CN106669613A - Amino porous carbon dioxide adsorbent and preparation method thereof - Google Patents

Amino porous carbon dioxide adsorbent and preparation method thereof Download PDF

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CN106669613A
CN106669613A CN201710035372A CN201710035372A CN106669613A CN 106669613 A CN106669613 A CN 106669613A CN 201710035372 A CN201710035372 A CN 201710035372A CN 201710035372 A CN201710035372 A CN 201710035372A CN 106669613 A CN106669613 A CN 106669613A
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carbon dioxide
amino
porous carbon
dioxide adsorbent
zsm
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CN201710035372A
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杜涛
王义松
刘丽影
宋延丽
房鑫
张斌
未艺超
周立峰
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东北大学
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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 by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/18Synthetic zeolitic molecular sieves
    • B01J20/186Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C10/00CO2 capture or storage
    • Y02C10/08Capture by adsorption

Abstract

The invention relates to an amino porous carbon dioxide adsorbent and a preparation method thereof. The amino porous carbon dioxide adsorbent is an amino functional material which is obtained by impregnating and modifying synthesized ZSM-5 zeolite by using tetraethylenepentamine. The preparation method comprises the following steps: mixing and stirring tetraethoxysilane, aluminum isopropoxide, tetrapropylammonium hydroxide, sodium chloride and deionized water in proportion; putting a mixed liquid in an oven to remove alcohols; then putting the mixed liquid without alcohols in a polytetrafluoroethylene reaction kettle, and performing crystallization, washing, filtration and drying to obtain ZSM-5 zeolite; mixing and stirring the ZSM-5 zeolite with an ethanol solution of tetraethylenepentamine in a mass ratio; and finally, fully drying the mixed liquid to obtain the amino porous carbon dioxide adsorbent. According to the amino porous carbon dioxide adsorbent and the preparation method thereof, the adsorbent is high in adsorption efficiency and good in selective adsorbability in a range of 60-80 DEG C.

Description

一种氨基多孔二氧化碳吸附剂及其制备方法 A porous adsorbent for carbon dioxide and a preparation method amino

技术领域 FIELD

[0001] 本发明涉及环保技术领域,尤其涉及一种氨基多孔二氧化碳吸附剂及其制备方法。 [0001] The present invention relates to the field of environmental technology, in particular, it relates to an amino porous carbon dioxide adsorbent and its preparation method.

背景技术 Background technique

[0002] 二氧化碳是大气中的一种主要的温室气体,随着世界经济的飞速发展,其工业排放量逐年增长。 [0002] Carbon dioxide is a major greenhouse gases in the atmosphere, with the rapid development of the world economy, its industrial emissions increased year by year. 目前的工业生产中,能源消耗以化石燃烧为主,尤其是锅炉中煤炭的燃烧,通过烟道向大气中排放大量二氧化碳。 The current industrial production, the energy consumption of fossil-based combustion, especially coal burning boiler, a large amount of carbon dioxide emissions into the atmosphere through a stack. 为了减缓全球气候变暖等一系列环境问题,需要对工业烟气中的二氧化碳进行分离和捕获,以达到减少温室气体排放的目的。 In order to slow down a series of environmental problems such as global warming, the need for industrial flue gas carbon dioxide separation and capture, in order to achieve the objective of reducing greenhouse gas emissions.

[0003]目前在分离工业烟气中二氧化碳的众多技术中,吸收分离法与吸附分离法较为成熟。 [0003] Currently many technologies of industrial separation of carbon dioxide in flue gas, the absorbent adsorptive separation separation method and more mature. 吸收分离法最普遍的是使用胺基溶剂,如一乙醇胺、二乙醇胺、甲基二乙醇胺和二异丙醇胺,该方法需要大量的能量消耗,而且使用的胺基溶剂容易腐蚀设备。 The most common method of separation is to use amine absorption solvent, such as monoethanolamine, diethanolamine, methyl diethanolamine and diisopropanolamine, this method requires a large energy consumption, and easy to use amine solvent etching apparatus. 吸附分离法最普遍的是使用常规的物理吸附剂,如活性炭和沸石吸附,其技术更加节能,并有效避免了设备腐蚀问题。 The most common physical adsorption separation method using a conventional adsorbent, such as activated carbon and zeolite adsorbent which more energy efficient technology, and to avoid corrosion problems the device. 沸石对极性分子(如二氧化碳)具有高的亲和力,因此沸石被认为是较为适合吸附二氧化碳的固体吸附剂。 Zeolites have a high affinity for polar molecules (such as carbon dioxide), and therefore is considered to be more suitable zeolite adsorbent solid carbon dioxide. 但针对工业烟气温度较高和二氧化碳分压较低的特点,其固有的孔结构和物理吸附的性质不能满足在该工业环境下的应用。 However, for industrial flue gas temperatures and higher carbon dioxide partial pressure lower features, applications in the industrial environment and its inherent pore structure can not meet the physical adsorption properties.

[0004]因此,亟需发明一种可以在工业烟气温度下,仍然具有较强的吸附性能,并且有较高的二氧化碳选择吸附性的二氧化碳吸附剂。 [0004] Accordingly, the need to invent a possible industrial flue gas temperature, still has strong adsorption performance, and a higher carbon dioxide adsorbent of choice.

[0005] ZSM-5型沸石具有更薄的孔壁,更丰富的孔结构。 [0005] ZSM-5 type zeolite having thinner cell walls, more extensive pore structure. 将氨基引入ZSM-5型沸石中可以提高其在较高温度下的吸附性能,并提高其二氧化碳选择吸附性。 The amino group introduced into ZSM-5 type zeolite adsorption performance can be improved at a higher temperature, and to increase their carbon dioxide selective adsorbent.

发明内容 SUMMARY

[0006](一)要解决的技术问题 [0006] (a) To solve technical problems

[0007] 为了解决现有技术的上述问题,本发明提供一种能够在工业烟气温度下,具有高吸附效率和较高二氧化碳选择吸附性的氨基多孔二氧化碳吸附剂及其制备方法,以解决现有技术的二氧化碳吸附剂在此温度范围内吸附效率低的问题。 [0007] In order to solve the aforementioned problems of the prior art, the present invention provides a flue gas temperature at the industrial, porous carbon dioxide adsorbent having an amino group and preparation method high adsorption efficiency and a higher carbon dioxide selective adsorbent to address now problem of low efficiency of adsorbing carbon dioxide adsorbent art within this temperature range.

[0008] (二)技术方案 [0008] (ii) Technical Solution

[0009] 为了达到上述目的,本发明采用的主要技术方案包括: [0009] To achieve the object, the main aspect of the present invention include:

[0010] 本发明提供一种氨基多孔二氧化碳吸附剂,该氨基多孔二氧化碳吸附剂是使用四乙烯五胺对合成的ZSM-5型沸石进行浸渍改性所得到的氨基功能化吸附材料。 [0010] The present invention provides an amino porous carbon dioxide adsorbent, the carbon dioxide adsorbent is a porous amino tetraethylene pentamine using the synthesized ZSM-5 type zeolite adsorbent amino functionalized Impregnated obtained.

[0011] 根据本发明,使用四乙烯五胺的乙醇溶液对合成的ZSM-5型沸石进行浸渍改性。 [0011] According to the present invention, using an ethanol solution of tetraethylene pentamine synthesis of ZSM-5 type zeolite Impregnated.

[0012] 根据本发明,氨基多孔二氧化碳吸附剂在温度60 0C -80 0C吸附,在温度100 °C _120°c脱附再生。 [0012] According to the present invention, the porous carbon dioxide adsorbent amino temperature 60 0C -80 0C adsorption, the regeneration at a temperature of 100 ° C _120 ° c desorption.

[0013] 本发明提供一种氨基多孔二氧化碳吸附剂的制备方法,具体包括以下步骤: [0013] The present invention provides a method of preparing a porous carbon dioxide adsorbent is an amino, includes the following steps:

[0014] S1:将ZSM-5型沸石与四乙烯五胺的乙醇溶液按一定质量比混合,搅拌0.5-3小时; [0014] S1: The ethanol solution of ZSM-5 type zeolite and tetraethylenepentamine according to a certain ratio of mass, stirred for 0.5-3 hours;

[0015] S2:将SI制得的混合液放入烘箱中,充分干燥后得到氨基多孔二氧化碳吸附剂。 [0015] S2: The obtained mixed SI put in an oven, and dried to give the amino sufficiently porous carbon adsorbent.

[0016] 根据本发明,在SI之前,还包括以下步骤: [0016] According to the present invention, prior to the SI, further comprising the step of:

[0017] Sll:将正硅酸乙酯、异丙醇铝、四丙基氢氧化铵、氯化钠和去离子水按比例充分混合,在室温下搅拌; [0017] Sll: The tetraethyl orthosilicate, aluminum isopropoxide, tetrapropyl ammonium hydroxide, sodium chloride, and deionized water were mixed in proportion, stirred at room temperature;

[0018] S12:将SI I制得的混合液放入烘箱中进行除醇; [0018] S12: The SI I obtained mixture was put in an oven for addition to an alcohol;

[0019] S13:将S12的混合液放入聚四氟乙烯反应釜中,在165 °C下晶化,然后反复洗涤,过滤和干燥后得到ZSM-5型沸石。 [0019] S13: S12 The mixture was placed in a Teflon autoclave, at 165 ° C crystallization, and then washed repeatedly, filtered, and dried to obtain a ZSM-5 type zeolite.

[0020] 根据本发明,SI中的ZSM-5型沸石与四乙烯五胺的质量比为1: 0.3_0.9。 [0020] The mass ratio of 1 of the present invention, ZSM-5 type zeolite with an SI of tetraethylene pentamine: 0.3_0.9.

[0021] 根据本发明,S2中烘箱的温度为40-80°C。 [0021] According to the invention, S2 in an oven at a temperature of 40-80 ° C.

[0022] 根据本发明,Sll中的正硅酸乙酯、异丙醇铝、四丙基氢氧化铵、氯化钠和去离子水的摩尔比为25-1000:1:9:1: 300-600 ; SI I中搅拌的时间为6_24小时。 [0022] The molar ratio of the present invention, the TEOS Sll, aluminum isopropoxide, tetrapropyl ammonium hydroxide, sodium chloride, and deionized water is 25-1000: 1: 9: 1: 300 -600; SI I 6_24 stirring time is hours.

[0023] 根据本发明,S12中除醇的温度为60_80°C,时间为1-4小时。 [0023] According to the present invention, the temperature in addition to alcohols S12 60_80 ° C, the time is 1-4 hours.

[0024] 根据本发明,S13中晶化的时间为12-72小时。 [0024] According to the present invention, S13 in crystallization time is 12-72 hours.

[0025](三)有益效果 [0025] (c) beneficial effect

[0026] 本发明的有益效果是: [0026] Advantageous effects of the present invention are:

[0027]四乙烯五胺作为ZSM-5型沸石的氨基功能化改性的物质,成本低、毒性低、二氧化碳吸附能力高,其较高密度的氨基和较少粘性的性质,提供了更多的用于相互作用的反应位点。 [0027] tetraethylenepentamine as the amino-functionalized modified ZSM-5 type zeolite material, low cost, low toxicity, high carbon dioxide adsorption capacity, amino and less viscous nature of its higher density, providing more reactive site for interaction.

[0028] 本发明的氨基多孔二氧化碳吸附剂,充分发挥了ZSM-5型沸石的孔结构体系优势,在其氨基功能化改性后提高了在60°C-80°C范围内对二氧化碳的吸附效率和选择吸附性,并且,该吸附剂在100°C-120°C脱附再生,再生过程能耗小,再生性能好。 [0028] amino porous carbon adsorbent of the present invention, full advantage of the architecture pore structure of ZSM-5 type zeolite, in which the amino functional modification improves the adsorption of carbon dioxide at 60 ° C-80 ° C range and selective adsorption efficiency, and the adsorbent at 100 ° C-120 ° C desorption regeneration, regeneration of small power consumption, good regeneration properties.

[0029] 本发明的氨基多孔二氧化碳吸附剂的制备方法,原料成本低、工艺简单易行,所制得的氨基多孔二氧化碳吸附剂在60°C-8(TC范围内对二氧化碳吸附能力较强,此温度区间为燃煤锅炉的烟气经脱硫工艺后的排烟温度范围,因此无需对烟气进行降温处理,减少了脱碳设备改造的成本。 [0029] The method of preparing a porous carbon dioxide adsorbent amino group of the present invention, a low raw material cost, simple and easy process, an amino porous carbon dioxide adsorbent prepared in a 60 ° C-8 (the range of the TC strong adsorption capacity for carbon dioxide, this temperature range is a temperature range of exhaust gas after flue gas desulfurization of coal-fired boilers, it is not necessary to cool the flue gas treatment, reducing the cost of equipment modification decarburization.

附图说明 BRIEF DESCRIPTION

[0030]图1为本发明实施例一中ZT5的吸附动力学曲线; [0030] FIG. 1 in an embodiment the adsorption kinetics data ZT5 embodiment of the invention;

[0031]图2为本发明实施例二中ZT7的吸附动力学曲线; [0031] FIG. 2 shows the adsorption kinetics ZT7 the second embodiment of the invention;

[0032]图3为本发明实施例中的ZT5和ZT7的X射线衍射分析(XRD)谱图; [0032] FIG Example 3 X-ray diffraction analysis of the ZT5 and ZT7 (XRD) spectra of embodiments of the present invention;

[0033]图4为本发明实施例中的ZT5和ZT7的傅里叶红外光谱分析(FT-1R)谱图。 [0033] The embodiment of FIG. 4 and ZT7 ZT5 Fourier infrared spectroscopy (FT-1R) spectrum of embodiments of the present invention.

具体实施方式 Detailed ways

[0034] 为了更好的解释本发明,以便于理解,下面结合附图,通过具体实施方式,对本发明作详细描述。 [0034] To better explain the present invention in order to be understood in conjunction with the following drawings, by way of specific embodiments, the present invention is described in detail.

[0035]首先将正硅酸乙脂、异丙醇铝、四丙基氢氧化铵、氯化钠和去离子水按摩尔比为25-1000:1:9:1: 300-600充分混合,在室温下搅拌6-24小时后,放入60°C_80°C的烘箱中除醇1-4小时。 [0035] First, tetraethyl orthosilicate, aluminum isopropoxide, tetrapropyl ammonium hydroxide, sodium chloride, and deionized water is 25-1000 molar ratio: 1: 9: 1: 300-600 thoroughly mixed, after stirring at room temperature for 6-24 hours, into a 60 ° C_80 ° C oven for 1-4 hours, in addition to the alcohol. 然后将该混合液放入聚四氟乙烯反应釜中,在165°C下晶化12-72小时,然后反复洗涤,过滤和干燥后得到固体粉末,即ZSM-5型沸石。 The mixture was then placed in a Teflon autoclave, crystallization at 165 ° C 12-72 hours and then washed repeatedly, filtered, and dried to obtain a solid powder, i.e. ZSM-5 type zeolite. 再将ZSM-5型沸石与四乙烯五胺的乙醇溶液混合后搅拌0.5-3小时,ZSM-5型沸石与四乙烯五胺的质量比为I:0.3-0.9。 After stirring and then mixing the ZSM-5 type zeolite tetraethylenepentamine ethanol solution for 0.5-3 hours, the quality of ZSM-5 type zeolite and tetraethylenepentamine ratio of I: 0.3-0.9. 最后将得到的混合液放入温度为40°C-80°C的烘箱中,充分干燥后得到所需的吸附剂。 Finally, the resulting mixture was placed in a temperature of 40 ° C-80 ° C in the oven was thoroughly dried to yield the desired adsorbent.

[0036] 进一步,本发明的氨基多孔二氧化碳吸附剂不仅可以用于气体中二氧化碳的吸附分离,也可以作为其他更广泛领域的吸附剂,例如对液体中重金属离子和染料等污染物的吸附,但相比之下,对于气体中的二氧化碳的吸附分离作用更好。 [0036] Further, amino porous carbon dioxide adsorbent may be used in the present invention is not adsorptive separation of carbon dioxide gas, it may be used as an adsorbent other broader field, such as adsorption of contaminants in the liquid heavy metal ions and dyes, etc., but in contrast, for separating action of carbon dioxide gas is adsorbed better.

[0037] 进一步,本发明的氨基多孔二氧化碳吸附剂在100°C以下都可以进行对二氧化碳的吸附分离,但本发明特别是针对燃煤锅炉中烟气的二氧化碳的吸收具有更好的效果,燃煤锅炉中的烟气经脱硫工艺后的排烟温度范围为60°C-8(TC左右,经过实验得出,本发明的氨基多孔二氧化碳吸附剂在温度为60°C-8(TC时的吸附效果最好。 [0037] Further, amino porous carbon dioxide adsorbent in the present invention is below 100 ° C can be adsorptive separation of carbon dioxide, but the present invention is in particular a better performance for the coal-fired boiler flue gas in the absorption of carbon dioxide, fuel coal boiler flue gas temperature range of the flue gas desulfurization process is about 60 ° C-8 (TC, obtained through experiments, the present invention is an amino porous carbon adsorbent at a temperature of 60 ° C-8 (the time TC best adsorption effect.

[0038] 进一步,本发明的氨基多孔二氧化碳吸附剂在100°C-120°C下脱附再生,再生过程能耗小,再生性能好。 [0038] Further, the present invention is an amino porous carbon dioxide adsorbent desorption regeneration at 100 ° C-120 ° C, a small energy regeneration, regeneration performance is good.

[0039] 实施例一 [0039] Example a

[0040] 首先将26.04g的正硅酸乙脂、1.02g的异丙醇铝、36.61g的四丙基氢氧化铵(25wt %水溶液)和0.29g氯化钠充分混合,在室温下搅拌12小时后,放入80 V的烘箱中除醇2小时。 [0040] First, 26.04g of TEOS, 1.02g of aluminum isopropoxide, 36.61g of tetrapropyl ammonium hydroxide (25wt% aqueous solution) 0.29 g of sodium chloride, and sufficiently mixed and stirred at room temperature for 12 after hours, placed in an oven to 80 V in addition to the alcohol for 2 hours. 然后将该混合液放入聚四氟乙烯反应釜中,在165°C下晶化24小时,然后反复洗涤,过滤和干燥后得到ZSM-5型沸石。 The mixture was then placed in a Teflon autoclave, crystallization at 165 ° C 24 hours, then washed repeatedly, filtered, and dried to obtain a ZSM-5 type zeolite. 再将制得的ZSM-5型沸石与四乙烯五胺的乙醇溶液混合后搅拌I小时,ZSM-5型沸石与四乙烯五胺的质量比为1: 0.5。 After stirring and then mixing the resulting ZSM-5 type zeolite and tetraethylenepentamine I hour in ethanol, the mass ratio of ZSM-5 type zeolite with tetraethylenepentamine was 1: 0.5. 最后将得到的混合液放入温度为80°C的烘箱中,充分干燥后得到所需的吸附剂。 Finally, the resulting mixture was placed in a temperature of the oven to 80 ° C, thoroughly dried to give the desired adsorbent. 按上述ZSM-5型沸石与四乙烯五胺的比例定义该吸附剂名称为ZT5。 The adsorbent is defined by the ratio of the name ZSM-5 type zeolite and tetraethylenepentamine is ZT5.

[0041] 实施例二 [0041] Second Embodiment

[0042] 首先将104.16g的正硅酸乙脂、1.02g的异丙醇铝、36.61g的四丙基氢氧化铵(25wt %水溶液)和0.29g氯化钠充分混合,在室温下搅拌24小时后,放入60 V的烘箱中除醇4小时。 [0042] First, the TEOS 104.16g, 1.02g of aluminum isopropoxide, 36.61g of tetrapropyl ammonium hydroxide (25wt% aqueous solution) 0.29 g of sodium chloride, and sufficiently mixed and stirred at room temperature for 24 after hours, placed in an oven at 60 V, in addition to the alcohol for 4 hours. 然后将该混合液放入聚四氟乙烯反应釜中,在165°C下晶化72小时,然后反复洗涤,过滤和干燥后得到ZSM-5型沸石。 The mixture was then placed in a Teflon autoclave, crystallization at 165 ° C 72 hours, then washed repeatedly, filtered, and dried to obtain a ZSM-5 type zeolite. 再将ZSM-5型沸石与四乙烯五胺的乙醇溶液混合后搅拌I小时,ZSM-5型沸石与四乙烯五胺的质量比为1:0.7。 After stirring and then mixing the ZSM-5 type zeolite tetraethylenepentamine ethanol solution of I hour, the mass ratio of ZSM-5 type zeolite with tetraethylenepentamine was 1: 0.7. 最后将得到的混合液放入温度为50°C的烘箱中,充分干燥后得到所需的吸附剂。 Finally, the resulting mixture was placed in a temperature oven at 50 ° C, thoroughly dried to give the desired adsorbent. 按上述ZSM-5型沸石与四乙烯五胺的比例定义该吸附剂名称为ZT7。 The adsorbent is defined by the ratio of the name ZSM-5 type zeolite and tetraethylenepentamine is ZT7.

[0043]图1的吸附动力学曲线由热重分析仪测量得到。 Adsorption kinetics [0043] FIG. 1 is obtained by a thermogravimetric analyzer. 先向仪器中通入流量为30ml/min的氩气,并将实施例一中得到的ZT5加热至100°C持续I小时来进行预处理。 Xianxiang instrument into flow 30ml / min of argon, and the first embodiment ZT5 obtained was heated to 100 ° C continued for I hour pretreatment. 然后将ZT5冷却至一定的测量温度下,通入流量为30ml/min的二氧化碳气体。 ZT5 then cooled to a certain lower measured temperature, was introduced at a flow 30ml / min of carbon dioxide gas. 随着二氧化碳被ZT5所吸附,ZT5的质量会随时间增加。 As the carbon dioxide is adsorbed ZT5, ZT5 quality increases with time. 某时刻下,ZT5增加的质量即为其二氧化碳吸附量,由此得到图1的吸附动力学曲线。 At a certain time, i.e. their mass ZT5 in the increased adsorption amount of carbon dioxide, thereby obtaining a graph of the adsorption kinetics.

[0044]图2的吸附动力学曲线由热重分析仪测量得到。 Adsorption kinetics [0044] FIG 2 is obtained by a thermogravimetric analyzer. 先向仪器中通入流量为30ml/min的氩气,并将实施例二中得到的ZT7加热至100°C持续I小时来进行预处理。 Xianxiang instrument into flow 30ml / min of argon, and the second embodiment ZT7 obtained was heated to 100 ° C continued for I hour pretreatment. 然后将ZT7冷却至一定的测量温度下,通入流量为30ml/min的二氧化碳气体。 Then cooled to a certain lower ZT7 measured temperature, was introduced at a flow 30ml / min of carbon dioxide gas. 随着二氧化碳被ZT7所吸附,ZT7的质量会随时间增加。 As the carbon dioxide is adsorbed ZT7, ZT7 quality increases with time. 某时刻下,ZT7增加的质量即为其二氧化碳吸附量,由此得到图2的吸附动力学曲线。 At a certain moment, ZT7 i.e. their mass increased adsorption amount of carbon dioxide, thereby obtaining a graph showing adsorption kinetics of two.

[0045] 参照图1、图2,相同温度的条件下,ZT7的二氧化碳吸附量比ZT5的大;对于同一实施例制得的二氧化碳吸附剂,较高温度下二氧化碳的吸附量比较低温度下二氧化碳的吸附量大;ZT5和ZT7都是在时间大约为0min-5min时,二氧化碳吸附量的增长速度很快,之后二氧化碳吸附量的增长缓慢。 [0045] Referring to FIG. 1, 2, under the same conditions of temperature, carbon dioxide adsorption ratio of ZT5 FIG ZT7 large; carbon dioxide adsorbents obtained in the same embodiment, the adsorption temperature of carbon dioxide is lower than the temperature of carbon dioxide at higher the adsorption capacity; ZT5 in the time and ZT7 are at about 0min-5min, the adsorption of carbon dioxide growing fast, then slow growth of carbon dioxide adsorption.

[0046] 参照图3,其中,横坐标2-Theta-Scale是指衍射角,纵坐标intensity是指衍射峰的强度。 [0046] Referring to FIG 3, wherein the 2-Theta-Scale abscissa refers to a diffraction angle, the ordinate refers to the intensity of the diffraction peak. 由图3所见,2Θ = 7.9,8.9,23.3,24.0,4.5是ZSM-5型沸石的特征峰,说明该沸石被浸渍改性后仍具有ZSM-5型沸石的晶体结构。 Seen from FIG. 3, 2Θ = 7.9,8.9,23.3,24.0,4.5 characteristic peak is ZSM-5 type zeolite, after the zeolite is impregnated described modified still has a crystal structure of ZSM-5 type zeolite.

[0047] 参照图4,其中,横坐标wavenumber是指波数,表示吸收峰的位置,纵坐标transmiss1n是指透过率,表示吸收强度。 [0047] Referring to Figure 4, where the abscissa is the number of wavenumber wave indicates the position of the absorption peak, the ordinate refers to the transmittance transmiss1n, represents absorption intensity. 由图4所见,波数为2933cm—1,2814cm—1,1563cm-1和1470cm—1的震动峰与制得的二氧化碳吸附剂被四乙烯五胺改性有关。 Seen from FIG. 4, the wave number of the carbon dioxide adsorbent is manufactured by vibration peak 2933cm-1,2814cm-1,1563cm-1 and 1470cm-1 is obtained is about tetraethylenepentamine modified. 其中波数为2933cm一1和2814cm—1处的伸缩震动峰是由于存在CH2CH2CH2-NH2基团中的C-H2,而在波数为1563cm—1和1470cm—1处的震动峰是由于与伯胺基团(RNH2)中的N-H2相关。 Wherein wavenumber telescoping a 1 2814cm-1 at and 2933cm vibration peaks are due to C-H2 CH2CH2CH2-NH2 radicals, and the wavenumber 1563cm-1 vibration peaks and 1470cm-1 at is due to primary amine group (RNH2,) is related to N-H2.

[0048]综上,本发明的氨基多孔二氧化碳吸附剂,充分发挥了 ZSM-5型沸石的孔结构体系优势,在其氨基功能化改性后提高了在60 0C-80 °C范围内对二氧化碳的吸附效率和选择吸附性,并且,该吸附剂在100°C-12(TC脱附再生,再生过程能耗小,再生性能好;本发明的氨基多孔二氧化碳吸附剂的制备方法,原料成本低、工艺简单易行,所制得的氨基多孔二氧化碳吸附剂在60°C-8(TC范围内对二氧化碳吸附能力较强,此温度区间为燃煤锅炉的烟气经脱硫工艺后的排烟温度范围,因此无需对烟气进行降温处理,减少了脱碳设备改造的成本。 [0048] In summary, amino porous carbon dioxide adsorbent present invention, full advantage of the architecture pore structure of ZSM-5 type zeolite, in which the amino functional modification increases the carbon dioxide in 60 0C-80 ° C range the selective adsorption and adsorption efficiency, and the adsorbent at 100 ° C-12 (TC desorption regeneration, the regeneration process is less energy consumption, better performance regeneration; amino preparing a porous carbon dioxide adsorbent of the present invention, the low cost of raw materials , simple and easy process, an amino prepared porous carbon dioxide adsorbent in the 60 ° C-8 (TC range for carbon dioxide adsorption ability, this temperature range is the temperature of exhaust gas after flue gas desulfurization of coal-fired boiler range, eliminating the need for flue gas temperatures, and reduce the cost of equipment modification of decarbonization.

[0049]需要理解的是,以上对本发明的具体实施例进行的描述只是为了说明本发明的技术路线和特点,其目的在于让本领域内的技术人员能够了解本发明的内容并据以实施,但本发明并不限于上述特定实施方式。 [0049] is to be understood that the above description of specific embodiments of the present invention is only to illustrate the technical route and features of the invention, its object is to allow those skilled in the art to understand the present invention and accordingly embodiment, However, the present invention is not limited to the specific embodiments. 凡是在本发明权利要求的范围内做出的各种变化或修饰,都应涵盖在本发明的保护范围内。 Those who make various changes or modifications within the scope of the claimed invention should fall within the protection scope of the present invention.

Claims (10)

1.一种氨基多孔二氧化碳吸附剂,其特征在于: 所述氨基多孔二氧化碳吸附剂是使用四乙烯五胺对合成的ZSM-5型沸石进行浸渍改性所得到的氨基功能化吸附材料。 An amino porous carbon dioxide adsorbent, characterized in that: said carbon dioxide adsorbent is a porous amino tetraethylenepentamine use of ZSM-5 type zeolite synthesis is an amino functionalized Impregnated adsorbent obtained.
2.如权利要求1所述的氨基多孔二氧化碳吸附剂,其特征在于: 使用所述四乙烯五胺的乙醇溶液对所述合成的ZSM-5型沸石进行浸渍改性。 2-amino-porous carbon dioxide adsorbent according to claim 1, characterized in that: the ethanol solution of tetraethylene pentamine of the ZSM-5 type synthetic zeolite Impregnated.
3.如权利要求1所述的氨基多孔二氧化碳吸附剂,其特征在于: 所述氨基多孔二氧化碳吸附剂在温度60°C-80°C吸附,在温度100°C-120°C脱附再生。 Amino porous carbon dioxide adsorbent according to claim 1, wherein: the amino porous carbon dioxide adsorbent at a temperature of 60 ° C-80 ° C adsorption, the regeneration at a temperature of 100 ° C-120 ° C desorption.
4.一种氨基多孔二氧化碳吸附剂的制备方法,其特征在于,具体包括以下步骤: S1:将ZSM-5型沸石与四乙烯五胺的乙醇溶液按一定质量比混合,搅拌0.5-3小时; S2:将所述SI制得的混合液放入烘箱中,充分干燥后得到所述氨基多孔二氧化碳吸附剂。 4. A method of preparing a porous carbon dioxide adsorbent is amino, characterized in that includes the following steps: S1: The ethanol solution of ZSM-5 type zeolite and tetraethylenepentamine according to a certain ratio of mass, stirred for 0.5-3 hours; S2: the SI obtained mixed into the oven, thoroughly dried to give the amino porous carbon dioxide adsorbent.
5.如权利要求4所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于,在所述SI之前,还包括以下步骤: Sll:将正硅酸乙酯、异丙醇铝、四丙基氢氧化铵、氯化钠和去离子水按比例充分混合,在室温下搅拌; S12:将所述SI I制得的混合液放入烘箱中进行除醇; S13:将所述S12的混合液放入聚四氟乙烯反应釜中,在165°C下晶化,然后反复洗涤,过滤和干燥后得到ZSM-5型沸石。 5. Preparation of 4-amino-porous carbon dioxide adsorbent according to claim, wherein, prior to said the SI, further comprising the step of: Sll: The tetraethyl orthosilicate, aluminum isopropoxide, tetrapropyl ammonium hydroxide, sodium chloride, and deionized water were mixed in proportion, stirred at room temperature; S12: the SI I obtained mixture was put in an oven for other alcohols; S13: S12 of the mixture placed in a Teflon autoclave, at 165 ° C crystallization, and then washed repeatedly, filtered, and dried to obtain a ZSM-5 type zeolite.
6.如权利要求4所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于: 所述SI中的ZSM-5型沸石与四乙烯五胺的质量比为1: 0.3-0.9。 6. Preparation of 4-amino-porous carbon dioxide adsorbent according to claim, wherein: the quality of the ZSM-5 type zeolite in the SI and tetraethylenepentamine ratio of 1: 0.3-0.9.
7.如权利要求4所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于: 所述S2中的烘箱温度为40-80 0C。 7. A method of preparing a porous carbon adsorbent amino claim 4, wherein: the oven temperature S2 is 40-80 0C.
8.如权利要求5所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于: 所述Sll中的正硅酸乙酯、异丙醇铝、四丙基氢氧化铵、氯化钠和去离子水的摩尔比为25-1000:1:9:1:300-600; 所述S11中搅拌的时间为6-24小时。 8. A method of preparing a porous carbon dioxide adsorbent amino group according to claim 5, wherein: said tetraethylorthosilicate in Sll, aluminum isopropoxide, tetrapropyl ammonium hydroxide, sodium chloride, and to molar ratio of deionized water is 25-1000: 1: 9: 1: 300-600; S11, the stirring time is 6-24 hours.
9.如权利要求5所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于: 所述S12中除醇的温度为60-80 °C,时间为1-4小时。 Amino preparing a porous carbon dioxide adsorbent according to claim 5, wherein: the temperature of the S12, in addition to alcohol is 60-80 ° C, the time is 1-4 hours.
10.如权利要求5所述的氨基多孔二氧化碳吸附剂的制备方法,其特征在于: 所述S13中晶化的时间为12-72小时。 Amino preparing a porous carbon dioxide adsorbent according to claim 5, characterized in that: in S13 crystallization time is 12-72 hours.
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