阅读说明：本技术 一种阴-非离子双子表面活性剂模板制备多级孔zsm-5分子筛的方法 (A kind of method that anion-nonionic Gemini surface active agent template prepares multi-stage porous ZSM-5 molecular sieve ) 是由 侯琳熙 李盼 郭英雄 阮任杰 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种阴-非离子双子表面活性剂模板制备多级孔ZSM-5分子筛的方法,属于分子筛技术领域。首先制备了一种廉价的、环保的、高效的介孔模板剂,并以此作模板,通过水热、煅烧等步骤得到多级孔ZSM-5分子筛。本发明最大特点在于制备的多级孔ZSM-5分子筛具有可调节的孔结构,模板剂阴-非离子双子表面活性剂结构易于调控,通过选择不同分子结构以及不同用量的双子表面活性剂可以制备不同孔道结构的微介孔材料。本发明的分子筛可用于催化剂和催化剂载体,适于工业化推广应用。(The invention discloses a kind of methods that anion-nonionic Gemini surface active agent template prepares multi-stage porous ZSM-5 molecular sieve, belong to technical field of molecular sieve.Be prepared for a kind of cheap, environmentally friendly, efficient mesoporous template first, and template made with this, by hydro-thermal, calcining and etc. obtain multi-stage porous ZSM-5 molecular sieve.Maximum feature of the invention is that the multi-stage porous ZSM-5 molecular sieve prepared has adjustable pore structure, template anion-nonionic Gemini surface active agent structure is easy to regulate and control, and micro- mesoporous material of different cellular structures can be prepared by the Gemini surface active agent of selection different molecular structures and different amounts.Molecular sieve of the invention can be used for catalyst and catalyst carrier, be suitable for industrial application.)

1. a kind of method that anion-nonionic Gemini surface active agent template prepares multi-stage porous ZSM-5 molecular sieve, which is characterized in that It is made of following step:

(1) silica-alumina gel is prepared, sodium hydroxide, sodium metaaluminate and 4-propyl bromide are dissolved into deionized water, then, In Lower tetraethyl orthosilicate of violent stirring and anion-nonionic Gemini surface active agent template are added in mixed solution, so that Molar ratio in mixture is SiO₂/Al₂O₃=13~50, Na₂O/SiO₂=0.1~0.5, TPABr/SiO₂=0.05~0.2, Gemini surface active agent template/SiO₂=0.04~0.15, H₂O/SiO₂=50~200, then synthesized gel rubber is stirred at room temperature 1-4 h；

(2) the gained mixture in step (1) is transferred in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, and by hydro-thermal reaction Kettle is put into constant temperature oven, is reacted 2~5 days under the conditions of 130~180 DEG C；

(3) after reaction, taking-up hydrothermal reaction kettle, which is put into cold water, is quenched, and reaction solution is poured into centrifuge tube and is centrifugated, Washing, ethyl alcohol are washed till neutrality, 100~120 DEG C drying 10~24 hours, obtain solid product；

(4) solid product that step (3) obtain is placed in Muffle furnace under moving air in 500~600 DEG C of 4~10 h of calcining Template agent removing is removed, G is obtained_xZSM-5 molecular sieve powder；

The Gemini surface active agent structure are as follows:

,

Wherein m=8,10,12,14,16,18;N=3,5,6,7,9,15,23, wherein-(CH₂CH₂O)_nPart For the non-ionic moiety of anion-nonionic Gemini surface active agent ,-CH₂SO₃Na is anion part.

2. the side that anion-nonionic Gemini surface active agent template according to claim 1 prepares multi-stage porous ZSM-5 molecular sieve Method, which is characterized in that the Gemini surface active agent is as made from following operating procedure: by 11.2 g itaconic anhydrides and 119.3 g ethoxylated dodecyl alcohols are added in the three-necked flask of 250 mL, be added 3 %w/w of itaconic anhydride to toluene sulphur Acid as catalyst reacts 12 h at 120 DEG C；Then the aqueous solution of sodium bisulfite that 20.3 mL mass fraction, 35 % is added exists Then 90 DEG C of 4 h of reaction are cooled to room temperature again with acetone recrystallization, obtain pale yellow powder.

Technical field

The invention belongs to Zeolite synthesis technical fields, and in particular to a kind of anion-nonionic Gemini surface active agent template The method for preparing multi-stage porous ZSM-5 molecular sieve.

Background technique

Zeolite molecular sieve zsm-5 have regular aperture structure, have wide range of applications, can be used for catalyst, catalyst carrier, Adsorbent and ion-exchanger can also be applied to the weight such as alkylating aromatic hydrocarbon, catalytic cracking, light-hydrocarbon aromatized, preparing gasoline by methanol In the industrial production wanted.Also, octane number can be improved when being used as the catalyst additive of FCC in ZSM-5 molecular sieve, increases Produce low-carbon alkene；Furthermore ZSM-5 molecular sieve also can be widely used to shape selective catalysis, such as p-Diethylbenzene catalyst, xylene isomerization Change catalyst.In addition, ZSM-5 molecular sieve aperture structure and acid strength, acid amount adjustable properties also become excellent industry Catalyst carrier.But actual Industrial Catalysis reaction in, in zeolite molecular sieve uniform narrow micropore canals there is also compared with More negative effects, is mainly reflected in the following aspects: (1) being unfavorable for macromolecular and participate in reaction, zeolite activity position utilization rate It is low；(2) diffusion and absorption of reactant or product in zeolite cavity seriously are hindered, causes reaction speed slower；(3) right The macromolecular generated in reaction cannot spread out out of zeolite cavity well and cause the generation of carbon distribution, greatly shorten Service life of zeolite catalyst.

Compared with micropore ZSM-5 molecular sieve, the higher external surface area of multi-stage porous ZSM-5 molecular sieve has preferably big point The accessibility of sub- reactant makes it have higher catalytic activity.In addition to this, multi-stage porous ZSM-5 molecular sieve pore size Short, diffusion is good, has adjustable pore structure, and surface utilisation is high, this makes it have the advantage of many uniquenesses, to big point The cracking ability of sub- reactant is significantly enhanced.Multi-orifice zeolite material is synthesized there are three types of strategy, the first strategy is using micro- The synergistic effect of pore structure directed agents and meso-hole structure directed agents passes through hydro-thermal solvent-thermal method one-step synthesis method porous zeotile； Second of strategy is to first pass through the amorphous mesopore molecular sieve of supramolecular-templating synthesis, is then carried out using microcellular structure directed agents brilliant Change processing, so that porous zeotile can be obtained；The third strategy is to synthesize first with microcellular structure directed agents containing only microcellular structure Zeolite, then obtain porous zeotile by some post-processing approach.But the common synthesis side of multi-stage porous ZSM-5 zeolite There are many problems for method, and if complex for operation step, synthesis process control is difficult, with high costs, environmental benefit is poor, pore performance is difficult to Modulation etc..

The Gemini surface active agent for synthesising mesoporous material pattern reported in document at present is mainly cationic, And it is concentrated mainly on quaternary ammonium salt Gemini surface active agent.For example, Ryoo et al. is template using bull cation quaternary ammonium salt Agent has synthesized the molecular sieve with hierarchical porous structure, uses eight ammonium head Bola type cationic surfaces in patent CN104402020A Activating agent synthesizes multistage porous molecular sieve.Xie Xianmei et al. discloses one kind in patent CN109399660A and CN106185972A The production method that quaternary ammonium salt Gemini surface active agent synthesizes multistage porous molecular sieve.Such Gemini surface active agent has many excellent Different performance, but one of critical defect-environmental benefit is poor-limits its further application and development.Meanwhile it Biodegradation rate it is slower, the halogen gas for decomposing and discharging is extremely harmful to atmospheric environment.Therefore, it researches and develops Environmentally friendly Gemini surface active is very necessary.For this purpose, this field be badly in need of seeking it is a kind of cheap, environmentally friendly, high The mesoporous template of effect prepares multi-stage porous ZSM-5 molecular sieve.

Summary of the invention

It is an object of the invention to the with high costs, environmental benefits for existing quaternaries cation Gemini surface active agent The disadvantage of difference, provides a kind of method that anion-nonionic Gemini surface active agent template prepares multi-stage porous ZSM-5 molecular sieve product. In order to achieve the object of the present invention, the technical solutions adopted are as follows.

(1) silica-alumina gel is prepared, a certain amount of sodium hydroxide, sodium metaaluminate and 4-propyl bromide are dissolved into deionization In water.Then, tetraethyl orthosilicate and anion-nonionic Gemini surface active agent template are added to mixing under violent stirring In solution.So that the molar ratio in mixture is SiO₂/Al₂O₃=13~50, Na₂O/SiO₂=0.1~0.5, TPABr/SiO₂ =0.05~0.2, Gemini surface active agent template/SiO₂=0.04~0.15, H₂O/SiO₂=50~200.Then synthesized gel rubber 1-4 h is stirred at room temperature.

(2) the gained mixture in step 1 is transferred in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, and by hydro-thermal Reaction kettle is put into constant temperature oven, is reacted 2~5 days under the conditions of 130~180 DEG C.

(3) after reaction, taking-up hydrothermal reaction kettle, which is put into cold water, is quenched, and reaction solution is poured into centrifugation point in centrifuge tube From, washing, ethyl alcohol are washed till neutrality, 100~120 DEG C drying 10~24 hours, obtain solid product.

(4) by step 3 obtain solid product be placed in Muffle furnace under moving air in 500~600 DEG C calcine 4~ 10 h remove template agent removing, obtain G_xZSM-5 molecular sieve powder.

Used Gemini surface active agent structure are as follows:

,

Wherein m=8,10,12,14,16,18;N=3,5,6,7,9,15,23, wherein-(CH₂CH₂O)_nPart For the non-ionic moiety of anion-nonionic Gemini surface active agent ,-CH₂SO₃Na is anion part.

The Gemini surface active agent is as made from following operating procedure: by 11.2 g itaconic anhydrides (IAn) and 119.3 g ethoxylated dodecyl alcohols (Gemini-12-9) are added in the three-necked flask of 250 mL, and 3 %(are added with respect to IAn Quality) p-methyl benzenesulfonic acid make catalyst, 12 h are reacted at 120 DEG C；Then the Asia of 20.3 mL mass fraction, 35 % is added Sodium bisulphate solution is in 90 DEG C of 4 h of reaction.Room temperature is cooled to then again with acetone recrystallization, after 50 mL acetone are added, 0 DEG C Solid is precipitated after cooling, obtains pale yellow powder after suction filtration.

Compared with the prior art, the advantages of the present invention are as follows:

1. template anion-nonionic Gemini surface active agent of the invention has at low cost, small toxicity, synthesis process simple, easy In control, it is biodegradable the advantages that, be suitble to industrial use needs, solve quaternary ammonium salt Gemini surface active agent synthesis it is more The poor technical problem of grade porous molecular sieve environmental benefit.

2. multi-stage porous ZSM-5 molecular sieve product synthesis process of the invention is simple, with common micropore ZSM-5 molecular sieve phase Than, due to mesoporous introducing, aperture size is bigger, and specific surface area is higher, the accessibility with better macromolecule reactant, It is set to have higher catalytic activity.

3. its maximum feature of multi-stage porous ZSM-5 molecular sieve product of the invention is there is adjustable pore structure, mould Plate agent anion-nonionic Gemini surface active agent structure is easy to regulate and control (such as hydrophilic chain length length), by selecting different molecular knot The Gemini surface active agent of structure and different amounts can prepare the mesoporous material of different cellular structures.

4. multi-stage porous ZSM-5 molecular sieve product of the invention can be used as catalyst and catalyst carrier, pass through adjusting Si/Al, thus it is possible to vary zeolite interior acidic site makes it reach excellent catalytic performance in corresponding catalysis reaction.

Detailed description of the invention

Fig. 1 is the multi-stage porous G that embodiment 1 obtains₉The XRD spectra of ZSM-5 molecular sieve.

Fig. 2 is the multi-stage porous G that embodiment 1 obtains₉The N of type ZSM 5 molecular sieve₂Adsorption desorption curve.

Fig. 3 is the multi-stage porous G that embodiment 1 obtains₉The BJH pore size distribution curve of type ZSM 5 molecular sieve.

Fig. 4 is the multi-stage porous G that embodiment 1 obtains₉The SEM photograph of type ZSM 5 molecular sieve.

The present invention is described in more detail for specific embodiment following example, but protection scope of the present invention is not only It is limited to these embodiments.

Preparation method for gemini surfactant: by 11.2 g itaconic anhydrides (IAn) and 119.3 g lauryl alcohol polyethylene glycol oxides Ether (Gemini-12-9) is added in the three-necked flask of 250 mL, be added 3 %(with respect to IAn mass) p-methyl benzenesulfonic acid urge Agent reacts 12 h at 120 DEG C；Then the aqueous solution of sodium bisulfite of 20.3 mL mass fraction, 35 % is added at 90 DEG C React 4 h.It is cooled to room temperature and solid then is precipitated after 0 DEG C of cooling after 50 mL acetone are added with acetone recrystallization again, filter After obtain pale yellow powder.