;最后65oC晶化4小时,离心、洗涤、60~80oC烘干;将产品在马弗炉中500oC空气气氛中焙烧4小时后得到催化剂表示为M2+ 2Mg2+Al3+(O)。(3) Preparation of M 2+ 2 Mg 2+ Al 3+ (O) catalyst: Transfer 1 g of graphite oxide to a 1L four-neck flask, dilute it with deionized water to 500 ml, and stir at 100W ~1000W frequency ultrasound for 0.5~2 hours to obtain a uniformly dispersed graphene oxide colloidal solution with a mass concentration of 2mg/ml; weigh 0.007~0.021 mol M 2+ (NO 3 ) 2 xH 2 O, M 2+ is One or more combinations of Cu 2+ , Co 2+ , Ni 2+ , Mn 2+ , 0.0035~0.0105 molMg (NO 3 ) 2 ·6H 2 O, 0.0035~0.0105 mol Al(NO 3 ) 3 ·9H 2 O was dissolved in 100 ml deionized water and poured into 500 ml graphene oxide colloidal solution, stirred for 30-60 minutes and assisted by ultrasound; then the molar ratio [Na 2 CO 3 ]/[Al(NO 3 ) 3 ·9H 2 O]=2, [NaOH]/[Na 2 CO 3 ]=3.2 The mixed lye is dropped into the flask and kept for 30-50 minutes, the pH of the solution is stable at 10±0.5 when the lye is added ; C was crystallized for 4 hours, centrifuged, washed, and dried at 60-80 o C; the product was calcined in a muffle furnace in an air atmosphere at 500 o C for 4 hours to obtain a catalyst expressed as M 2+ 2 Mg 2+ Al 3+ ( O).
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