Preparation method and application of surfactant and ZSM-5 molecular sieve

Abstract

The invention discloses a surfactant, and a preparation method and application of a ZSM-5 molecular sieve, and belongs to the technical field of molecular sieves. The surfactant has a structure as shown in a formula I, wherein-O-Ar-O-is a chiral naphthol group as shown in a formula II, and Ar < 0 > is phenyl, naphthyl, anthryl or phenanthryl; n is an integer between 2 and 14; r is a quaternary ammonium group as shown in a formula III, X is a halogen anion, and t is an integer between 2 and 6. According to the embodiment of the invention, the spherical nano ZSM-5 molecular sieve with a two-dimensional layered mesoporous structure is successfully synthesized by using the surfactant and preferably assisted by means of seed crystal and two-stage temperature crystallization. The ZSM-5 molecular sieve prepared by the embodiment of the invention is relatively high in specific surface area, has the characteristic of rich hierarchical pore structures, and is beneficial to application in light hydrocarbon cracking reaction. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of molecular sieves, and in particular to a surfactant, a preparation method of ZSM-5 molecular sieve and applications thereof. Background Art

[0002] Zeolite molecular sieves are inorganic crystals with a regular microporous structure, commonly used as industrial adsorbents and catalysts. ZSM-5 zeolite, a new type of zeolite molecular sieve containing organic amine cations, was synthesized by the American company Mobil in the late 1960s. It can be used as a catalyst for catalytic cracking reactions, among other things. Its common preparation method involves mixing raw materials such as a silicon source, an aluminum source, a template (such as an organic amine), and water, followed by a crystallization reaction at a certain temperature and pressure, followed by washing, drying, and calcination. However, the mass transfer resistance caused by the narrow micropores of zeolite molecular sieves seriously hinders their specific applications in some fields. To improve this problem, researchers are committed to synthesizing molecular sieves with mesoporous structures, primarily to increase their specific surface area and thereby improve the mass transfer rate of the substrate.

[0003] Currently, the molecular sieve synthesis methods that have attracted widespread attention include nano-molecular sieve assembly, demetallization, hard templates, and soft templates. The soft template method primarily utilizes templates (such as micelles) that maintain their specific structure through weak interactions. This allows the synthesis of mesoporous molecular sieves with varying pore sizes through molecular self-assembly, offering certain advantages. However, the specific surface area of ZSM-5 molecular sieves prepared using existing techniques still needs to be improved. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a surfactant, a preparation method and application of ZSM-5 molecular sieve. The present invention utilizes the surfactant to prepare a molecular sieve with a high specific surface area, which has good application prospects in reactions such as light hydrocarbon cracking.

[0005] The present invention provides a surfactant having a structure of Formula I:

[0006]

[0007] Wherein, -O-Ar-O- is a chiral naphthol group shown in Formula II, Ar0 is phenyl, naphthyl, anthracenyl or phenanthrenyl; n is an integer between 2 and 14; R is a quaternary ammonium group shown in Formula III, X is a halogen anion, and t is an integer between 2 and 6;

[0008]

[0009] Preferably, the formula I satisfies at least one of the following conditions: n is an integer between 4 and 12; X is a chloride ion or a bromide ion; and t is an integer between 4 and 6.

[0010] The present invention provides a method for synthesizing the aforementioned surfactant, comprising:

[0011] Naphthol, a disubstituted alkylating agent, N,N,N',N'-tetramethyl-alkyldiamine, a dihalogenated alkane and N,N-dimethyl-alkylamine are reacted to obtain a surfactant represented by Formula I;

[0012] The naphthol is (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, (S)-3,3'-bis(naphthyl)-1,1'-bis-2-naphthol, (S)-3,3'-di-9-phenanthrenyl-1,1'-binaphthol or (S)-3,3'-di-9-anthryl-1,1'-di-2-naphthol;

[0013] The number of alkyl groups in the disubstituted alkylating agent is 2 to 14;

[0014] The number of alkyl groups in the N,N,N',N'-tetramethyl-dialkylamine, dihalogenated alkane and N,N-dimethyl-alkylamine is 2-6.

[0015] The present invention provides a method for preparing a ZSM-5 molecular sieve, comprising the following steps:

[0016] The surfactant, seed crystals, aluminum source, silicon source, alkaline substance and water are mixed to obtain a gel;

[0017] crystallizing the gel to obtain a molecular sieve solid;

[0018] The molecular sieve solid is ion-exchanged using ammonium salt, and then calcined to obtain a ZSM-5 molecular sieve with a special morphology.

[0019] Preferably, the preparation method satisfies at least one of the following: the aluminum source is one or more of aluminum hydroxide, aluminate and aluminum sulfate; the silicon source is one or more of silica gel, ethyl orthosilicate, silica sol and water glass; the alkaline substance includes one or more of organic bases and inorganic bases.

[0020] Preferably, the molar ratio of SiO2 / Al2O3 in the silicon source and the aluminum source is 25-100:1; and / or the molar ratio of the aluminum source calculated as Al2O3 to the alkali is 1:9-15.

[0021] Preferably, the crystallization comprises: firstly performing low-temperature pre-crystallization at a temperature below 100° C. for at least 6 hours, and then performing high-temperature crystallization treatment at a temperature above 150° C. to obtain a molecular sieve solid.

[0022] Preferably, the temperature of the high temperature crystallization treatment is 150°C to 200°C, and the time is more than 24 hours;

[0023] After the high temperature crystallization treatment, the method further comprises: calcining the crystallized molecular sieve at a temperature of 550-700° C. for 4-6 hours to obtain a molecular sieve solid.

[0024] Preferably, the ZSM-5 molecular sieve with special morphology has a two-dimensional layered mesoporous structure with a specific surface area of 300m 2 / g or above.

[0025] The present invention provides a method for cracking light hydrocarbons, comprising the following steps:

[0026] The ZSM-5 molecular sieve obtained by the preparation method described above is used as a catalytic active component, and a light hydrocarbon raw material is subjected to a catalytic cracking reaction to obtain a cracking product.

[0027] The present invention provides a novel quaternary ammonium surfactant, as shown in Formula I, comprising a chiral naphthol group as shown in Formula II and a quaternary ammonium group as shown in Formula III. The surfactant has a chiral hydrophobic binaphthyl molecular center-connected structure, with hydrophobic long chains of a certain length symmetrical about this center, and contains a quaternary ammonium salt group, thereby exhibiting excellent surface activity and other characteristics.

[0028] The embodiment of the present invention utilizes the surfactant, preferably with the aid of seed crystals and two-stage temperature crystallization, to successfully synthesize a spherical nano ZSM-5 molecular sieve with a two-dimensional layered mesoporous structure. In the present invention, the surfactant with a chiral hydrophobic center self-assembles to form a spiral cylindrical unit, thereby guiding the growth of the two-dimensional molecular sieve. Specifically, the two naphthyl groups of the binaphthyl molecule can rotate along the CC single bond to adjust its spatial conformation to form a spiral cylindrical unit; the quaternary ammonium salt group connected to the binaphthyl molecule can interact with the silicon source and the aluminum source to form a molecular sieve skeleton; the long hydrophobic chain of the surfactant destroys the growth of the molecular sieve into block crystals and adjusts the spacing length to match the molecular sieve MFI framework, thereby forming a ZSM-5 molecular sieve with a two-dimensional layered mesoporous structure.

[0029] Under this premise, the embodiment of the present invention adds seed crystals to the system and makes the quaternary ammonium salt groups in the surfactant and the molecular sieve more tightly bound and dispersed more evenly during the low-temperature pre-crystallization stage. Then, after complete crystallization at high temperature, a spherical nano ZSM-5 molecular sieve with a two-dimensional layered mesoporous structure is formed. The ZSM-5 molecular sieve prepared by the embodiment of the present invention has a high specific surface area and a rich multi-level pore structure, which is beneficial to its application in light hydrocarbon cracking reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of the synthesis process of surfactants according to some embodiments of the present invention;

[0031] Figure 2 The powder X-ray diffraction spectra of the molecular sieves in Example 1 and Comparative Example 1 of the present invention are as follows;

[0032] Figure 3 The scanning electron microscope images of the molecular sieves in Example 1 and Comparative Example 1 are shown. DETAILED DESCRIPTION

[0033] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, the technical solutions of the present invention are described in detail below in conjunction with specific embodiments. The described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0034] The present invention provides a surfactant having a structure of Formula I:

[0035]

[0036] Wherein, -O-Ar-O- is a chiral naphthol group shown in Formula II, Ar0 is phenyl, naphthyl, anthracenyl or phenanthrenyl; n is an integer between 2 and 14; R is a quaternary ammonium group shown in Formula III, X is a halogen anion, and t is an integer between 2 and 6;

[0037]

[0038] The surfactant provided by the present invention has a unique structure and has the characteristics of good surface activity and the like.

[0039] The general structure of the surfactant of the present invention is shown in Formula I, which mainly has a symmetrical molecular structure and belongs to Gemini surfactant. Among them, the linker is a chiral binaphthyl structure substituted by an aromatic group, the hydrophilic head group is -O-, and the hydrophobic chain is R-(CH2) n -.

[0040] Formula II of the present invention shows a chiral naphthol group, which contains a hydrophilic head group but does not exhibit chiral characteristics. In Formula II, the substituent on the binaphthyl molecule is phenyl, naphthyl, anthracenyl or phenanthrenyl, located in the ortho position of -O-.

[0041] Formula III of the present invention shows a hydrophobic group containing a quaternary ammonium structure, wherein X is a halogen anion, further a chloride ion or a bromide ion, more preferably a bromide ion. t is an integer between 2 and 6, specifically 2, 3, 4, 5, 6, preferably 6. For some preferred embodiments, X in Formula III is a bromide ion (Br - ), and t is 6. And, R-(CH2) n- is a hydrophobic straight chain; n is an integer between 2 and 14, preferably an integer between 4 and 12, including 4, 6, 8, 10, 11, 12, and more preferably an even number. In addition, the "*" represents a connecting bond; and the methyl group (CH3) can be abbreviated as a single bond. Specifically, the surfactants described in some embodiments of the present invention have the following structure:

[0042]

[0043]

[0044]

[0045]

[0046] The embodiment of the present invention provides a method for synthesizing the surfactant described above, comprising: reacting naphthol, a disubstituted alkylating agent, N,N,N',N'-tetramethyl-dialkylamine, a dihalogenated alkane, and N,N-dimethyl-alkylamine to obtain a surfactant represented by formula I;

[0047] The naphthol is (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, (S)-3,3'-bis(naphthyl)-1,1'-bis-2-naphthol, (S)-3,3'-di-9-phenanthrenyl-1,1'-binaphthol or (S)-3,3'-di-9-anthryl-1,1'-bis-2-naphthol; the number of alkyl groups in the disubstituted alkylating agent is 2 to 14, and can further be 3 to 13 or 4 to 12; the number of alkyl groups in the N,N,N',N'-tetramethyl-alkyldiamine, dihalogenated alkane and N,N-dimethyl-alkylamine is 2 to 6, and preferably 4 to 6.

[0048] Wherein, the disubstituted alkylating agent is preferably a dihalogenated alkane, more preferably a dibromoalkane. Further, the N,N,N',N'-tetramethyl-alkyldiamine, dihalogenated alkane and N,N-dimethyl-alkylamine are specifically N,N,N',N'-tetramethyl-1,6-hexanediamine, 1,6-dibromohexane and N,N-dimethyl-hexylamine, respectively. The above-mentioned raw materials are reacted in a solvent in the presence of a catalyst to obtain the surfactant. The solvent includes but is not limited to acetone and acetonitrile, and its amount can dissolve the raw materials; the catalyst is preferably potassium carbonate (K2CO3), and its amount is the catalyst amount in alkylation and substitution reactions well known to those skilled in the art. In addition, the reaction is carried out under an inert atmosphere, such as refluxing for a certain time under a nitrogen (N2) atmosphere.

[0049] In a specific embodiment of the present invention, the method for synthesizing the surfactant comprises the following steps:

[0050] (1) A certain amount of naphthol, dibromoalkane, K2CO3 and acetone are mixed and refluxed for a certain period of time under N2 atmosphere. After filtration, alkylated naphthol is obtained, which is recorded as substance A.

[0051] (2) Substance A is mixed with a certain amount of N,N,N',N'-tetramethyl-1,6-hexanediamine and acetonitrile, and refluxed at a certain temperature for a certain time. After filtering, washing, and drying, an alkyl naphthol containing hexyl quaternary ammonium is obtained, which is recorded as substance B.

[0052] (3) Substance B is mixed with a certain amount of 1,6-dibromohexane and acetonitrile, and refluxed at a certain temperature for a certain time. After filtering, washing, and drying, an alkyl naphthol with an extended alkyl chain is obtained, which is recorded as substance C.

[0053] (4) Substance C is mixed with a certain amount of N,N-dimethylhexylamine and acetonitrile, and refluxed at a certain temperature for a certain time. After filtering, washing, and drying, the surfactant is obtained, which can be recorded as product D.

[0054] In step (1), the naphthol is one or more of (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, (S)-3,3'-bis(naphthyl)-1,1'-bis-2-naphthol, (S)-3,3'-di-9-phenanthrenyl-1,1'-binaphthol, and (S)-3,3'-di-9-anthryl-1,1'-bis-2-naphthol, all of which have the following structural formulas and are commercially available products. The dibromoalkane may be one or more of 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, 1,11-dibromondecane, and 1,12-dibromododecane; the molar ratio of the naphthol to the dibromoalkane is preferably 1:15-30, for example, 1:15, 1:20, 1:25, or 1:30. The molar ratio of naphthol to K2CO3 can be 1:15-20, for example, 1:15, 1:18, or 1:20; the molar ratio of naphthol, dibromoalkane, K2CO3, and acetone can be 1:15-30:15-20:240-320; and the reflux reaction time is preferably 20-30 h.

[0055]

[0056] In step (2), the molar ratio of substance A to N,N,N',N'-tetramethyl-1,6-hexanediamine can be 1:15-25, for example, 1:15, 1:16, 1:20, or 1:25; the molar ratio of substance A to N,N,N',N'-tetramethyl-1,6-hexanediamine to acetonitrile can be 1:15-25:560-960. The reflux reaction temperature is preferably 75-90°C, and the predetermined time can be 20-30 hours.

[0057] In step (3), the molar ratio of substance B to 1,6-dibromohexane can be 1:15-25, and the molar ratio of substance B, 1,6-dibromohexane, and acetonitrile can be 1:15-25:640-1000. The certain temperature is preferably 75-90°C, and the certain time can be 20-30 hours.

[0058] In step (4), the molar ratio of the substance C to N,N-dimethylhexylamine is preferably 1:2-4, and the molar ratio of the substance C:N,N-dimethylhexylamine:acetonitrile is 1:2-4:560-960; the certain temperature is 75-90°C, and the certain time is 20-30h.

[0059] The filtration, washing and drying in steps (1) to (4) are all conventional operations in the art. The solvent used for the washing is preferably diethyl ether; the drying temperature can be 60-100°C and the drying time can be 6-12 hours.

[0060] Taking (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol and 1,4-dibromobutane as raw materials, the synthesis process is as follows Figure 1 Wherein, (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol reacts with 1,4-dibromobutane, and the reaction product reacts with N,N,N',N'-tetramethyl-1,6-hexanediamine, 1,6-dibromohexane, and N,N-dimethylhexylamine in sequence to obtain the product.

[0061] The present invention provides a method for preparing ZSM-5 molecular sieve, comprising the following steps:

[0062] The surfactant, seed crystals, aluminum source, silicon source, alkaline substance and water are mixed to obtain a gel;

[0063] crystallizing the gel to obtain a molecular sieve solid;

[0064] The molecular sieve solid is ion-exchanged using ammonium salt, and then calcined to obtain a ZSM-5 molecular sieve with a special morphology.

[0065] Based on the surfactant, the embodiment of the present invention can produce a ZSM-5 molecular sieve with a high specific surface area and a multi-level pore structure, and the ZSM-5 molecular sieve has special morphological characteristics.

[0066] In a specific embodiment of the present invention, a method for preparing a ZSM-5 molecular sieve with a special morphology is provided, comprising the following steps:

[0067] Step 1) Mix an aluminum source, an alkaline substance, and a homemade surfactant (the surfactant described above) with water in a certain proportion and stir them evenly to obtain a first solution.

[0068] Step 2) adding a silicon source to the first solution to obtain a first gel.

[0069] Step 3) adding a certain amount of seed crystals to the first gel to obtain a second gel.

[0070] Step 4) Transfer the second gel to a round-bottom flask and pre-crystallize it at a certain temperature for a period of time to obtain a third gel.

[0071] Step 5) Transfer the third gel to a crystallization kettle and crystallize it at a certain temperature for a certain time.

[0072] Step 6) washing, drying, and calcining the crystallized molecular sieve to obtain a molecular sieve solid, which is referred to as solid a.

[0073] Step 7) using ammonium salt to perform ion exchange on solid a, and then calcining at a certain temperature and time to obtain the ZSM-5 molecular sieve with a special morphology, which can be recorded as solid b.

[0074] In step 1), the aluminum source is preferably one or more of aluminum hydroxide, sodium aluminate, and aluminum sulfate; the alkaline substance includes one or more of an organic base and an inorganic base, such as sodium hydroxide. The molar ratio of the aluminum source (calculated as Al2O3) to the surfactant is preferably 1:1-5; the molar ratio of the aluminum source (Al2O3): surfactant: water: base can be 1:1-5: 500-2000: 9-15. The mixture can be uniformly mixed by stirring to obtain a first solution.

[0075] In step 2), the silicon source is preferably one or more of silica gel, tetraethyl orthosilicate, silica sol, and water glass, and further preferably silica gel, tetraethyl orthosilicate, or silica sol. The silicon source and aluminum source have a molar ratio of SiO₂:Al₂O₃ of 25-100; corresponding commercially available products can be used.

[0076] Preferably, the seed crystals in step 3) are one or both of S-1 seed crystals and ZSM-5 seed crystals, which are conventional molecular sieve seed crystals available on the market; the mass ratio of seed crystals: (SiO2 + Al2O3) is preferably 0.05-5wt%, more preferably 0.1-4.5wt%.

[0077] In the embodiments of the present invention, a surfactant having the aforementioned structure is used to mix an aluminum source and a silicon source in water to produce a first gel, which is then supplemented with seed crystals to produce a second gel. Subsequently, the embodiments of the present invention undergo a two-stage crystallization process: low-temperature pre-crystallization and high-temperature crystallization, to produce a molecular sieve solid. The low-temperature pre-crystallization stage allows the quaternary ammonium salt groups in the surfactant to bind more tightly to the molecular sieve, resulting in a more uniform dispersion.

[0078] The step 4) is a specific low-temperature pre-crystallization, the pre-crystallization temperature is preferably 60-100°C, and the time can be 6-24 hours. The step 5) is a high-temperature crystallization treatment stage, the crystallization temperature is preferably 150-200°C, and the time can be 24-72 hours.

[0079] After crystallization, embodiments of the present invention preferably further include calcination to obtain a relatively stable molecular sieve solid. Preferably, the calcination temperature in step 6) is 550-700°C, preferably 600-700°C, for 4-6 hours. The present invention does not specifically limit washing and drying.

[0080] Preferably, in step 7), the ammonium salt is one or more of ammonium nitrate, ammonium chloride, and ammonium acetate; the ion exchange treatment can be performed at a solid-liquid ratio of 1:10. The calcination temperature after the ion exchange can be 550-700°C for 4-6 hours.

[0081] In the embodiment of the present invention, the ZSM-5 molecular sieve with special morphology has a two-dimensional layered mesoporous structure with a specific surface area of 300m 2 Specifically, the prepared ZSM-5 molecular sieve has a special morphological feature, and the crystals present a nano-sized two-dimensional layer stacked sponge sphere morphology, are rich in stacked mesopores, and have a high specific surface area.

[0082] In this embodiment of the present invention, this molecular sieve is used as the active ingredient in a light hydrocarbon cracking catalyst, demonstrating excellent diene selectivity in the light hydrocarbon cracking reaction. The light hydrocarbon catalytic cracking catalyst prepared in this embodiment of the present invention can improve substrate diffusion rate, reaction conversion rate, and diene selectivity, making it particularly suitable for use in refinery light hydrocarbon cracking to increase diene production.

[0083] An embodiment of the present invention provides a method for cracking light hydrocarbons, comprising the following steps:

[0084] The ZSM-5 molecular sieve obtained by the preparation method described above is used as a catalytic active component, and a light hydrocarbon raw material is subjected to a catalytic cracking reaction to obtain a cracking product.

[0085] In a specific embodiment of the present invention, the ZSM-5 molecular sieve solid b can be used as the catalyst active component, uniformly mixed with a certain proportion of a matrix (also known as a carrier, such as kaolin) and a binder, and then ball-milled and atomized to form catalyst microspheres. For example, the catalyst comprises: 20-40% kaolin; 30-50% of the molecular sieve; and 10-30% of the binder. The binder includes, but is not limited to, a mixture of one or more of alumina sol, silica sol, acidified pseudo-boehmite, water glass, and aluminum phosphate. The microspheres can have a particle size of 20-80 microns.

[0086] In this embodiment of the present invention, the catalyst microspheres are calcined, for example, at 500°C for 2 hours. The resulting sample is then subjected to a catalytic cracking reaction of a light hydrocarbon feedstock in a fixed fluidized bed reactor. The catalytic cracking feedstock is one or a mixture of C5-C8 alkanes, alkenes, and aromatics. The resulting cracking products include ethylene, propylene, and the like.

[0087] In some embodiments, the catalytic evaluation test method for the fixed fluidized bed reactor is as follows: 200 g of catalyst is added to the fixed fluidized bed reactor, and the system temperature is set at 630°C, the nitrogen flow rate is 200 mL / min, and the water flow rate is 6 g / min. After nitrogen fluidization and temperature increase, the oil pump is refluxed for 1 minute, 20 g of oil is introduced, the reaction is continued for 8 minutes, and stripping is performed for 20 minutes. The temperature is then raised to 750°C and regenerated for 120 minutes. After the reaction is completed, the water, oil, and air inflow rates are recorded. Refinery gas is analyzed, and the liquid product is collected.

[0088] In the light hydrocarbon cracking reaction, the embodiments of the present invention have a high mass transfer rate, which allows the reaction substrate and the acidic sites to quickly contact and disengage, improves the catalytic efficiency, inhibits the occurrence of secondary reactions, is beneficial to improving the reaction conversion rate and diene selectivity, and inhibits the formation of coke.

[0089] In order to better illustrate the present invention, the following examples are provided to further illustrate the present invention. In the examples, all raw reagents and materials are commercially available, and the experimental methods without specific experimental conditions are conventional methods and conditions well known in the art.

[0090] In this embodiment of the present invention, surfactants represented by Formulas 1 to 20 were synthesized using raw materials including naphthol, various dibromoalkanes, N,N,N',N'-tetramethyl-1,6-hexanediamine, 1,6-dibromohexane, and N,N-dimethylhexylamine; acetone and acetonitrile as solvents; and K2CO3 as a catalyst. The specific steps are as described above.

[0091] The H NMR spectra of the above 20 surfactants are:

[0092] (1)1H-NMR (500MHz, D2O): δ8.13-7.03(m,20H,Ar-H),4.11(t,2H,OCH2),3.94(t,2H,OCH2),3.02-3.26(m,24H,CH2-N + -CH2),2.91-3.02(s,36H,N + (CH3)2),2.53(m,4H,OCH2CH2),2.42(m,4H,OCH2CH2CH2),1.51-1.73(m,28H,CH2CH2CH2CH2,CH2CH2(CH2)2CH2CH 2,CH2CH2(CH2)2CH2CH3),1.11-1.44(m,28H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0093] (2)1H-NMR(500MHz,D2O):δ8.15-7.02(m,24H,Ar-H),4.13(t,2H,OCH2),3.92(t,2H,OCH2),3.05-3.25(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.59(m,4H,OCH2CH2),2.48(m,4H,OCH2CH2CH2),1.50-1.75(m,28H,CH2CH2CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.15-1.45(m,28H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.80(t,6H,CH3)。

[0094] (3)1H-NMR(500MHz,D2O):δ8.14-7.01(m,28H,Ar-H),4.14(t,2H,OCH2),3.93(t,2H,OCH2),3.08-3.26(m,24H,CH2-N + -CH2),2.93-3.00(s,36H,N + (CH3)2),2.57(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.51-1.75(m,28H,CH2CH2CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.16-1.47(m,28H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0095] (4)1H-NMR(500MHz,D2O):δ8.17-7.04(m,28H,Ar-H),4.17(t,2H,OCH2),3.95(t,2H,OCH2),3.05-3.23(m,24H,CH2-N + -CH2),2.90-3.05(s,36H,N+ (CH3)2),2.52(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.57-1.77(m,28H,CH2CH2CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.13-1.45(m,28H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.83(t,6H,CH3)。

[0096] (5)1H-NMR(500MHz,D2O):δ8.14-7.01(m,20H,Ar-H),4.14(t,2H,OCH2),3.95(t,2H,OCH2),3.05-3.21(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.54(m,4H,OCH2CH2),2.45(m,4H,OCH2CH2CH2),1.52-1.75(m,28H,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.14-1.46(m,36H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.79(t,6H,CH3)。

[0097] (6)1H-NMR(500MHz,D2O):δ8.13-7.06(m,24H,Ar-H),4.17(t,2H,OCH2),3.94(t,2H,OCH2),3.05-3.27(m,24H,CH2-N + -CH2),2.93-3.01(s,36H,N + (CH3)2),2.61(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.50-1.77(m,28H,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.17-1.44(m,36H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.82(t,6H,CH3)。

[0098] (7)1H-NMR(500MHz,D2O):δ8.16-7.04(m,28H,Ar-H),4.15(t,2H,OCH2),3.94(t,2H,OCH2),3.05-3.26(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.57(m,4H,OCH2CH2),2.47(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.15-1.47(m,36H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.84(t,6H,CH3)。

[0099] (8)1H-NMR(500MHz,D2O):δ8.17-7.03(m,28H,Ar-H),4.13(t,2H,OCH2),3.97(t,2H,OCH2),3.07-3.23(m,24H,CH2-N + -CH2),2.90-3.07(s,36H,N + (CH3)2),2.57(m,4H,OCH2CH2),2.47(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.15-1.44(m,36H,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.80(t,6H,CH3)。

[0100] (9)1H-NMR(500MHz,D2O):δ8.17-7.02(m,20H,Ar-H),4.13(t,2H,OCH2),3.94(t,2H,OCH2),3.05-3.26(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.57(m,4H,OCH2CH2),2.47(m,4H,OCH2CH2CH2),1.51-1.76(m,28H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH 2,CH2CH2(CH2)2CH2CH3),1.16-1.46(m,44H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0101] (10)1H-NMR(500MHz,D2O):δ8.16-7.03(m,24H,Ar-H),4.16(t,2H,OCH2),3.92(t,2H,OCH2),3.05-3.26(m,24H,CH2-N + -CH2),2.90-3.02(s,36H,N + (CH3)2),2.57(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.50-1.77(m,28H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.17-1.45(m,44H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.82(t,6H,CH3)。

[0102] (11)1H-NMR(500MHz,D2O):δ8.16-7.06(m,28H,Ar-H),4.13(t,2H,OCH2),3.92(t,2H,OCH2),3.05-3.26(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.58(m,4H,OCH2CH2),2.45(m,4H,OCH2CH2CH2),1.50-1.77(m,28H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.17-1.45(m,44H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0103] (12)1H-NMR(500MHz,D2O):δ8.14-7.02(m,28H,Ar-H),4.13(t,2H,OCH2),3.91(t,2H,OCH2),3.04-3.25(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.55(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.50-1.73(m,28H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.13-1.43(m,44H,CH2CH2(CH2)4CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.80(t,6H,CH3)。

[0104] (13)1H-NMR(500MHz,D2O):δ8.15-7.06(m,20H,Ar-H),4.15(t,2H,OCH2),3.93(t,2H,OCH2),3.06-3.25(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.56(m,4H,OCH2CH2),2.45(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.16-1.45(m,52H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0105] (14)1H-NMR(500MHz,D2O):δ8.18-7.02(m,24H,Ar-H),4.13(t,2H,OCH2),3.92(t,2H,OCH2),3.05-3.28(m,24H,CH2-N + -CH2),2.90-3.02(s,36H,N +(CH3)2),2.58(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.50-1.78(m,28H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.18-1.45(m,52H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.82(t,6H,CH3)。

[0106] (15)1H-NMR(500MHz,D2O):δ8.15-7.05(m,28H,Ar-H),4.15(t,2H,OCH2),3.94(t,2H,OCH2),3.04-3.25(m,24H,CH2-N + -CH2),2.90-3.02(s,36H,N + (CH3)2),2.58(m,4H,OCH2CH2),2.48(m,4H,OCH2CH2CH2),1.50-1.78(m,28H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.18-1.45(m,52H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.80(t,6H,CH3)。

[0107] (16)1H-NMR(500MHz,D2O):δ8.15-7.03(m,28H,Ar-H),4.13(t,2H,OCH2),3.93(t,2H,OCH2),3.05-3.24(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.59(m,4H,OCH2CH2),2.46(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH 2,CH2CH2(CH2)2CH2CH3),1.14-1.46(m,52H,CH2CH2(CH2)6CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.82(t,6H,CH3)。

[0108] (17)1H-NMR(500MHz,D2O):δ8.15-7.03(m,20H,Ar-H),4.14(t,2H,OCH2),3.93(t,2H,OCH2),3.05-3.24(m,24H,CH2-N + -CH2),2.90-3.00(s,36H,N + (CH3)2),2.61(m,4H,OCH2CH2),2.49(m,4H,OCH2CH2CH2),1.50-1.77(m,28H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.16-1.45(m,60H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.82(t,6H,CH3)。

[0109] (18)1H-NMR(500MHz,D2O):δ8.14-7.04(m,24H,Ar-H),4.13(t,2H,OCH2),3.95(t,2H,OCH2),3.04-3.25(m,24H,CH2-N + -CH2),2.91-3.02(s,36H,N + (CH3)2),2.58(m,4H,OCH2CH2),2.49(m,4H,OCH2CH2CH2),1.51-1.76(m,28H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.16-1.44(m,60H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.81(t,6H,CH3)。

[0110] (19)1H-NMR(500MHz,D2O): δ8.16-7.02(m,28H,Ar-H),4.13(t,2H,OCH2),3.96(t,2H,OCH2),3.05-3.24(m,24H,CH2-N + -CH2), 2.90-3.01(s,36H,N + (CH3)2),2.56(m,4H,OCH2CH2),2.43(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.16-1.45(m,60H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.83(t,6H,CH3).

[0111] (20)1H-NMR(500MHz,D2O): δ8.17-7.03(m,28H,Ar-H),4.13(t,2H,OCH2),3.97(t,2H,OCH2),3.07-3.25(m,24H,CH2-N + -CH2), 2.93-3.03(s,36H,N + (CH3)2),2.58(m,4H,OCH2CH2),2.47(m,4H,OCH2CH2CH2),1.50-1.76(m,28H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH 2, CH2CH2(CH2)2CH2CH3),1.14-1.44(m,60H,CH2CH2(CH2)8CH2CH2,CH2CH2(CH2)2CH2CH2,CH2CH2(CH2)2CH2CH3),0.83(t,6H,CH3).

[0112] Example 1

[0113] (1) 1 mol (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, 25 mol 1,10-dibromodecane, 18 mol K2CO3 and 280 mol acetone were mixed, refluxed for 24 h under N2 atmosphere, and filtered to obtain substance A.

[0114] (2) 0.7 mol of substance A, 14 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 420 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0115] (3) 0.6 mol of substance B, 12 mol of 1,6-dibromohexane, and 480 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0116] (4) 0.5 mol of substance C was mixed with 1.5 mol of N,N-dimethylhexylamine and 300 mol of acetonitrile, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0117] (5) 0.1 mol of sodium aluminate (calculated as Al2O3), 0.9 mol of sodium hydroxide, 0.5 mol of D product and 100 mol of water were mixed and stirred to obtain a first solution.

[0118] (6) Add 2.5 mol of silica sol (calculated as SiO2) to the first solution to obtain a first gel.

[0119] (7) Add 1 wt% of ZSM-5 seed crystals to the first gel to obtain a second gel.

[0120] (8) The second gel was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain the third gel.

[0121] (9) The third gel was transferred to a crystallization kettle and crystallized at 150°C for 72 h.

[0122] (10) The crystallized molecular sieve was washed, dried at 60 °C for 24 h, and calcined at 550 °C for 6 h to obtain solid a.

[0123] (11) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain ZSM-5 molecular sieve solid b.

[0124] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of the molecular sieve, and 130 g of silica sol were added in this order, mixed, and stirred into a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0125] (13) The prepared catalyst microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0126] Example 2

[0127] (1) 1 mol (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, 30 mol 1,10-dibromodecane, 20 mol K2CO3 and 320 mol acetone were mixed, refluxed under N2 atmosphere for 24 h, and filtered to obtain substance A.

[0128] (2) 0.7 mol of substance A, 17.5 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 672 mol of acetonitrile were mixed, refluxed at 75°C for 30 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0129] (3) 0.6 mol of substance B, 15 mol of 1,6-dibromohexane, and 600 mol of acetonitrile were mixed, refluxed at 75°C for 30 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0130] (4) 0.5 mol of substance C was mixed with 2 mol of N,N-dimethylhexylamine and 480 mol of acetonitrile, refluxed at 75°C for 30 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0131] (5) 0.1 mol of sodium aluminate (calculated as Al2O3), 1.2 mol of potassium hydroxide, 0.5 mol of product D and 50 mol of water were mixed and stirred to obtain solution A.

[0132] (6) Add 5 mol of silica sol (calculated as SiO2) to solution A to obtain gel B.

[0133] (7) 0.05 wt% of ZSM-5 seeds were added to gel B to obtain gel C.

[0134] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 80 °C for 12 h to obtain gel D.

[0135] (9) Gel D was transferred to a crystallization reactor and crystallized at 180 °C for 48 h.

[0136] (10) The crystallized molecular sieve was washed, dried at 60°C for 24 h, and calcined at 600°C for 5 h to obtain solid a.

[0137] (11) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 600 °C for 5 h to obtain solid b.

[0138] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0139] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0140] Example 3

[0141] (1) 1 mol (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, 15 mol 1,10-dibromodecane, 15 mol K2CO3 and 240 mol acetone were mixed, refluxed for 30 h under N2 atmosphere, and filtered to obtain substance A.

[0142] (2) 0.7 mol of substance A, 10.5 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 392 mol of acetonitrile were mixed, refluxed at 90°C for 20 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0143] (3) 0.6 mol of substance B, 9 mol of 1,6-dibromohexane, and 384 mol of acetonitrile were mixed, refluxed at 90°C for 20 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0144] (4) 0.5 mol of substance C was mixed with 1 mol of N,N-dimethylhexylamine and 280 mol of acetonitrile, refluxed at 90°C for 20 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0145] (5) 0.1 mol of sodium aluminate (calculated as Al2O3), 1.5 mol of potassium hydroxide, 0.3 mol of product D, and 200 mol of water were mixed and stirred to obtain solution A.

[0146] (6) Add 10 mol of silica sol (calculated as SiO2) to solution A to obtain gel B.

[0147] (7) Add 5 wt% of ZSM-5 seeds to gel B to obtain gel C.

[0148] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 100 °C for 6 h to obtain gel D.

[0149] (9) Gel D was transferred to a crystallization reactor and crystallized at 200 °C for 24 h.

[0150] (10) The crystallized molecular sieve was washed, dried at 60°C for 24 h, and calcined at 700°C for 4 h to obtain solid a.

[0151] (11) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 700 °C for 4 h to obtain solid b.

[0152] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0153] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0154] Among them, Examples 1 to 3 can all synthesize surfactants of this structure within a certain range of synthesis ratios, and prepare products such as ZSM-5 molecular sieves.

[0155] Example 4

[0156] (1) 1 mol (S)-3,3'-bis(naphthyl)-1,1'-bis-2-naphthol, 25 mol 1,4-dibromobutane, 18 mol K2CO3 and 280 mol acetone were mixed, refluxed for 24 h under N2 atmosphere, and filtered to obtain substance A.

[0157] (2) 0.7 mol of substance A, 14 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 420 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0158] (3) 0.6 mol of substance B, 12 mol of 1,6-dibromohexane, and 480 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0159] (4) 0.5 mol of substance C was mixed with 1.5 mol of N,N-dimethylhexylamine and 300 mol of acetonitrile, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0160] (5) 0.1 mol of aluminum sulfate (calculated as Al2O3), 0.9 mol of potassium hydroxide, 0.5 mol of product D, and 100 mol of water were mixed and stirred to obtain solution A.

[0161] (6) Add 2.5 mol of silica gel (calculated as SiO2) to solution A to obtain gel B.

[0162] (7) Add 1 wt% of S-1 seed crystals to gel B to obtain gel C.

[0163] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain gel D.

[0164] (9) Gel D was transferred to a crystallization reactor and crystallized at 150 °C for 72 h.

[0165] (10) The crystallized molecular sieve was washed, dried at 60 °C for 24 h, and calcined at 550 °C for 6 h to obtain solid a.

[0166] (11) Solid a was ion exchanged with ammonium acetate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain solid b.

[0167] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0168] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0169] Example 5

[0170] (1) 1 mol of (S)-3,3'-di-9-phenanthrenyl-1,1'-binaphthol, 25 mol of 1,6-dibromohexane, 18 mol of K2CO3, and 280 mol of acetone were mixed, refluxed under N2 atmosphere for 24 h, and filtered to obtain substance A.

[0171] (2) 0.7 mol of substance A, 14 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 420 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0172] (3) 0.6 mol of substance B, 12 mol of 1,6-dibromohexane, and 480 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0173] (4) 0.5 mol of substance C was mixed with 1.5 mol of N,N-dimethylhexylamine and 300 mol of acetonitrile, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0174] (5) 0.1 mol of aluminum hydroxide (calculated as Al2O3), 0.9 mol of sodium carbonate, 0.5 mol of product D, and 100 mol of water were mixed and stirred to obtain solution A.

[0175] (6) Add 2.5 mol of ethyl orthosilicate (calculated as SiO2) to solution A to obtain gel B.

[0176] (7) 1 wt% ZSM-5 seed crystals were added to gel B to obtain gel C.

[0177] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain gel D.

[0178] (9) Gel D was transferred to a crystallization reactor and crystallized at 150 °C for 72 h.

[0179] (10) The crystallized molecular sieve was washed, dried at 60 °C for 24 h, and calcined at 550 °C for 6 h to obtain solid a.

[0180] (11) Solid a was ion exchanged with ammonium chloride solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain solid b.

[0181] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of addition, mixed and stirred to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0182] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0183] Example 6

[0184] (1) 1 mol (S)-3,3′-di-9-anthryl-1,1′-di-2-naphthol, 25 mol 1,8-dibromooctane, 18 mol K2CO3 and 280 mol acetone were mixed, refluxed for 24 h under N2 atmosphere, and filtered to obtain substance A.

[0185] (2) 0.7 mol of substance A, 14 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 420 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0186] (3) 0.6 mol of substance B, 12 mol of 1,6-dibromohexane, and 480 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0187] (4) 0.5 mol of substance C was mixed with 1.5 mol of N,N-dimethylhexylamine and 300 mol of acetonitrile, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0188] (5) 0.1 mol of sodium aluminate (calculated as Al2O3), 0.9 mol of tetrapropylammonium hydroxide, 0.5 mol of product D and 100 mol of water were mixed and stirred to obtain solution A.

[0189] (6) Add 2.5 mol of water glass (calculated as SiO2) to solution A to obtain gel B.

[0190] (7) 1 wt% ZSM-5 seed crystals were added to gel B to obtain gel C.

[0191] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain gel D.

[0192] (9) Gel D was transferred to a crystallization reactor and crystallized at 150 °C for 72 h.

[0193] (10) The crystallized molecular sieve was washed, dried at 60 °C for 24 h, and calcined at 550 °C for 6 h to obtain solid a.

[0194] (11) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain solid b.

[0195] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0196] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0197] Example 7

[0198] (1) 1 mol (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, 25 mol 1,12-dibromododecane, 18 mol K2CO3 and 280 mol acetone were mixed, refluxed under N2 atmosphere for 24 h, and filtered to obtain substance A.

[0199] (2) 0.7 mol of substance A, 14 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 420 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance B.

[0200] (3) 0.6 mol of substance B, 12 mol of 1,6-dibromohexane, and 480 mol of acetonitrile were mixed, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain substance C.

[0201] (4) 0.5 mol of substance C was mixed with 1.5 mol of N,N-dimethylhexylamine and 300 mol of acetonitrile, refluxed at 80°C for 24 h, filtered, washed with ether, and dried at 60°C for 6 h to obtain product D.

[0202] (5) 0.1 mol of sodium aluminate (calculated as Al2O3), 0.9 mol of tetraethylammonium hydroxide, 0.5 mol of product D and 100 mol of water were mixed and stirred to obtain solution A.

[0203] (6) Add 2.5 mol of silica sol to solution A to obtain gel B.

[0204] (7) 1 wt% ZSM-5 seed crystals were added to gel B to obtain gel C.

[0205] (8) Gel C was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain gel D.

[0206] (9) Gel D was transferred to a crystallization reactor and crystallized at 150 °C for 72 h.

[0207] (10) The crystallized molecular sieve was washed, dried at 60 °C for 24 h, and calcined at 550 °C for 6 h to obtain solid a.

[0208] (11) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain solid b.

[0209] (12) With solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0210] (13) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0211] Examples 4 to 7 were performed according to different synthetic formulas and different raw materials in different proportions to verify that these raw materials and proportions can prepare ZSM-5 molecular sieves with special morphologies, and to carry out catalyst preparation and application.

[0212] Comparative Example 1

[0213] (1) 0.1 mol of sodium aluminate (calculated as Al2O3), 0.9 mol of sodium hydroxide, and 100 mol of water were mixed and stirred to obtain solution A.

[0214] (2) Add 2.5 mol of silica sol (calculated as SiO2) to solution A to obtain gel B.

[0215] (3) Add 1 wt% of ZSM-5 seed crystals to gel B to obtain gel C.

[0216] (4) Gel C was transferred to a round-bottom flask and pre-crystallized at 60 °C for 24 h to obtain gel D.

[0217] (5) Gel D was transferred to a crystallization reactor and crystallized at 150 °C for 72 h.

[0218] (6) The crystallized molecular sieve was washed, dried at 60°C for 24 h, and calcined at 550°C for 6 h to obtain solid a.

[0219] (7) Solid a was ion exchanged with ammonium nitrate solution at a concentration of 0.1 mol / L at a solid-liquid ratio of 1:10, and then calcined at 550 °C for 6 h to obtain solid b.

[0220] (8) Using solid b as the active component of the catalyst, 600 g of kaolin, 130 g of aluminum sol, 70 g of phosphoric acid, 400 g of molecular sieve, and 130 g of silica sol were added in the order of mixing and stirring to form a slurry. After ball milling, the slurry was spray-formed in a spray dryer.

[0221] (9) The prepared microsphere particles were calcined at 500 °C for 2 h, and the obtained samples were evaluated using a fixed fluidized bed reactor.

[0222] The following are the test results of the molecular sieve samples obtained in the examples and comparative examples:

[0223] Table 1 Surface area and pore volume test results of molecular sieve (solid b)

[0224]

[0225] Figure 2 The X-ray diffraction patterns (XRD) of the molecular sieves in Example 1 and Comparative Example 1 of the present invention are shown in FIG. Figure 3 The following are scanning electron microscope photos (SEM photos) of the molecular sieves in Example 1 and Comparative Example 1.

[0226] from Figure 2 It can be seen from the XRD diagram that, compared with the standard MFI diffraction peak spectrum, both Example 1 and Comparative Example 1 have and only have the characteristic diffraction peaks of the MFI phase, indicating that the materials prepared by the two preparation methods are both ZSM-5 molecular sieves. Figure 3 It can be seen from the SEM photos that the ZSM-5 molecular sieve with a special morphology prepared by the present invention is a spherical nano ZSM-5 molecular sieve with a two-dimensional layered mesoporous structure, which is about 400nm. At the same time, it can also be clearly observed that the sample of Example 1 has a rich pore structure. This can also be seen from the surface area and pore volume test results of Examples 1-7. In summary, the embodiments of the present invention use a homemade surfactant, and are supplemented by seed crystals and two-end temperature crystallization to prepare ZSM-5 molecular sieves, which have the advantages of special morphology, high specific surface area, and rich mesopores.

[0227] The following are the evaluation results of light hydrocarbon cracking, and the evaluation test method is as described above.

[0228] Table 2 Physical properties and catalytic performance of catalyst samples used in the examples

[0229]

[0230] Note: The raw material parameters of cracking catalysis are attached.

[0231] As can be seen from Table 2, Examples 1-7 prepared using special surfactants have higher conversion rates and diene yields and lower coke than Comparative Example 1. This is because the ZSM-5 molecular sieves prepared in Examples 1-7 have higher specific surface area and mesopore volume. In the light hydrocarbon cracking reaction, the mass transfer rate is improved, so that the reaction substrate and the acidic site are quickly contacted and disengaged, the catalytic efficiency is improved, the occurrence of secondary reactions is suppressed, it is conducive to improving reaction conversion rate and diene selectivity, and suppressing the generation of coke.

[0232] Table 3 Physical properties of crude oil

[0233]

[0234] The present invention is not restricted by the above-mentioned embodiments. Any other modification, modification, simplification, combination and substitution that does not deviate from the essence and principle of the present invention are within the scope of protection of this patent.

Claims

1. A surfactant, characterized in that Having the structure of formula I: Wherein, -O-Ar-O- is a chiral naphthol group shown in Formula II, Ar0 is phenyl, naphthyl, anthracenyl or phenanthrenyl; n is an integer between 2 and 14; R is a quaternary ammonium group shown in Formula III, X is a halogen anion, and t is an integer between 2 and 6; 2. The surfactant according to claim 1, characterized in that The formula I satisfies at least one of the following: n is an integer between 4 and 12; X is a chloride ion or a bromide ion; and t is an integer between 4 and 6.

3. The method for synthesizing a surfactant according to claim 1 or 2, wherein: include: Naphthol, a disubstituted alkylating agent, N,N,N',N'-tetramethyl-alkyldiamine, a dihalogenated alkane and N,N-dimethyl-alkylamine are reacted to obtain a surfactant represented by Formula I; The naphthol is (S)-3,3'-bis(phenyl)-1,1'-bis-2-naphthol, (S)-3,3'-bis(naphthyl)-1,1'-bis-2-naphthol, (S)-3,3'-di-9-phenanthrenyl-1,1'-binaphthol or (S)-3,3'-di-9-anthryl-1,1'-di-2-naphthol; The number of alkyl groups in the disubstituted alkylating agent is 2 to 14; The number of alkyl groups in the N,N,N',N'-tetramethyl-dialkylamine, dihalogenated alkane and N,N-dimethyl-alkylamine is 2-6.

4. A method for preparing ZSM-5 molecular sieve, characterized in that: The following steps are involved: Mixing the surfactant according to claim 1 or 2, seed crystals, an aluminum source, a silicon source, an alkaline substance and water to obtain a gel; crystallizing the gel to obtain a molecular sieve solid; The molecular sieve solid is ion-exchanged using ammonium salt, and then calcined to obtain a ZSM-5 molecular sieve with a special morphology.

5. The preparation method according to claim 4, characterized in that At least one of the following is satisfied: the aluminum source is one or more of aluminum hydroxide, aluminate and aluminum sulfate; the silicon source is one or more of silica gel, ethyl orthosilicate, silica sol and water glass; the alkaline substance includes one or more of organic base and inorganic base.

6. The preparation method according to claim 4, characterized in that The molar ratio of SiO2 / Al2O3 in the silicon source and the aluminum source is 25-100:1; and / or the molar ratio of the aluminum source calculated as Al2O3 to the alkali is 1:9-15.

7. The preparation method according to any one of claims 4 to 6, characterized in that The crystallization comprises: firstly performing low-temperature pre-crystallization at a temperature below 100° C. for at least 6 hours, and then performing high-temperature crystallization treatment at a temperature above 150° C. to obtain a molecular sieve solid.

8. The preparation method according to claim 7, characterized in that The temperature of the high temperature crystallization treatment is 150°C to 200°C, and the time is more than 24 hours; After the high temperature crystallization treatment, the method further comprises: calcining the crystallized molecular sieve at a temperature of 550-700° C. for 4-6 hours to obtain a molecular sieve solid.

9. The preparation method according to claim 7, characterized in that The ZSM-5 molecular sieve with special morphology has a two-dimensional layered mesoporous structure and a specific surface area of 300m 2 / g or above.

10. A method for cracking light hydrocarbons, characterized in that: The following steps are involved: The ZSM-5 molecular sieve obtained by the preparation method according to any one of claims 4 to 9 is used as a catalytic active component to carry out a catalytic cracking reaction on a light hydrocarbon raw material to obtain a cracking product.

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