CN100453459C - A kind of amine (nitrogen) skeleton hybrid basic microporous material and preparation method thereof - Google Patents

A kind of amine (nitrogen) skeleton hybrid basic microporous material and preparation method thereof Download PDF

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CN100453459C
CN100453459C CNB2004100179747A CN200410017974A CN100453459C CN 100453459 C CN100453459 C CN 100453459C CN B2004100179747 A CNB2004100179747 A CN B2004100179747A CN 200410017974 A CN200410017974 A CN 200410017974A CN 100453459 C CN100453459 C CN 100453459C
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microporous material
nitrogen
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CN1569634A (en
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韩爱杰
贺鹤勇
郭娟
龙英才
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Fudan University
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Abstract

本发明属于微孔材料技术领域,具体为一种胺(氮)骨架杂化碱性微孔材料及其制备方法。其中,胺骨架杂化碱性微孔材料是由骨架含氧微孔材料中1-20%的骨架用胺基替代而获得,其制备方法包括将基底材料与胺的水溶液混合,然后进行水热反应,温度100-200℃,时间10-50小时,即得胺取代骨架杂化微孔材料;对该材料进一步焙烧,即得到氮骨架氮化碱性微孔材料。该材料的合成条件温和、重复性好、制备简便、价格低廉、环境友好,适合于工业化生产。The invention belongs to the technical field of microporous materials, in particular to an amine (nitrogen) skeleton hybrid basic microporous material and a preparation method thereof. Among them, the amine-skeleton hybrid alkaline microporous material is obtained by replacing 1-20% of the skeleton in the skeleton oxygen-containing microporous material with amine groups. The preparation method includes mixing the base material with an amine aqueous solution, and then performing hydrothermal Reaction, the temperature is 100-200 DEG C, and the time is 10-50 hours, the amine-substituted skeleton hybrid microporous material is obtained; the material is further calcined, and the nitrogen skeleton nitrided basic microporous material is obtained. The synthesis condition of the material is mild, the repeatability is good, the preparation is simple, the price is low, the environment is friendly, and it is suitable for industrial production.

Description

一种胺(氮)骨架杂化碱性微孔材料及其制备方法 A kind of amine (nitrogen) skeleton hybrid basic microporous material and preparation method thereof

技术领域 technical field

本发明属于微孔材料技术领域,具体涉及一种胺(氮)骨架杂化碱性微孔材料及其制备方法。该材料在催化及吸附分离等方面有广泛应用前景。The invention belongs to the technical field of microporous materials, and in particular relates to an amine (nitrogen) skeleton hybrid basic microporous material and a preparation method thereof. The material has wide application prospects in catalysis and adsorption separation.

背景技术 Background technique

与传统的固体酸性沸石不同,骨架胺(氮)杂化微孔材料(如沸石分子筛)具有比表面高,可控制和调变的固体碱性,赋择形选择性等特点,作为催化剂具有高活性、高选择性、反应条件温和、产物易于分离等优点,可望成为新一代环境友好催化材料。碱性沸石催化剂可以用于烃类的部分氧化和卤素消化以及催化Knoevenagel缩合等,在合成精细化工产品方面具有良好的产业化应用前景。该材料也可用于从含有强酸的废水中吸附除去浓缩酸。Different from traditional solid acidic zeolites, framework amine (nitrogen) hybrid microporous materials (such as zeolite molecular sieves) have the characteristics of high specific surface area, controllable and adjustable solid alkalinity, and shape-selective selectivity. The advantages of activity, high selectivity, mild reaction conditions, and easy separation of products are expected to become a new generation of environmentally friendly catalytic materials. Basic zeolite catalysts can be used for partial oxidation of hydrocarbons, digestion of halogens, and catalysis of Knoevenagel condensation, etc., and have good industrial application prospects in the synthesis of fine chemical products. The material can also be used for the adsorptive removal of concentrated acids from wastewater containing strong acids.

J.B.Peri报道(J.Phys.Chem.,1966,70(9):2937-2945),预先将硅溶胶在800℃焙烧后,氨气(NH3)可以缓慢的吸附在其表面。增加压强和时间,NH3的吸附量会增加,在100mmHg的压强下吸附8天后可以得到NH3的最大吸附量,但也仅为每100A2吸附1.3到1.4个分子的NH3。NH3取代硅溶胶表面OH,在硅溶胶表面形成NH2基团。JBPeri reported (J. Phys. Chem., 1966, 70(9): 2937-2945) that ammonia (NH 3 ) can be slowly adsorbed on the surface of silica sol after pre-calcined at 800°C. Increase the pressure and time, the adsorption amount of NH 3 will increase, the maximum adsorption amount of NH 3 can be obtained after adsorption under the pressure of 100mmHg for 8 days, but only 1.3 to 1.4 molecules of NH 3 can be adsorbed per 100A 2 . NH 3 replaces the OH on the surface of the silica sol to form NH 2 groups on the surface of the silica sol.

Mobil公司的G.T.Kerr和G.F.Shipman报道(J.Phys.Chem.,1968,79(8):3071-3072),氢型的Y沸石(HY)的骨架氧原子可以在500℃高温条件下被氨气(NH3)取代,得到氨化沸石(amidozeolite)。GTKerr and GF Shipman of Mobil Company reported (J.Phys.Chem., 1968,79 (8): 3071-3072), the skeleton oxygen atom of the Y zeolite (HY) of hydrogen type can be destroyed by ammonia gas ( NH 3 ) to give ammoniated zeolite (amidozeolite).

P.W.Lednor和R.de Ruiter报道(J.Chem.Soc.,Chem.Commun.,1989,320-321),氨气(NH3)与不同形式的SiO2(全硅MFI沸石和硅胶)在1100℃的高温下反应得到Si2N2O。他们发现这种硅氧氮物质具有碱性,并用其催化Knoevenagel缩合反应(J.Chem.Soc.,Chem.Commun.,1991,1625-1626)。PWLednor and R.de Ruiter reported (J.Chem.Soc., Chem.Commun., 1989, 320-321), ammonia (NH 3 ) and different forms of SiO 2 (silica MFI zeolite and silica gel) at 1100 ° C Si 2 N 2 O is obtained by reacting at high temperature. They found that this silicon oxygen nitrogen substance is basic and used it to catalyze the Knoevenagel condensation reaction (J.Chem.Soc., Chem.Commun., 1991, 1625-1626).

J.Sjoberg和R.Pompe报道(J.Am.Ceram.Soc.,1992,75(8):2189-2193),氨气(NH3)与无定形SiO2在800℃高温以上才可以发生体相反应。当温度达到1050℃时,氮化达到最大量,可以得到Si2N2O硅氧氮物质。J.Sjoberg and R.Pompe reported (J.Am.Ceram.Soc., 1992, 75(8):2189-2193), ammonia (NH 3 ) and amorphous SiO 2 can only be formed at a high temperature above 800°C. Respond instead. When the temperature reaches 1050°C, the nitriding reaches the maximum amount, and Si 2 N 2 O silicon oxynitride substances can be obtained.

A.Steinz,B.Wehrle和M.Jansen报通(Zeolites,1993,13:291-298),在900℃以上的温度下,AlPO4-5(一种磷酸盐分子筛)在NH3或NH3/CO的混合气氛中反应得到P-NH2基团,骨架氧原子被氮原子取代。A.Steinz, B.Wehrle and M.Jansen reported (Zeolites, 1993, 13:291-298), at a temperature above 900 ° C, AlPO 4 -5 (a phosphate molecular sieve) in NH 3 or NH 3 The reaction in a mixed atmosphere of CO/CO yields the P- NH2 group, and the skeleton oxygen atoms are replaced by nitrogen atoms.

P.Grange等人报道含氮的磷酸盐分子筛(aluminophosphate oxynitrides)具有碱性,可用做新型的催化剂(Appl.Catal.A:Gen,1994,114,L191-L196;Appl.Catal.A:Gen,1996,137,9-23)。P.Grange et al. report that nitrogen-containing phosphate molecular sieves (aluminophosphate oxynitrides) are basic and can be used as novel catalysts (Appl.Catal.A: Gen, 1994,114, L191-L196; Appl.Catal.A: Gen, 1996, 137, 9-23).

M.J.Climent等人报道(J.Catal.,1996,163:392-398;Catal.Lett.,1999,59:33-38),在800℃高温下磷铝分子筛可以和氨气反应,得到的含氮的磷酸盐分子筛(aluminophosphateoxynitrides)被用做新型的碱性催化剂。他们还从理论上计算了含氮的磷酸盐分子筛的稳定性和碱性(J.Mol.Catal.A:1998,133:241-250)。M.J.Climent et al. reported (J.Catal., 1996, 163: 392-398; Catal. Lett., 1999, 59: 33-38), that phosphorus aluminum molecular sieves can react with ammonia at a high temperature of 800°C, and the obtained Nitrogen phosphate molecular sieves (aluminophosphateoxynitrides) are used as new basic catalysts. They also theoretically calculated the stability and basicity of nitrogen-containing phosphate molecular sieves (J. Mol. Catal. A: 1998, 133: 241-250).

S.Ernst等人报道(Appl.Catal.A:Gen,2000,200:117-123),在800℃以上的高温下沸石(NaY)和磷铝分子筛可以和氨气反应,制备的含氮沸石分子筛被用来催化Knoevenagel缩合反应。S. Ernst et al. reported (Appl. Catal. A: Gen, 2000, 200: 117-123) that zeolite (NaY) and aluminum phosphorus molecular sieves can react with ammonia at high temperatures above 800 ° C, and the prepared nitrogen-containing zeolite Molecular sieves were used to catalyze the Knoevenagel condensation reaction.

J.El Haskouri等人报道(Adv.Mater.,2001,13(3):192-195),介孔硅和氨气在950℃高温下反应制备含氮的介孔硅。J. El Haskouri et al. reported (Adv. Mater., 2001, 13(3): 192-195) that nitrogen-containing mesoporous silicon was prepared by reacting mesoporous silicon and ammonia at a high temperature of 950°C.

上述报道的含氮微孔材料均采用气/固相反应制备,即通常在500℃以上的高温下用氨气对基底材料进行作用,反应条件苛刻。The nitrogen-containing microporous materials reported above are all prepared by gas/solid phase reaction, that is, ammonia gas is usually used to act on the substrate material at a high temperature above 500°C, and the reaction conditions are harsh.

发明内容 Contents of the invention

本发明的目的在于提出一种催化性能好、制造成本低的胺(氮)骨架杂化碱性微孔材料及其制备方法。The purpose of the present invention is to propose an amine (nitrogen) skeleton hybrid basic microporous material with good catalytic performance and low manufacturing cost and a preparation method thereof.

本发明提出的胺骨架杂化碱性微孔材料,是将骨架含氧微孔材料中1-20%的骨架氧用胺基替代而获得,其中胺基为-NHR,或NR1R2,这里R1、R2分别为C1-C4的烃类。The amine-skeleton hybrid alkaline microporous material proposed by the present invention is obtained by replacing 1-20% of the skeleton oxygen in the skeleton oxygen-containing microporous material with amine groups, wherein the amine group is -NHR, or NR 1 R 2 , Here R 1 and R 2 are C 1 -C 4 hydrocarbons respectively.

上述微孔材料中,所述骨架含氧微孔材料可以是晶态的沸石分子筛,磷酸铝分子筛,介孔分子筛,以及非晶态的硅胶,白炭黑等。Among the above microporous materials, the skeleton oxygen-containing microporous material can be crystalline zeolite molecular sieve, aluminum phosphate molecular sieve, mesoporous molecular sieve, and amorphous silica gel, white carbon black and the like.

胺类比氨气的碱性更强,一级胺,二级胺上胺基中的氢原子可以作为反应位,率先进攻微孔材料的Si-O-Si骨架。因此,胺的反应活性比氨气高,反应所需温度低。微孔材料的部分骨架氧原子被胺基团取代以后,由于胺基团上氮原子更低的电负性,导致材料的碱性增强,成为一种新型的微孔催化材料。Amines are more basic than ammonia, and the hydrogen atoms in the amine groups on the primary and secondary amines can be used as reaction sites to attack the Si-O-Si skeleton of the microporous material first. Therefore, the reactivity of amine is higher than that of ammonia, and the temperature required for the reaction is lower. After some of the skeleton oxygen atoms of the microporous material are replaced by amine groups, the basicity of the material is enhanced due to the lower electronegativity of the nitrogen atoms on the amine groups, and it becomes a new type of microporous catalytic material.

上述胺(氮)骨架杂化碱性微孔材料的制备方法如下:The preparation method of the above-mentioned amine (nitrogen) skeleton hybrid basic microporous material is as follows:

将基底材料与胺的水溶液混合,置于反应釜中,进行水热反应,温度100-200℃,时间10-50小时,得到胺取代骨架杂化微孔材料;或将胺的水溶液置于反应釜底层,基底材料置于上层,进行水热反应,温度100-200℃,时间10-50小时,利用加热时产生的蒸汽与基底材料发生气/固相反应,制备得胺取代骨架杂化微孔材料。Mix the base material with an aqueous solution of amine, place it in a reaction kettle, and conduct a hydrothermal reaction at a temperature of 100-200°C for 10-50 hours to obtain a hybrid microporous material with an amine-substituted skeleton; or place the aqueous solution of amine in the reaction The bottom layer of the kettle, the base material is placed on the upper layer, and the hydrothermal reaction is carried out at a temperature of 100-200°C and a time of 10-50 hours. The steam generated during heating is used for gas/solid phase reaction with the base material, and the amine-substituted skeleton hybrid microstructure is prepared. hole material.

将上述胺取代骨架杂化微孔材料在400-800℃焙烧1-3h,得到骨架氮杂化微孔催化材料。即该材料以氮原子替代了骨架含氧微孔材料中1-20%的骨架氧。Calcining the above-mentioned amine-substituted skeleton hybrid microporous material at 400-800° C. for 1-3 hours to obtain a skeleton nitrogen hybrid microporous catalytic material. That is, the material replaces 1-20% of the skeleton oxygen in the skeleton oxygen-containing microporous material with nitrogen atoms.

上述方法中,所述基底材料可采用商品沸石分子筛、磷酸铝分子筛、介孔分子筛、白炭黑或硅胶等,基底材料与胺类低温水热反应或发生气/固相反应,制得骨架胺杂化碱性微孔新材料,再经焙烧,获得具有碱性的骨架氮杂化微孔材料。以甲胺杂化的MFI沸石为例,经不同方式处理后酸碱性变化见图1所示,表1和表2分别给出了酸碱性变化的数据和不同方式测定的微孔材料的氮含量。In the above method, the base material can be commercial zeolite molecular sieve, aluminum phosphate molecular sieve, mesoporous molecular sieve, white carbon black or silica gel, etc., and the base material reacts with amines in low-temperature hydrothermal reaction or undergoes gas/solid phase reaction to obtain the skeleton amine The new basic microporous material is hybridized, and then calcined to obtain a nitrogen-hybridized microporous material with basic skeleton. Taking the MFI zeolite hybridized with methylamine as an example, the changes in acidity and alkalinity after treatment in different ways are shown in Figure 1. Table 1 and Table 2 respectively give the data of acidity and alkalinity changes and the properties of microporous materials measured in different ways. nitrogen content.

本发明材料的制备方法简便,反应条件温和,生产成本低,得到的骨架胺(氮)杂化碱性微孔材料可作为催化剂和吸附剂,适用范围广,具有良好的工业应用前景。The preparation method of the material of the invention is simple, the reaction condition is mild, and the production cost is low. The obtained framework amine (nitrogen) hybrid basic microporous material can be used as a catalyst and an adsorbent, has a wide application range, and has good industrial application prospects.

附图说明 Description of drawings

图1MFI沸石经不同方式处理后酸碱性变化的程序升温脱附(TPD)图。其中,(A)NH3/TPD显示酸性质的变化(B)CO2/TPD显示碱性质的变化。图中(a)基底MFI沸石;(b)甲胺杂化的MFI沸石;(c)500℃焙烧得到的氮杂化的MFI沸石;(d)800℃焙烧得到的氮杂化的MFI沸石。Figure 1 Temperature-programmed desorption (TPD) diagram of the acid-base change of MFI zeolite treated in different ways. Among them, (A) NH 3 /TPD shows changes in acidic properties (B) CO 2 /TPD shows changes in basic properties. In the figure (a) base MFI zeolite; (b) methylamine hybridized MFI zeolite; (c) nitrogenated MFI zeolite calcined at 500°C; (d) nitrogenated MFI zeolite calcined at 800°C.

具体实施方式 Detailed ways

下面通过实施实例进一步描述本发明:The present invention is further described below by implementing examples:

实施例1:Example 1:

基底MFI沸石按以下步骤与甲胺作用,制备骨架胺杂化的MFI沸石:The base MFI zeolite reacts with methylamine according to the following steps to prepare the framework amine hybrid MFI zeolite:

1、将甲胺的水溶液与MFI沸石混合置于反应釜中。或将甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of methylamine and MFI zeolite in the reaction kettle. Or place the aqueous solution of methylamine on the bottom of the reaction kettle, place the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应2天,反应产物经过滤,洗涤,烘干,得到骨架甲胺杂化MFI沸石。2. Put the reaction kettle in an oven at 200°C, and react for 2 days under self-generated pressure. The reaction product is filtered, washed, and dried to obtain a skeleton methylamine hybrid MFI zeolite.

3、骨架甲胺杂化MFI沸石在500℃焙烧2h,得到骨架氮杂化MFI沸石。3. Skeleton methylamine hybrid MFI zeolite was calcined at 500° C. for 2 hours to obtain skeleton nitrogen hybrid MFI zeolite.

实施例2:Example 2:

基底MFI沸石按以下步骤与二甲胺作用,制备骨架二甲胺杂化的MFI沸石:The base MFI zeolite reacts with dimethylamine according to the following steps to prepare the framework dimethylamine hybrid MFI zeolite:

1、将二甲胺的水溶液与MFI沸石混合置于反应釜中。或将二甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of dimethylamine and MFI zeolite in the reaction kettle. Or put the aqueous solution of dimethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于150℃烘箱中,在自生成压力下反应50小时。2. Put the reaction kettle in an oven at 150°C, and react for 50 hours under self-generated pressure.

3、反应产物经过滤,洗涤,烘干,在500℃焙烧2h,得到骨架二甲胺杂化MFI沸石。3. The reaction product is filtered, washed, dried, and calcined at 500° C. for 2 hours to obtain a skeleton dimethylamine hybrid MFI zeolite.

实施例3:Example 3:

基底MFI沸石按以下步骤与乙胺作用,制备骨架乙胺杂化的MFI沸石:The base MFI zeolite reacts with ethylamine according to the following steps to prepare the MFI zeolite with skeleton ethylamine hybridization:

1、将乙胺与MFI沸石混合置于反应釜中。或将乙胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix ethylamine and MFI zeolite in the reaction kettle. Or put the aqueous solution of ethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应10小时,反应产物经过滤,洗涤,烘干,制得骨架乙胺杂化MFI沸石。2. Put the reaction kettle in an oven at 200°C, and react for 10 hours under self-generated pressure. The reaction product is filtered, washed, and dried to obtain a skeleton ethylamine hybrid MFI zeolite.

3、该骨架乙胺杂化MFI沸石,在500℃焙烧2h,得到骨架氮杂化MFI沸石。3. The framework ethylamine hybrid MFI zeolite is calcined at 500° C. for 2 hours to obtain the framework nitrogen hybrid MFI zeolite.

实施例4:Example 4:

基底材料MCM-41分子筛按以下步骤与甲胺作用,制备骨架胺杂化的MCM-41分子筛:The base material MCM-41 molecular sieve reacts with methylamine according to the following steps to prepare the MCM-41 molecular sieve with skeleton amine hybridization:

1、将甲胺的水溶液与MCM-41分子筛混合置于反应釜中。或将甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of methylamine with MCM-41 molecular sieve and place it in the reaction kettle. Or place the aqueous solution of methylamine on the bottom of the reaction kettle, place the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于150℃烘箱中,在自生成压力下反应48小时,反应产物经过滤,洗涤,烘干,得到骨架甲胺杂化MCM-41分子筛。2. Put the reaction kettle in an oven at 150°C, and react for 48 hours under self-generated pressure. The reaction product is filtered, washed, and dried to obtain the skeleton methylamine hybrid MCM-41 molecular sieve.

3、骨架甲胺杂化MFI沸石在400℃焙烧2h,得到骨架氮杂化MCM-41分子筛。3. Skeleton methylamine hybrid MFI zeolite was calcined at 400°C for 2 hours to obtain skeleton nitrogen hybrid MCM-41 molecular sieve.

实施例5:Example 5:

基底材料MCM-41分子筛按以下步骤与二甲胺作用,制备骨架二甲胺杂化的MCM-41分子筛:The base material MCM-41 molecular sieve reacts with dimethylamine according to the following steps to prepare the MCM-41 molecular sieve with dimethylamine hybridization in the skeleton:

1、将二甲胺的水溶液与MCM-41分子筛混合置于反应釜中。或将二甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of dimethylamine and MCM-41 molecular sieve into the reaction kettle. Or put the aqueous solution of dimethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应20小时。2. Put the reaction kettle in an oven at 200°C, and react for 20 hours under self-generated pressure.

3、反应产物经过滤,洗涤,烘干,在800℃焙烧1h,得到骨架氮杂化MCM-41分子筛。3. The reaction product was filtered, washed, dried, and calcined at 800° C. for 1 hour to obtain the framework nitrogen hybridized MCM-41 molecular sieve.

实施例6:Embodiment 6:

基底材料MCM-41分子筛按以下步骤与乙胺作用,制备骨架乙胺杂化的MCM-41分子筛:The base material MCM-41 molecular sieve reacts with ethylamine according to the following steps to prepare the MCM-41 molecular sieve with skeleton ethylamine hybridization:

1、将乙胺与MCM-41分子筛混合置于反应釜中。或将乙胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix ethylamine with MCM-41 molecular sieve and place in the reaction kettle. Or put the aqueous solution of ethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于100℃烘箱中,在自生成压力下反应48小时,反应产物经过滤,洗涤,烘干,制得骨架乙胺杂化MCM-41分子筛。2. Put the reaction kettle in an oven at 100°C, and react for 48 hours under self-generated pressure. The reaction product is filtered, washed, and dried to prepare the skeleton ethylamine hybrid MCM-41 molecular sieve.

3、该骨架乙胺杂化MFI沸石,在400℃焙烧3h,得到骨架氮杂化MCM-41分子筛。3. The skeleton ethylamine hybridized MFI zeolite was calcined at 400° C. for 3 hours to obtain the skeleton nitrogen hybridized MCM-41 molecular sieve.

实施例7:Embodiment 7:

基底材料硅胶按以下步骤与甲胺作用,制备骨架胺杂化的硅胶:The base material silica gel reacts with methylamine according to the following steps to prepare skeleton amine hybrid silica gel:

1、将甲胺的水溶液与硅胶混合置于反应釜中。或将甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of methylamine and silica gel and place it in the reaction kettle. Or place the aqueous solution of methylamine on the bottom of the reaction kettle, place the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应2天,反应产物经过滤,洗涤,烘干,得到骨架甲胺杂化硅胶。2. Put the reaction kettle in an oven at 200°C, and react for 2 days under self-generated pressure. The reaction product is filtered, washed, and dried to obtain a skeleton methylamine hybrid silica gel.

3、骨架甲胺杂化硅胶在500℃焙烧2h,得到骨架氮杂化硅胶。3. Skeleton methylamine hybrid silica gel was roasted at 500°C for 2 hours to obtain skeleton nitrogen hybrid silica gel.

实施例8:Embodiment 8:

基底材料硅胶按以下步骤与二甲胺作用,制备骨架二甲胺杂化的硅胶:The base material silica gel reacts with dimethylamine according to the following steps to prepare the silica gel hybridized with dimethylamine in the skeleton:

1、将二甲胺的水溶液与硅胶混合置于反应釜中。或将二甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of dimethylamine and silica gel and place it in the reaction kettle. Or put the aqueous solution of dimethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应40小时。2. Put the reaction kettle in an oven at 200°C, and react for 40 hours under self-generated pressure.

3、反应产物经过滤,洗涤,烘干,在800℃焙烧1h,得到骨架氮杂化硅胶。3. The reaction product is filtered, washed, dried, and calcined at 800°C for 1 hour to obtain the skeleton nitrogen hybrid silica gel.

实施例9:Embodiment 9:

基底材料硅胶按以下步骤与乙胺作用,制备骨架乙胺杂化的硅胶:The base material silica gel reacts with ethylamine according to the following steps to prepare skeleton ethylamine hybrid silica gel:

1、将乙胺与硅胶混合置于反应釜中。或将乙胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix ethylamine and silica gel and place in a reaction kettle. Or put the aqueous solution of ethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于150℃烘箱中,在自生成压力下反应48小时,反应产物经过滤,洗涤,烘干,制得骨架乙胺杂化硅胶。2. Put the reaction kettle in an oven at 150°C, and react for 48 hours under self-generated pressure. The reaction product is filtered, washed, and dried to obtain a skeleton ethylamine hybrid silica gel.

3、该骨架乙胺杂化硅胶,在800℃焙烧2h,得到骨架氮杂化硅胶。3. The skeleton ethylamine hybrid silica gel was calcined at 800° C. for 2 hours to obtain the skeleton nitrogen hybrid silica gel.

实施例10:Example 10:

微孔材料白炭黑按以下步骤与甲胺作用,制备骨架甲胺杂化的白炭黑:Microporous material silica reacts with methylamine according to the following steps to prepare skeleton methylamine hybridized silica:

1、将甲胺的水溶液与白炭黑混合置于反应釜中。或将甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of methylamine and white carbon black and place it in the reaction kettle. Or place the aqueous solution of methylamine on the bottom of the reaction kettle, place the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应2天,反应产物经过滤,洗涤,烘干,得到骨架甲胺杂化白炭黑。2. Put the reaction kettle in an oven at 200°C, and react for 2 days under self-generated pressure. The reaction product is filtered, washed, and dried to obtain skeleton methylamine hybrid silica.

3、骨架甲胺杂化材料在500℃焙烧2h,得到骨架氮杂化白炭黑。3. Skeleton methylamine hybrid material is calcined at 500°C for 2 hours to obtain skeleton nitrogen hybridized white carbon black.

实施例11:Example 11:

微孔材料白炭黑按以下步骤与二甲胺作用,制备骨架二甲胺杂化的白炭黑:Microporous material silica reacts with dimethylamine according to the following steps to prepare skeleton dimethylamine hybridized silica:

1、将二甲胺的水溶液与白炭黑混合置于反应釜中。或将二甲胺的水溶液置于反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix the aqueous solution of dimethylamine and white carbon black in the reaction kettle. Or put the aqueous solution of dimethylamine on the bottom of the reaction kettle, put the base material on the upper layer, and separate it with a screen in the middle.

2、将反应釜置于200℃烘箱中,在自生成压力下反应2天,反应产物经过滤,洗涤,烘干,制得骨架二甲胺杂化白炭黑。3.骨架二甲胺杂化白炭黑,在500℃焙烧2h,得到骨架氮杂化白炭黑。2. Put the reaction kettle in an oven at 200°C, and react for 2 days under self-generated pressure. The reaction product is filtered, washed, and dried to obtain skeleton dimethylamine hybrid white carbon black. 3. Skeleton dimethylamine hybridized silica, calcined at 500°C for 2 hours to obtain skeleton nitrogen hybridized silica.

实施例12:Example 12:

微孔材料白炭黑按以下步骤与乙胺作用,制备骨架乙胺杂化的白炭黑:Microporous material silica reacts with ethylamine according to the following steps to prepare skeleton ethylamine hybridized silica:

1、将乙胺与白炭黑混合置于反应釜中。或将乙胺的水溶液置

Figure C20041001797400071
反应釜底层,基底材料置于上层,中间以筛网隔开。1. Mix ethylamine and white carbon black in the reaction kettle. Or the aqueous solution of ethylamine
Figure C20041001797400071
The bottom of the reaction kettle, the base material is placed on the upper layer, and the middle is separated by a screen.

2、将反应釜置于200℃烘箱中,在自生成压力下反应2天。2. Put the reaction kettle in an oven at 200°C, and react for 2 days under self-generated pressure.

3、反应产物经过滤,洗涤,烘干,在500℃焙烧2h,得到骨架氮杂化白炭黑。3. The reaction product was filtered, washed, dried, and calcined at 500°C for 2 hours to obtain skeleton nitrogen-hybridized white carbon black.

表1MFI经不同方式处理后酸碱性质变化的数据Table 1 The data of the change of acid-base properties of MFI after being treated in different ways

Figure C20041001797400081
Figure C20041001797400081

表2不同方式测定微孔材料的氮含量Table 2 Different ways to measure the nitrogen content of microporous materials

  XPS XPS   克氏定氮法 Kjeldahl nitrogen method   甲醛定氮法 Formaldehyde nitrogen determination method   甲胺杂化MFI Methylamine hybrid MFI   16.2% 16.2%   13.1% 13.1%   14.8% 14.8%   氮杂化MFI Nitrogenated MFI   13.8% 13.8%   / /   / /   甲胺杂化白炭黑 Methylamine hybrid silica   16.8% 16.8%   14% 14%   / /   氮杂化白炭黑 Nitrogenated silica   16.2% 16.2%   12.3% 12.3%   / /

Claims (5)

1、一种胺骨架杂化碱性微孔材料,其特征在于是将骨架含氧微孔材料中1-20%的骨架氧用胺基替代而获得,其中胺基为甲胺、乙胺或二甲胺。1. An amine-skeleton hybrid alkaline microporous material, characterized in that it is obtained by replacing 1-20% of the skeleton oxygen in the skeleton oxygen-containing microporous material with amine groups, wherein the amine groups are methylamine, ethylamine or Dimethylamine. 2、根据权利要求1所述的微孔材料,其特征在于所述的骨架含氧微孔材料是晶态的沸石分子筛,磷酸铝分子筛,介孔分子筛,非晶态的硅胶或白炭黑。2. The microporous material according to claim 1, characterized in that the skeleton oxygen-containing microporous material is crystalline zeolite molecular sieve, aluminum phosphate molecular sieve, mesoporous molecular sieve, amorphous silica gel or white carbon black. 3、一种氮骨架杂化碱性微孔材料,其特征在于由权利要求1所述的胺骨架杂化碱性微孔材料经400-800℃焙烧1-3小时制备获得。3. A nitrogen-skeleton hybrid basic microporous material, characterized in that it is prepared from the amine-skeleton hybrid basic microporous material as claimed in claim 1, which is calcined at 400-800°C for 1-3 hours. 4、一种如权利要求1所述的碱性微孔材料的制备方法,其特征在于将基底材料与胺的水溶液混合,置于反应釜中,进行水热反应,温度100-200℃,时间10-50小时,得到胺取代骨架杂化微孔材料;或将胺置于反应釜底层,基底材料置于上层,进行水热反应,温度100-200℃,时间10-50小时,利用加热时产生的蒸汽与基底材料发生气/固相反应,制备得胺取代骨架杂化微孔催化材料。4. A method for preparing an alkaline microporous material as claimed in claim 1, characterized in that the base material is mixed with an aqueous solution of amine, placed in a reaction kettle, and subjected to a hydrothermal reaction at a temperature of 100-200°C and a time of 10-50 hours to obtain the amine-substituted skeleton hybrid microporous material; or put the amine on the bottom of the reactor and the base material on the upper layer to carry out hydrothermal reaction at a temperature of 100-200°C and a time of 10-50 hours. The generated steam undergoes a gas/solid phase reaction with the base material, and the amine-substituted skeleton hybrid microporous catalytic material is prepared. 5、一种如权利要求3所述的碱性微孔材料的制备方法,其特征在于将权利要求4所得材料进一步经400~800℃的温度焙烧1~3小时,制得骨架氮杂化碱性微孔材料。5. A method for preparing an alkaline microporous material as claimed in claim 3, characterized in that the material obtained in claim 4 is further calcined at a temperature of 400-800°C for 1-3 hours to obtain a skeleton nitrogen hybrid alkali microporous material.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479354A1 (en) * 1990-09-12 1992-04-08 Shell Internationale Researchmaatschappij B.V. Nitrided silica
WO2003097531A1 (en) * 2002-05-01 2003-11-27 Exxonmobil Chemical Patents Inc. Synthetic porous crystalline mcm-71, its synthesis and use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479354A1 (en) * 1990-09-12 1992-04-08 Shell Internationale Researchmaatschappij B.V. Nitrided silica
WO2003097531A1 (en) * 2002-05-01 2003-11-27 Exxonmobil Chemical Patents Inc. Synthetic porous crystalline mcm-71, its synthesis and use

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