CN118062825A - A granular carbon molecular sieve capable of screening ethylene/ethane and its preparation method and application - Google Patents

A granular carbon molecular sieve capable of screening ethylene/ethane and its preparation method and application Download PDF

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CN118062825A
CN118062825A CN202410184557.9A CN202410184557A CN118062825A CN 118062825 A CN118062825 A CN 118062825A CN 202410184557 A CN202410184557 A CN 202410184557A CN 118062825 A CN118062825 A CN 118062825A
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ethylene
ethane
molecular sieve
granular carbon
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周欣
周道浩
李忠
罗皓元
夏启斌
梁祎然
赵亚鹏
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South China University of Technology SCUT
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    • 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
    • B01D53/04Separation 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 with stationary adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

本发明公开了一种可筛分乙烯/乙烷的颗粒炭分子筛及其制备方法与应用,该制备方法包括如下步骤:(1)将生物质碳源颗粒破碎,筛选目标粒度尺寸的颗粒,用一定浓度的盐溶液浸渍、过滤、烘干,然后在N2氛围和一定温度下,将颗粒炭进行初步的热解和碳化,制得具有一定结构和化学组成的碳前驱体,并冷却至室温;(2)将经过热解和碳化后得到的颗粒炭放置在C4烯烃混合气体中进行吸附;(3)将多孔炭材料加热,制得到能对乙烯/乙烷进行分子筛分分离的颗粒炭分子筛。

The present invention discloses a granular carbon molecular sieve capable of screening ethylene/ethane, and a preparation method and application thereof. The preparation method comprises the following steps: (1) crushing biomass carbon source particles, screening particles of target particle size, impregnating with a salt solution of a certain concentration, filtering, and drying, and then preliminarily pyrolyzing and carbonizing the granular carbon in a N2 atmosphere and at a certain temperature to obtain a carbon precursor with a certain structure and chemical composition, and cooling to room temperature; (2) placing the granular carbon obtained after pyrolysis and carbonization in a C4 olefin mixed gas for adsorption; and (3) heating the porous carbon material to obtain a granular carbon molecular sieve capable of molecular screening and separation of ethylene/ethane.

Description

一种可筛分乙烯/乙烷的颗粒炭分子筛及其制备方法与应用A granular carbon molecular sieve capable of screening ethylene/ethane and its preparation method and application

技术领域Technical Field

本发明属于颗粒炭分子筛制备领域,具体涉及一种可分子筛分乙烯/乙烷的颗粒炭分子筛及其制备方法与应用。The invention belongs to the field of preparation of granular carbon molecular sieves, and in particular relates to a granular carbon molecular sieve capable of molecularly sieving ethylene/ethane, and a preparation method and application thereof.

背景技术Background technique

乙烯是全球最大宗的基本有机化学品,2022年全球乙烯总产能达到2.18亿吨/年,我国也是全球最大的乙烯生产国。乙烯及其衍生物以占据石化产品的70%,乙烯的生产和利用水平被认为是衡量一个国家石油化工发展水平的重要标志。Ethylene is the world's largest basic organic chemical. In 2022, the global ethylene production capacity will reach 218 million tons/year. my country is also the world's largest ethylene producer. Ethylene and its derivatives account for 70% of petrochemical products. The production and utilization level of ethylene is considered an important indicator of a country's petrochemical development level.

乙烯作为化工原料进行后续的加工生产,需要达到一定的纯度。以生产聚乙烯为例,原料乙烯需要达到99.95%以上的纯度。工业上生产乙烯通常是由石脑油和蒸汽高温裂解产生,产物中不可避免产生未反应完全的乙烷杂质,因此需要进一步分离纯化以制备聚合纯乙烯。目前对于乙烯的提纯主要采用高压低温精馏工艺。由于主要的杂质是乙烷,并且乙烯和乙烷的物理性质接近,采用高压低温精馏分离工艺能耗很高,分离成本占据了总生产成本的70%。因此,急需开发一种能在常温下高效低能耗的乙烯/乙烷分离技术。Ethylene needs to reach a certain purity for subsequent processing and production as a chemical raw material. Taking the production of polyethylene as an example, the raw material ethylene needs to reach a purity of more than 99.95%. Industrial production of ethylene is usually produced by high-temperature cracking of naphtha and steam. In the product, unreacted ethane impurities are inevitably produced, so further separation and purification are required to prepare polymerized pure ethylene. At present, the purification of ethylene mainly adopts high-pressure and low-temperature distillation process. Since the main impurity is ethane, and the physical properties of ethylene and ethane are similar, the high-pressure and low-temperature distillation separation process has high energy consumption, and the separation cost accounts for 70% of the total production cost. Therefore, it is urgent to develop an ethylene/ethane separation technology that can be efficient and energy-saving at room temperature.

吸附分离技术可实现常温常压下的乙烯/乙烷分离,与高压低温精馏技术相比,分离能耗可降低75%。吸附材料是关键。然而乙烯和乙烷的动力学直径分别是两者的差值仅为/>分离的难度明显高于分离丙烯和丙烷(/>)。因此对于乙烯/乙烷的筛分分离需要更狭窄的孔隙结构以及更加集中的孔径分布。目前,有几个金属-有机框架(MOFs),负载银的沸石分子筛和微孔炭材料已被报道具有筛分乙烯/乙烷的性能。然而,要成为工业吸附剂,吸附材料必须同时满足具有良好的稳定性、优异选择性、高吸附容量,容易颗粒成型和低的制备成本的要求。目前的MOFs材料大部分不稳定,且成本很高;沸石分子筛分离烯烃易积碳,循环稳定性不好;Du等以多巴胺为原料,实现了多孔炭材料对于乙烯/乙烷的完全筛分分离(Du S,Huang J,Ryder M,etal.Probing sub-5Angstrom micropores in carbon for precise light olefin/paraffin separation[J].Nat Commun,2023,14(1):1197.)。然而,这种碳分子筛主要是选用价格昂贵的多巴胺为碳源,所得的样品粉末状的,不具备可直接工业应用特性。若通过添加粘合剂成型,会降低吸附容量,并且由此产生次生孔导致选择性下降。Adsorption separation technology can achieve ethylene/ethane separation at room temperature and pressure. Compared with high-pressure and low-temperature distillation technology, separation energy consumption can be reduced by 75%. Adsorption materials are the key. However, the kinetic diameters of ethylene and ethane are and The difference between the two is only The difficulty of separation is significantly higher than that of separating propylene and propane (/> and ). Therefore, a narrower pore structure and a more concentrated pore size distribution are required for the screening and separation of ethylene/ethane. At present, several metal-organic frameworks (MOFs), silver-loaded zeolite molecular sieves and microporous carbon materials have been reported to have the performance of screening ethylene/ethane. However, to become an industrial adsorbent, the adsorbent material must simultaneously meet the requirements of good stability, excellent selectivity, high adsorption capacity, easy particle forming and low preparation cost. Most of the current MOFs materials are unstable and very expensive; zeolite molecular sieves are prone to carbon deposition when separating olefins and have poor cyclic stability; Du et al. used dopamine as a raw material to achieve complete screening and separation of ethylene/ethane by porous carbon materials (Du S, Huang J, Ryder M, et al. Probing sub-5Angstrom micropores in carbon for precise light olefin/paraffin separation [J]. Nat Commun, 2023, 14 (1): 1197.). However, this carbon molecular sieve mainly uses expensive dopamine as a carbon source, and the resulting sample is in powder form and does not have the characteristics of direct industrial application. If the crystalline nanoparticles are formed by adding a binder, the adsorption capacity will be reduced, and the secondary pores generated will lead to a decrease in selectivity.

发明内容Summary of the invention

为了制备一种价格低廉并且可直接应用于分离乙烯和乙烷的颗粒炭分子筛,本发明提出了一种分离乙烯/乙烷的颗粒炭分子筛的普适性制备方法。本发明选择天然的颗粒生物质为碳源,经过破碎、筛选和预处理,可控热解碳化,得到具有特定孔径分布的微孔碳材料,然后用与乙烷分子尺寸具有匹配的丁二烯及其混合气吸附到碳材料的部分孔道中,接着加热进行积碳反应,堵住原本能吸附乙烷的孔道,从而对孔隙结构进行精准调控,实现选择性吸附乙烯而不吸附乙烷,制得高效筛分乙烯/乙烷的颗粒炭分子筛。In order to prepare a low-cost granular carbon molecular sieve that can be directly used to separate ethylene and ethane, the present invention proposes a universal preparation method for granular carbon molecular sieves for separating ethylene/ethane. The present invention selects natural granular biomass as a carbon source, and after crushing, screening and pretreatment, controllable pyrolysis and carbonization, obtains a microporous carbon material with a specific pore size distribution, and then uses butadiene and its mixed gas that match the size of ethane molecules to adsorb into part of the pores of the carbon material, and then heats it for carbon deposition reaction to block the pores that can originally adsorb ethane, thereby accurately controlling the pore structure, achieving selective adsorption of ethylene without adsorbing ethane, and obtaining a granular carbon molecular sieve that efficiently screens ethylene/ethane.

本发明目的通过以下技术方案实现。The purpose of the present invention is achieved through the following technical solutions.

一种可筛分乙烯/乙烷的颗粒炭分子筛的制备方法,包含以下步骤:A method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane comprises the following steps:

(1)将生物质碳源颗粒破碎,过筛,然后用盐溶液浸渍,再将此颗粒炭前驱体进行热解和碳化;(1) crushing the biomass carbon source particles, sieving them, and then impregnating them with a salt solution, and then pyrolyzing and carbonizing the particle carbon precursor;

(2)将经过步骤(1)处理的颗粒炭置于含有C4烯烃的氛围中进行吸附,然后再加热,使C4烯烃在碳材料孔道表面进行碳化反应,即制得可筛分乙烯/乙烷的颗粒炭分子筛。(2) placing the granular carbon treated in step (1) in an atmosphere containing C4 olefins for adsorption, and then heating to allow the C4 olefins to undergo a carbonization reaction on the surface of the carbon material pores, thereby obtaining a granular carbon molecular sieve capable of screening ethylene/ethane.

优选的,步骤(1)所述生物质碳源颗粒包括但不限于椰子壳、咖啡豆、棕榈壳、大米和小米中的一种或多种;所述生物质碳源颗粒经破碎后筛选的粒度范围为10-40目。Preferably, the biomass carbon source particles in step (1) include but are not limited to one or more of coconut shells, coffee beans, palm shells, rice and millet; the particle size range of the biomass carbon source particles after crushing and screening is 10-40 mesh.

优选的,步骤(1)所述盐溶液主要是Fe盐、Cu盐或两种盐的混合物,盐溶液的浓度为0.001-0.1mol/L,两种盐的摩尔比例为Fe:Cu=0.005-1:1,浸渍的时间为1-8小时,温度为室温至40℃。Preferably, the salt solution in step (1) is mainly Fe salt, Cu salt or a mixture of the two salts, the concentration of the salt solution is 0.001-0.1 mol/L, the molar ratio of the two salts is Fe:Cu=0.005-1:1, the immersion time is 1-8 hours, and the temperature is room temperature to 40°C.

优选的,步骤(1)所述热解和碳化是在N2和/或惰性气体氛围下,将颗粒炭进行初步的热解和碳化的温度为250-900℃,时间为1-4小时。Preferably, the pyrolysis and carbonization in step (1) is carried out in an atmosphere of N2 and/or an inert gas, and the temperature for preliminary pyrolysis and carbonization of the granular carbon is 250-900°C and the time is 1-4 hours.

优选的,步骤(2)所述C4烯烃包括但不限于1,3-丁二烯1-丁烯中的一种或两种及以上气体的混合气。Preferably, the C4 olefin in step (2) includes but is not limited to 1,3-butadiene 1-Butene One or a mixture of two or more gases.

优选的,步骤(2)所述含有C4烯烃的氛围中,1,3-丁二烯的体积占比为1%-100%,其余为其它C4烯烃和N2Preferably, in the atmosphere containing C4 olefins in step (2), the volume proportion of 1,3-butadiene is 1%-100%, and the rest is other C4 olefins and N 2 .

优选的,步骤(2)所述含有C4烯烃的氛围中,总压力为0.1-2bar,平衡吸附的时间为0.5-6小时。Preferably, in the atmosphere containing C4 olefins in step (2), the total pressure is 0.1-2 bar, and the equilibrium adsorption time is 0.5-6 hours.

优选的,步骤(2)所述加热的温度为60-130℃,碳化反应的时间为0.5-2小时。Preferably, the heating temperature in step (2) is 60-130° C., and the carbonization reaction time is 0.5-2 hours.

由以上任一项所述的制备方法制得的一种颗粒炭分子筛,常温常压下对乙烯/乙烷具有分子筛分分离性能,对乙烯/乙烷的吸附量之比大于8(在298K和1bar条件下)。A granular carbon molecular sieve prepared by any of the preparation methods described above has molecular sieving separation performance for ethylene/ethane at room temperature and pressure, and the adsorption ratio of ethylene/ethane is greater than 8 (at 298K and 1 bar).

以上所述的一种颗粒炭分子筛应用于乙烯/乙烷的吸附分离。The above-mentioned granular carbon molecular sieve is used for the adsorption separation of ethylene/ethane.

本发明思路是:选择天然可再生的颗粒生物质碳源,例如,椰壳、棕榈壳、大米以及小米等(可以降低成本);接下来面对的难题是,不同种类、产地、生长年限或部位的生物质颗粒碳,其初始结构不同,受热后结构演变的路径不同,这就导致应用现有的热解技术很难在次埃米精度上,成批量地控制碳材料的孔道尺寸,制备出合格的碳分子筛。为克服这一难题,本发明将这些生物质碳源颗粒破碎到一定的颗粒尺寸,然后用热解碳化方法,制成有一定孔隙率且孔道尺寸分布可控的碳前驱体,然后再在一定负压条件下的环境中,将一定量的C4烯烃混合物,通过吸附方式插入到材料的孔道中,在密闭的条件下加热到一定的温度,使这些烯烃化合物在多孔碳材料孔道表面形成聚合碳化,将尺寸大于乙烷分子动力学直径的孔道封住,从而达到精准调控筛分孔道的尺寸,使其排斥乙烷而仅吸附乙烯,实现对乙烷和乙烷进的分子筛分分离。The idea of the present invention is to select natural and renewable particulate biomass carbon sources, such as coconut shells, palm shells, rice and millet (which can reduce costs); the next problem is that biomass particulate carbon of different types, origins, growth years or parts has different initial structures and different paths of structural evolution after heating, which makes it difficult to control the pore size of carbon materials in batches with sub-angstrom accuracy using existing pyrolysis technology to prepare qualified carbon molecular sieves. To overcome this problem, the present invention crushes these biomass carbon source particles into a certain particle size, and then uses a pyrolysis carbonization method to make a carbon precursor with a certain porosity and controllable pore size distribution. Then, in an environment under certain negative pressure conditions, a certain amount of C4 olefin mixture is inserted into the pores of the material by adsorption, and heated to a certain temperature under closed conditions, so that these olefin compounds form polymerization carbonization on the pore surface of the porous carbon material, and the pores with a size larger than the molecular dynamics diameter of ethane are sealed, thereby achieving precise control of the size of the screening pores, so that ethane is repelled and only ethylene is adsorbed, thereby realizing the molecular screening separation of ethane and ethane.

本发明的优势在于:由于选择天然的颗粒生物质为碳源,制备成本低;采用微量的C4烯烃混合物,插入到材料的孔道中进行一次性控制孔道尺寸,具有操作简单,能精准控制,适用于不同来源生物质碳源的制备碳分子筛,它可以避免热解法面临的温度敏感引起碳分子筛筛分孔道难以控制的问题,易于工业化制备;由于选择天然的颗粒生物质为碳源,所制得的材料为颗粒碳材料,不需要进行后续的成型,粒度可以在10-60目(可根据需要筛选)之间进行控制。The advantages of the present invention are as follows: since natural granular biomass is selected as the carbon source, the preparation cost is low; a trace amount of C4 olefin mixture is used and inserted into the pores of the material to control the pore size at one time, the operation is simple, the control can be precise, and the carbon molecular sieve is suitable for preparing carbon molecular sieves from biomass carbon sources of different sources. The problem of temperature sensitivity faced by the pyrolysis method causing the sieving pores of the carbon molecular sieve to be difficult to control is avoided, and the industrial preparation is easy; since natural granular biomass is selected as the carbon source, the prepared material is a granular carbon material, which does not require subsequent molding, and the particle size can be controlled between 10-60 meshes (can be screened as needed).

与现有技术相比,本发明具有以下优点与有益效果:Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1)本发明制备的颗粒炭分子筛能够实现乙烯/乙烷的分子筛分,在常温常压下对乙烯/乙烷吸附容量之比大于8,可满足工业上分离纯化乙烯的需求。(1) The granular carbon molecular sieve prepared by the present invention can achieve molecular sieving of ethylene/ethane, and the ratio of ethylene/ethane adsorption capacity at room temperature and pressure is greater than 8, which can meet the needs of industrial separation and purification of ethylene.

(2)本发明制备的颗粒炭分子筛结构稳定,成本低;本发明制备的炭分子筛是颗粒状的,可以直接装填在吸附柱分离装置中,具有可直接工程应用的特性。(2) The granular carbon molecular sieve prepared by the present invention has a stable structure and low cost; the carbon molecular sieve prepared by the present invention is granular and can be directly loaded into an adsorption column separation device, and has the characteristic of being directly applicable to engineering.

(3)本发明采用独特的原理制备出能够实现对乙烯/乙烷进行分子筛分的颗粒炭分子筛,其独特的筛分孔调控策略,使人们能够更加广泛地选择天然的颗粒碳源,制备出性能稳定的颗粒炭分子筛。(3) The present invention adopts a unique principle to prepare a granular carbon molecular sieve capable of molecular sieving ethylene/ethane. Its unique sieving pore control strategy enables people to more widely select natural granular carbon sources and prepare granular carbon molecular sieves with stable performance.

(4)本发明不使用粘合剂和高污染性活化剂,绿色环保。(4) The present invention does not use adhesives and highly polluting activators, and is green and environmentally friendly.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1-图5是实施例1-5所得产物在298K下对乙烯/乙烷的吸附等温线图。Figures 1 to 5 are adsorption isotherms of the products obtained in Examples 1 to 5 for ethylene/ethane at 298K.

图6是实施例1和对比例1所得产物在298K下对乙烯/乙烷的吸附等温线图。FIG. 6 is an adsorption isotherm diagram of ethylene/ethane for the products obtained in Example 1 and Comparative Example 1 at 298K.

图7是对比例2所得产物在298K下对乙烯/乙烷的吸附等温线图。FIG. 7 is an adsorption isotherm diagram of the product obtained in Comparative Example 2 for ethylene/ethane at 298K.

图8是实施例1-5所得产物在298K、1bar下对乙烯/乙烷吸附量之比对比图。FIG8 is a comparison chart of the ratio of ethylene/ethane adsorption of the products obtained in Examples 1-5 at 298K and 1 bar.

图9是实施例1和对比例1所得产物在273K下二氧化碳吸脱附等温线图。FIG. 9 is a graph showing the carbon dioxide adsorption and desorption isotherms of the products obtained in Example 1 and Comparative Example 1 at 273K.

图10是实施例1和对比例1所得产物通过273K下二氧化碳吸脱附等温线计算得到的孔径分布图(GCMC模型)。FIG. 10 is a pore size distribution diagram (GCMC model) of the products obtained in Example 1 and Comparative Example 1 calculated by carbon dioxide adsorption-desorption isotherms at 273 K.

具体实施方式Detailed ways

下面结合实施例和附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。The present invention is further described in detail below in conjunction with examples and drawings, but the embodiments of the present invention are not limited thereto.

本发明实施例中未注明具体条件者,按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等,均为可以通过市售购买获得的常规产品。If no specific conditions are specified in the examples of the present invention, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. All raw materials, reagents, etc., whose manufacturers are not specified, are conventional products that can be purchased commercially.

实施例1Example 1

将一定量大米破碎,筛选出10-40目的颗粒,用清水清洗,滤干,然后浸泡在浓度为0.001mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=1:1)中3小时,过滤干燥,把干燥后的大米置于管式炉中,在N2氛围中以5℃/min升温加热管式炉至300℃进行热解碳化1小时,随后再以5℃/min升温至800℃热解碳化1小时,降温后得到微孔碳材料;将这些微孔碳材料置于密闭容器中,抽真空后充入1bar的1,3-丁二烯气体,静态吸附5小时后,将反应器加热至100℃加热,维持1小时,然后冷却至室温,得到产物标记为CMC1#。A certain amount of rice was crushed, and particles of 10-40 mesh were screened out. The rice was washed with clean water, filtered, and then soaked in a 0.001 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride = 1:1) for 3 hours, filtered and dried. The dried rice was placed in a tubular furnace, and the tubular furnace was heated to 300°C at 5°C/min in a N2 atmosphere for pyrolysis and carbonization for 1 hour, and then the temperature was increased to 800°C at 5°C/min for pyrolysis and carbonization for 1 hour, and then the temperature was cooled to obtain a microporous carbon material; the microporous carbon materials were placed in a closed container, evacuated and filled with 1 bar of 1,3-butadiene gas, and after static adsorption for 5 hours, the reactor was heated to 100°C and maintained for 1 hour, and then cooled to room temperature to obtain a product marked as CMC1#.

实施例2Example 2

将一定量经过初步碳化的椰壳碳破碎,筛选出10-40目的颗粒,用清水清洗,滤干,然后浸泡在浓度为0.1mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=0.5:1)中5小时,过滤干燥,把干燥后的椰壳颗粒置于的管式炉中,在N2氛围中以5℃/min升温加热管式炉至400℃进行热解碳化1小时,随后再以5℃/min升温至700℃热解碳化3小时,降温后得到微孔碳材料;将这些微孔碳材料置于密闭容器中,抽真空后充入0.5bar的1,3-丁二烯气体,静态吸附2小时后,将反应器加热至120℃加热,维持1小时,然后冷却至室温,得到产物标记为CMC2#。A certain amount of coconut shell carbon that has undergone preliminary carbonization is crushed, and particles of 10-40 mesh are screened out. The particles are washed with clean water, filtered, and then immersed in a 0.1 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride = 0.5:1) for 5 hours, filtered and dried. The dried coconut shell particles are placed in a tubular furnace, and the tubular furnace is heated to 400°C at 5°C/min in a N2 atmosphere for pyrolysis and carbonization for 1 hour, and then the temperature is increased to 700°C at 5°C/min for pyrolysis and carbonization for 3 hours, and microporous carbon materials are obtained after cooling; these microporous carbon materials are placed in a closed container, evacuated and filled with 0.5 bar of 1,3-butadiene gas, and after static adsorption for 2 hours, the reactor is heated to 120°C and maintained for 1 hour, and then cooled to room temperature to obtain a product marked as CMC2#.

实施例3Example 3

将一定量经过初步碳化的咖啡豆破碎,筛选出10-40目的颗粒,用清水清洗,滤干,然后浸泡在浓度为0.01mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=0.1:1)中8小时,过滤干燥,把干燥后的咖啡豆颗粒置于的管式炉中,在N2氛围中以3℃/min升温加热管式炉至850℃进行热解碳化1.8小时,降温后得到微孔碳材料;将这些微孔碳材料置于密闭容器中,抽真空后充入1.5bar的1,3-丁二烯(2%)+1-丁烯(2%)+N2(96%)混合气,静置6小时后于60℃加热0.5小时,得到产物标记为CMC3#。A certain amount of coffee beans that have undergone preliminary carbonization are crushed, and particles of 10-40 mesh are screened out. The particles are washed with clean water, filtered, and then immersed in a 0.01 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride=0.1:1) for 8 hours, filtered and dried. The dried coffee bean particles are placed in a tubular furnace, and the tubular furnace is heated to 850°C at 3°C/min in a N2 atmosphere for pyrolysis and carbonization for 1.8 hours. After cooling, microporous carbon materials are obtained; these microporous carbon materials are placed in a sealed container, evacuated, and filled with a 1.5 bar mixed gas of 1,3-butadiene (2%) + 1-butene (2%) + N2 (96%), and then allowed to stand for 6 hours and then heated at 60°C for 0.5 hour to obtain a product marked as CMC3#.

实施例4Example 4

将一定量经过初步碳化的棕榈壳碳破碎,筛选出10-40目的颗粒,用清水清洗,滤干,然后浸泡在浓度为0.003mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=0.005:1)中1小时,过滤干燥,把干燥后的椰壳颗粒置于的管式炉中,在N2氛围中以5℃/min升温加热管式炉至250℃进行热解碳化1小时,随后再以5℃/min升温至700℃热解碳化2小时,降温后得到微孔碳材料;将这些微孔碳材料置于密闭容器中,抽真空后充入0.1bar的1,3-丁二烯气体,静态吸附1小时后,将反应器加热至80℃加热,维持2小时,然后冷却至室温,得到产物标记为CMC4#。A certain amount of palm shell carbon that has undergone preliminary carbonization is crushed, and particles of 10-40 mesh are screened out, washed with clean water, filtered, and then immersed in a 0.003 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride = 0.005:1) for 1 hour, filtered and dried, and the dried coconut shell particles are placed in a tubular furnace, and the tubular furnace is heated to 250°C at 5°C/min in a N2 atmosphere for pyrolysis and carbonization for 1 hour, and then the temperature is increased to 700°C at 5°C/min for pyrolysis and carbonization for 2 hours, and microporous carbon materials are obtained after cooling; these microporous carbon materials are placed in a closed container, evacuated and filled with 0.1 bar of 1,3-butadiene gas, and after static adsorption for 1 hour, the reactor is heated to 80°C and maintained for 2 hours, and then cooled to room temperature to obtain a product marked as CMC4#.

实施例5Example 5

将一定量小米筛选出10-40目的颗粒,用清水清洗,滤干,然后浸泡在浓度为0.005mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=0.5:1)中4小时,过滤干燥,把干燥后的大米置于管式炉中,在N2氛围中以5℃/min升温加热管式炉至300℃进行热解碳化1小时,随后再以5℃/min升温至750℃热解碳化1小时,降温后得到微孔碳材料;将这些微孔碳材料置于密闭容器中,抽真空后充入2bar的1,3-丁二烯气体,静态吸附4小时后,将反应器加热至130℃加热,维持1小时,然后冷却至室温,得到产物标记为CMC5#。A certain amount of millet was screened to obtain particles of 10-40 mesh, washed with clean water, filtered, and then soaked in a 0.005 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride = 0.5:1) for 4 hours, filtered and dried, and the dried rice was placed in a tubular furnace, and the tubular furnace was heated to 300°C at 5°C/min in a N2 atmosphere for pyrolysis and carbonization for 1 hour, and then the temperature was increased to 750°C at 5°C/min for pyrolysis and carbonization for 1 hour, and then the temperature was cooled to obtain a microporous carbon material; these microporous carbon materials were placed in a closed container, evacuated and filled with 2 bar of 1,3-butadiene gas, and after static adsorption for 4 hours, the reactor was heated to 130°C and maintained for 1 hour, and then cooled to room temperature to obtain a product marked as CMC5#.

对比例1Comparative Example 1

将一定量大米破碎,筛选出10-40目的颗粒,然后浸泡在浓度为0.001mol/L的氯化铁/氯化铜混合溶液(其中氯化铁:氯化铜摩尔比=1:1)中3小时,过滤干燥,把干燥后的大米置于管式炉中,在N2氛围中以5℃/min升温加热管式炉至300℃进行热解碳化1小时,随后再以5℃/min升温至800℃热解碳化1小时,降温后得到对比例1所得产物。A certain amount of rice was crushed, and particles of 10-40 mesh were screened out, and then soaked in a 0.001 mol/L ferric chloride/copper chloride mixed solution (wherein the molar ratio of ferric chloride:copper chloride = 1:1) for 3 hours, filtered and dried, and the dried rice was placed in a tubular furnace, and the tubular furnace was heated to 300° C. at 5° C./min in a N 2 atmosphere for pyrolysis and carbonization for 1 hour, and then the temperature was increased to 800° C. at 5° C./min for pyrolysis and carbonization for 1 hour, and the product obtained in Comparative Example 1 was obtained after cooling.

对比例2Comparative Example 2

将一定量商用椰壳活性炭置于密闭容器中,抽真空后充入1bar的1,3-丁二烯气体,静态吸附5小时后,将反应器加热至100℃加热,维持1小时,然后冷却至室温,得到对比例2所得产物。A certain amount of commercial coconut shell activated carbon was placed in a sealed container, and after evacuation, 1 bar of 1,3-butadiene gas was filled in. After static adsorption for 5 hours, the reactor was heated to 100°C, maintained for 1 hour, and then cooled to room temperature to obtain the product obtained in Comparative Example 2.

图1-图5为实施例1-5所得产物在298K下对乙烯/乙烷的吸附等温线图。由此可见,本发明制备的颗粒炭分子筛几乎不吸附乙烷(小于0.2mmol/g),展现出优异的乙烯/乙烷筛分分离效果。其中,实施例3所得产物具有较高的乙烯吸附容量(1.38mmol/g),实施例5所得产物具有极低的乙烷吸附量(0.014mmol/g),实施例1所得产物兼具吸附容量和选择性。Figures 1 to 5 are the adsorption isotherms of ethylene/ethane for the products obtained in Examples 1 to 5 at 298K. It can be seen that the granular carbon molecular sieve prepared by the present invention hardly adsorbs ethane (less than 0.2 mmol/g), showing excellent ethylene/ethane screening and separation effect. Among them, the product obtained in Example 3 has a higher ethylene adsorption capacity (1.38 mmol/g), the product obtained in Example 5 has an extremely low ethane adsorption amount (0.014 mmol/g), and the product obtained in Example 1 has both adsorption capacity and selectivity.

图6是实施例1和对比例1所得产物在298K下对乙烯/乙烷的吸附等温线图。由等温线图可以看出,经过C4烯烃氛围静置、加热等步骤后,相比于对比例,实施例1所得产物对乙烯的吸附容量有所下降,但对乙烷的吸附量从1.10mmol/g下降至0.069mmol/g,使其对乙烯/乙烷的选择性得到极大的提升。Fig. 6 is an adsorption isotherm diagram of ethylene/ethane for the products obtained in Example 1 and Comparative Example 1 at 298 K. It can be seen from the isotherm diagram that after the steps of standing and heating in a C4 olefin atmosphere, the adsorption capacity of ethylene for the product obtained in Example 1 decreased compared with the comparative example, but the adsorption amount of ethane decreased from 1.10 mmol/g to 0.069 mmol/g, which greatly improved its selectivity for ethylene/ethane.

图7是对比例2所得产物在298下对乙烯/乙烷的吸附等温线图。对比例2所得产物具有一定的乙烯/乙烷分离性能,但未实现筛分效果。7 is an adsorption isotherm diagram of ethylene/ethane at 298°C for the product obtained in Comparative Example 2. The product obtained in Comparative Example 2 has a certain ethylene/ethane separation performance, but does not achieve a screening effect.

图8是实施例1-5所得产物在298K、1bar下对乙烯/乙烷吸附量之比对比图。在常温常压下实施例1-5所得产物对乙烯/乙烷的吸附容量之比均大于8,其中实施例5所得产物对乙烯/乙烷的吸附容量之比高达60.29,表现出了优异的乙烯/乙烷筛分性能。Figure 8 is a comparison chart of the ratio of ethylene/ethane adsorption capacity of the products obtained in Examples 1-5 at 298K and 1 bar. At room temperature and pressure, the ratio of ethylene/ethane adsorption capacity of the products obtained in Examples 1-5 is greater than 8, among which the ratio of ethylene/ethane adsorption capacity of the product obtained in Example 5 is as high as 60.29, showing excellent ethylene/ethane screening performance.

图9和图10是实施例1和对比例1所得产物在273K下二氧化碳吸脱附等温线以及GCMC模型计算得到的孔径分布图。由二氧化碳吸脱附等温线可以看出,经过C4烯烃氛围静置、加热等步骤后,相比于对比例,实施例1所得产物对二氧化碳的吸附量下降,这是因为材料的孔容降低所致。由孔径分布可以看出,实施例1所得产物位于的孔隙结构失效,使其展现出优异的乙烯/乙烷筛分性能。Figures 9 and 10 are the carbon dioxide adsorption and desorption isotherms of the products obtained in Example 1 and Comparative Example 1 at 273K and the pore size distribution calculated by the GCMC model. It can be seen from the carbon dioxide adsorption and desorption isotherms that after standing and heating in a C4 olefin atmosphere, the adsorption of carbon dioxide by the product obtained in Example 1 decreases compared to the comparative example, which is due to the decrease in the pore volume of the material. It can be seen from the pore size distribution that the product obtained in Example 1 is located at The pore structure of the nanostructured carbon nanotubes fails, resulting in excellent ethylene/ethane screening performance.

上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims (10)

1. A process for the preparation of a granular carbon molecular sieve capable of sieving ethylene/ethane comprising the steps of:
(1) Crushing biomass carbon source particles, sieving, then impregnating with a salt solution, and carrying out pyrolysis and carbonization on the particle carbon precursor;
(2) And (3) placing the granular carbon treated in the step (1) in an atmosphere containing C4 olefin for adsorption, and heating to enable the C4 olefin to carry out carbonization reaction on the surface of a pore canal of a carbon material, thus obtaining the granular carbon molecular sieve capable of screening ethylene/ethane.
2. The method of preparing a granular carbon molecular sieve from ethylene/ethane according to claim 1, wherein the biomass carbon source of step (1) comprises one or more of coconut shell, coffee beans, palm shell, rice and millet; the preferred particle size range of the biomass carbon source after particle breakage is 10-40 mesh.
3. The method for preparing the granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the salt solution in the step (1) is mainly Fe salt, cu salt or a mixture of two salts, the concentration of the salt solution is 0.001-0.1mol/L, and the molar ratio of the two salts is Fe: cu=0.005-1:1, the time of impregnation is 1-8 hours, the temperature is room temperature to 40 ℃.
4. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the pyrolysis and carbonization in the step (1) is performed under the atmosphere of N 2 and/or inert gas, the temperature of the granular carbon is 250-900 ℃ and the time is 1-4 hours.
5. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the C4 olefin in the step (2) comprises one or more of 1, 3-butadiene and 1-butene.
6. The method of preparing a granular carbon molecular sieve for ethylene/ethane screening according to claim 1, wherein in the atmosphere containing C4 olefins in step (2), the volume ratio of 1, 3-butadiene is 1% to 100%, and the balance is other C4 olefins and N 2.
7. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the total pressure in the atmosphere containing C4 olefins in step (2) is 0.1 to 2bar and the adsorption time is 0.5 to 6 hours.
8. The method for preparing a granular carbon molecular sieve capable of screening ethylene/ethane according to claim 1, wherein the heating temperature in the step (2) is 60-130 ℃, and the carbonization reaction time is 0.5-2 hours.
9. A granular carbon molecular sieve produced by the method of any one of claims 1-8.
10. A granular carbon molecular sieve as claimed in claim 9 for use in the adsorptive separation of ethylene/ethane.
CN202410184557.9A 2024-02-19 2024-02-19 A granular carbon molecular sieve capable of screening ethylene/ethane and its preparation method and application Pending CN118062825A (en)

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