Preparation method of molecular sieve and hydrogen type molecular sieve catalyst and application of hydrogen type molecular sieve catalyst in cyclohexene hydration reaction

Abstract

The application discloses a molecular sieve, a preparation method of a hydrogen type molecular sieve catalyst and application of the hydrogen type molecular sieve catalyst in a cyclohexene hydration reaction, and comprises the following steps: mixing raw materials containing a silicon source, an aluminum source, an alkali source, cyclohexylamine and water, and performing dynamic crystallization to obtain a ZSM-5 / ZSM-11 co-crystallization molecular sieve. Compared with a traditional tetrabutylammonium bromide and 1,6-hexanediamine template system, the catalyst prepared from the molecular sieve synthesized by using the system has higher cyclohexene conversion rate in the cyclohexene hydration reaction.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a molecular sieve and a hydrogen type molecular sieve catalyst and application of the molecular sieve and the hydrogen type molecular sieve catalyst in a cyclohexene hydration reaction and belongs to the technical field of chemical catalyst preparation. BACKGROUND

[0002] Cyclohexanol is an important chemical raw material. It is often applied to the production of chemical products such as resin paint, perfume and insecticide. In the production of chemical products, cyclohexanol is mainly used in the production of adipic acid, nylon 66 and caprolactam and the like. In the textile industry, cyclohexanol is often used as a scouring and bleaching aid and a dye solvent. In the coating industry, cyclohexanol can be used as a solvent for paint, varnish and shellac; in the synthesis of detergents, the stabilizer and uniformizer of emulsion also often use cyclohexanol. In addition, because cyclohexanol has good emulsifying capacity, it can also be used as a textile soap and a matting agent. At the same time, cyclohexanol is also a raw material for preparing perfume, rubber anti-aging agent and fruit mildew inhibitor.

[0003] The hydration of cyclohexene to generate cyclohexanol is a typical acid catalysis reaction, and the catalysts applied to the reaction mainly include ion exchange resin, mineral acid, benzene sulfonic acid, sulfuric acid and solid molecular sieve. Compared with the homogeneous catalysis using inorganic acid as the catalyst, the method for catalyzing the hydration of cyclohexene to generate cyclohexanol by using the solid molecular sieve as the catalyst has the advantages of good reaction performance, simple separation, easy recovery of the catalyst and no acid corrosion of equipment and is an environment-friendly chemical process.

[0004] At present, the silicon-aluminum molecular sieve with acid catalysis is often used as the catalyst for the hydration reaction of cyclohexene, such as ZSM-5, mordenite, zeolite and mesoporous molecular sieve material. The ZSM-5 molecular sieve has excellent catalytic effect and has realized industrial application. As early as 1983, Japanese patents JP83-209150 and JP60104031A disclosed a method for catalyzing the hydration of cyclohexene to generate cyclohexanol by using a solid acid molecular sieve. Subsequently, researchers have improved the catalytic performance of the solid acid molecular sieve. CN1257840C discloses a preparation method of small-grained ZSM-5 zeolite, and the obtained ZSM-5 zeolite has good catalytic effect on the hydration of cyclohexene to generate cyclohexanol. CN201110460030 discloses a ZSM-5 molecular sieve and a preparation method thereof, and the obtained ZSM-5 molecular sieve shows excellent activity and selectivity in the hydration of cyclohexene to generate cyclohexanol. CN201310654055 discloses a preparation method of nano Fe-MCM-41 molecular sieve, and the obtained molecular sieve also shows excellent activity and selectivity of cyclohexanol in the reaction of the hydration of cyclohexene to generate cyclohexanol.

[0005] CN105237356A discloses a method for preparing cyclohexanol by hydrating cyclohexene, the catalyst is an inactivated iron-containing molecular sieve with MFI structure or a mixture of an inactivated iron-containing molecular sieve with MFI structure and an inactivated iron-containing molecular sieve with MWW structure. The invention utilizes waste, and the reaction process is simple. CN201811454101.0 discloses a preparation method of a multi-level hole ZSM-5 molecular sieve, and the obtained ZSM-5 molecular sieve has good cyclohexene conversion rate and catalyst stability.

[0006] In 1980, Mobil synthesized ZSM-5 / ZSM-11 co-crystalline zeolite with intermediate structure between ZSM-5 and ZSM-11 by using quaternary ammonium salt as a template (USP 4229424), and further reported the catalytic application of the zeolite in processes such as methanol to gasoline, olefin oligomerization, aromatic alkylation, xylene isomerization and catalytic cracking of hydrocarbons (USP 4289607). CN1137022, USP 5869021 and USP 6093866 disclose a synthesis method of rare earth ZSM-5 / ZSM-11 co-crystalline zeolite, which uses C2-C8 binary amine as a template, and can be applied to catalytic processes such as alkylation of rare ethylene with benzene, aromatization of low-carbon alkanes and methanol to low-carbon olefins. At present, ZSM-5 / ZSM-11 co-crystalline zeolite has successfully realized industrial application of alkylation of ethylene in catalytic cracking dry gas with benzene, and the required raw material dry gas can be reacted with benzene to prepare ethylbenzene without special refining. The catalyst developed by using the co-crystalline zeolite is the key to this technology.

[0007] The cyclohexene hydration reaction using a molecular sieve as a catalyst is a three-phase reaction, that is, there are cyclohexene phase, water phase and solid catalyst phase, and the catalyst exists in the water phase. Like other heterogeneous catalytic reactions, the reactant cyclohexene first diffuses to the surface of the catalyst, chemisorbs on the active center site, and then undergoes chemical reaction to generate products, which desorb from the surface of the catalyst and enter the liquid phase. Since the hydration reaction rate depends on the protonation rate [Xing Qiyi, Xu Ruiqi, Zhou Zheng, Pei Weiwei. Basic Organic Chemistry. Beijing: Higher Education Press, 1993. 180], as the molecular sieve grain becomes finer, on the one hand, the surface area of the molecular sieve increases, increasing the contact probability of cyclohexene and the molecular sieve, and on the other hand, the number of active centers near the molecular sieve pore increases, effectively reducing the diffusion resistance of cyclohexene to the active center and improving the catalytic efficiency, thereby increasing the hydration reaction activity of cyclohexene.

[0008] At present, the most commonly used template for synthesizing ZSM-5 / ZSM-11 co-crystalline molecular sieve is tetrabutylammonium bromide / tetrabutylammonium hydroxide of quaternary ammonium salt / quaternary ammonium base, and binary amine 1,6-hexanediamine. SUMMARY

[0009] The application aims to provide a preparation method of a ZSM-5 / ZSM-11 co-crystallized molecular sieve catalyst applied to a cyclohexene hydration reaction for preparing cyclohexanol, wherein the ZSM-5 / ZSM-11 co-crystallized molecular sieve is synthesized by using a cyclic structure cyclohexylamine, the method has simple operation process, and the product has high crystallinity, and has wide application prospect. Compared with the ZSM-5 / ZSM-11 co-crystallized molecular sieve synthesized in a conventional system, the ZSM-5 / ZSM-11 co-crystallized molecular sieve has higher catalytic activity in the cyclohexene hydration reaction, and has higher cyclohexene conversion rate.

[0010] In one aspect of the application, a preparation method of a molecular sieve is provided, including ZSM-5 / ZSM-11 co-crystallized molecular sieve synthesis, including the following steps:

[0011] Mixing raw materials containing a silicon source, an aluminum source, an alkali source, cyclohexylamine and water, and performing dynamic crystallization to obtain the ZSM-5 / ZSM-11 co-crystallized molecular sieve.

[0012] Optionally, the silicon source is selected from at least one of solid silica gel, silica sol, tetraethyl orthosilicate or white carbon black;

[0013] The aluminum source is selected from at least one of sodium metaaluminate, aluminum sulfate, aluminum hydroxide or pseudo-boehmite;

[0014] The alkali source is selected from at least one of sodium hydroxide or potassium hydroxide.

[0015] Optionally, a molar ratio (SiO2 / Al2O3) of the silicon source to the aluminum source is 20-120;

[0016] A molar ratio (H2O / SiO2) of the water to the silicon source is 12-60;

[0017] A molar ratio (M+ / SiO2) of the alkali source to the silicon source is 0.03-0.20; wherein, the metal M represents Na or K;

[0018] A molar ratio (CHA / SiO2) of the cyclohexylamine (CHA) to the silicon source is 0.01-2.0;

[0019] The molar number of the silicon source is counted by the molar number of SiO2 contained in the silicon source;

[0020] The molar number of the aluminum source is counted by the molar number of Al2O3 contained in the aluminum source;

[0021] The molar number of the water is counted by the molar number of itself;

[0022] The molar number of the alkali source is counted by the molar number of alkali metal ions contained in the alkali source;

[0023] The molar number of the cyclohexylamine is counted by the molar number of itself.

[0024] Optionally, the molar ratio of the silicon source to the aluminum source is independently selected from any value or any value between any two points of the following group: 20, 30.3, 50.0, 60.6, 80, 100, 12.

[0025] Optionally, the molar ratio of the water to the silicon source is independently selected from any value or any value between any two points of the following group: 12, 16, 22, 50, 58, 60.

[0026] Optionally, the molar ratio of the base source to the silicon source is independently selected from any value or any value between any two points of the following group: 0.03, 0.078, 0.09, 0.093, 0.15, 0.2.

[0027] Optionally, the molar ratio of the cyclohexylamine to the silicon source is independently selected from any value or any value between any two points of the following group: 0.01, 0.2, 0.3, 0.5, 1.0, 1.2, 1.5, 1.8, 2.0.

[0028] Optionally, the raw material further comprises seeds.

[0029] The seeds are selected from at least one of ZSM-5, ZSM-11, ZSM-5 / ZSM-11.

[0030] Optionally, the mass of the seeds is 0-20% of the mass of the silicon source, wherein the mass of the silicon source is the mass of SiO2 contained therein.

[0031] Optionally, the mass of the seeds is independently selected from any value or any value between any two points of the following group: 0, 1%, 5%, 8%, 10%, 12%, 15%, 18%, 20% of the mass of the silicon source.

[0032] Optionally, the crystallization temperature of the dynamic crystallization is 140-200℃, and the crystallization time is 24-192h.

[0033] Optionally, the crystallization temperature is independently selected from any value or any value between any two points of the following group: 140℃, 155℃, 162℃, 170℃, 178℃, 190℃, 200℃.

[0034] Optionally, the crystallization time is independently selected from any value or any value between any two points of the following group: 24h, 40h, 60h, 84h, 100h, 120h, 140h, 160h, 180h, 192h.

[0035] Optionally, the dynamic crystallization is carried out at a rotation speed of 5-200rpm.

[0036] Optionally, the dynamic crystallization is performed in an oven, wherein the rotation speed of the reaction kettle is 5-200 rpm.

[0037] Optionally, the rotation speed is independently selected from any value or any value between any two points of the following: 5 rpm, 15 rpm, 30 rpm, 50 rpm, 80 rpm, 100 rpm, 120 rpm, 150 rpm, 180 rpm, 200 rpm.

[0038] Optionally, the micro-morphology of the ZSM-5 / ZSM-11 co-crystallized molecular sieve is rod-like structure.

[0039] In another aspect of the present application, a preparation method of a hydrogen-type molecular sieve catalyst is provided, which comprises: subjecting the above ZSM-5 / ZSM-11 co-crystallized molecular sieve to calcination I, ion exchange, and calcination II, to obtain the hydrogen-type molecular sieve catalyst.

[0040] Optionally, the calcination I is performed under the following conditions: a calcination temperature of 460-600℃, a calcination time of 2-20 h, a temperature rising rate of 0.5-3℃ / min, and an air atmosphere.

[0041] Optionally, the calcination I temperature is independently selected from any value or any value between any two points of the following: 460℃, 500℃, 550℃, 600℃.

[0042] Optionally, the calcination I time is independently selected from any value or any value between any two points of the following: 2 h, 6 h, 10 h, 12 h, 16 h, 20 h.

[0043] Optionally, the temperature rising rate I is independently selected from any value or any value between any two points of the following: 0.5℃ / min, 1℃ / min, 1.5℃ / min, 2℃ / min.

[0044] Optionally, the calcination II is performed under the following conditions: a calcination temperature of 460-600℃, a calcination time of 2-20 h, a temperature rising rate of 0.5-3℃ / min, and an air atmosphere.

[0045] Optionally, the calcination II temperature is independently selected from any value or any value between any two points of the following: 460℃, 500℃, 550℃, 600℃.

[0046] Optionally, the calcination II time is independently selected from any value or any value between any two points of the following: 2 h, 3 h, 5 h, 8 h, 10 h, 12 h, 16 h, 20 h.

[0047] Optionally, the temperature rising rate II is independently selected from any value or any value between any two points of 0.5℃ / min, 1℃ / min, 1.5℃ / min, 2℃ / min.

[0048] Optionally, the ion exchange includes at least one of ammonium exchange, acid exchange;

[0049] Optionally, the ammonium exchange agent used in the ammonium exchange is at least one selected from ammonium chloride, ammonium nitrate;

[0050] The acid exchange agent used in the acid exchange is at least one selected from oxalic acid, hydrochloric acid;

[0051] Optionally, the ion exchange conditions are that the exchange is carried out at 60-80℃, the exchange is carried out for 3 times, the single exchange time is 1h, and the weight ratio of the ZSM-5 / ZSM-11 co-crystallized molecular sieve to the ion exchange agent is 1:3-5;

[0052] Optionally, the temperature of the ion exchange is independently selected from any value or any value between any two points of 60℃, 70℃, 80℃.

[0053] Optionally, the weight ratio of the ZSM-5 / ZSM-11 co-crystallized molecular sieve to the ion exchange agent is independently selected from any value or any value between any two points of 1:3, 1:4, 1:5.

[0054] Optionally, the ion exchange is further dried, the drying temperature is 80-130℃, and the drying time is 5-10h;

[0055] Optionally, the drying temperature is independently selected from any value or any value between any two points of 80℃, 100℃, 120℃, 130℃.

[0056] Optionally, the drying time is independently selected from any value or any value between any two points of 5h, 6h, 7h, 8h, 9h, 10h.

[0057] As a specific embodiment, the preparation method includes ZSM-5 / ZSM-11 co-crystallized molecular sieve synthesis and subsequent treatment;

[0058] The ZSM-5 / ZSM-11 co-crystallized molecular sieve is synthesized by fully mixing a silicon source, an aluminum source, an inorganic base, cyclohexylamine, deionized water, seed crystals and other raw materials, and dynamically crystallizing at a certain temperature to obtain the ZSM-5 / ZSM-11 co-crystallized molecular sieve.

[0059] The subsequent treatment process comprises: firstly, heating the raw molecular sieve powder to 460-600℃ at a heating rate of 0.5-3℃ / min, and keeping for 2-20h; secondly, ion exchange with oxalic acid, hydrochloric acid, ammonium chloride or ammonium nitrate solution at 60-80℃, drying at 80-130℃ after the exchange, and finally, heating to 460-600℃ at a heating rate of 0.5-3℃ / min, and keeping for 2-20h.

[0060] In another aspect of the present application, a method for preparing cyclohexanol by hydrating cyclohexene is provided, which comprises reacting a raw material containing cyclohexene, water and a catalyst to obtain a product containing cyclohexanol.

[0061] The catalyst is selected from the hydrogen-type molecular sieve catalyst obtained by the above preparation method.

[0062] Optionally, the mass ratio of water to cyclohexene is (0.6-2):1.

[0063] The mass ratio of the catalyst to cyclohexene is (0.03-0.30):1.

[0064] Optionally, the mass ratio of water to cyclohexene is independently selected from any value of 0.6:1, 1:1, 1.5:1, 2:1 or any value between any two of the above values.

[0065] Optionally, the mass ratio of the catalyst to cyclohexene is independently selected from any value of 0.03:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1 or any value between any two of the above values.

[0066] Optionally, the reaction temperature is 90-160℃.

[0067] The reaction is carried out at a rotation speed of 500-800r / min.

[0068] The reaction pressure is 0.1-2.0MPa.

[0069] The reaction time is 0.5-6h.

[0070] Optionally, the reaction temperature is independently selected from any value of 90℃, 110℃, 125℃, 140℃, 160℃ or any value between any two of the above values.

[0071] Optionally, the rotation speed is independently selected from any value of 500r / min, 600r / min, 700r / min, 800r / min or any value between any two of the above values.

[0072] Optionally, the reaction pressure is independently selected from any value or any value between any two points of 0.1 MPa, 0.5 MPa, 1.5 MPa, 2 MPa.

[0073] Optionally, the reaction time is independently selected from any value or any value between any two points of 0.5 h, 1 h, 2 h, 4 h, 6 h.

[0074] As a specific embodiment, the whole process of the present application comprises:

[0075] The gel formed by mixing the silicon source, aluminum source, base, cyclohexylamine template, deionized water, and seed crystals is crystallized at 140-200°C for 24-192h to hydrothermally synthesize ZSM-5 / ZSM-11 co-crystalline molecular sieve. After calcining the molecular sieve at 460-600°C for 2-20h in air to remove the cyclohexylamine template, and exchanging with oxalic acid, hydrochloric acid, ammonium chloride or ammonium nitrate solution, and calcining to obtain a hydrogen type molecular sieve catalyst, the cyclohexene hydration reaction is carried out at 90-160°C, 0.1-2.0 MPa, a water to cyclohexene molar ratio of (0.6-2):1, and a mass ratio of catalyst to cyclohexene of (0.03-0.30):1. The specific steps are as follows:

[0076] 1) The silicon source, aluminum source, inorganic base, cyclohexylamine template, deionized water, and seed crystals are slowly added to the reaction kettle under stirring to form a raw material mixture with a molar composition of SiO2 / Al2O3 = 20-120, H2O / SiO2 = 12-60, OH- / SiO2 = 0.03-0.20, M + / SiO2 = 0.03-0.20, R / SiO2 = 0.01-2.0, Seed / SiO2 = 0-20%. Wherein R is cyclohexylamine; M is an alkali metal element, including Na, K, etc., and Seed is at least one of ZSM-5, ZSM-11, and ZSM-5 / ZSM-11.

[0077] It is well known that adding seed crystals can change the morphology and physicochemical properties of the product during the synthesis of molecular sieves. In the present application, the amount of seed crystals Seed is 0%, representing no addition of seed crystals.

[0078] 2) The gel after mixing the raw materials is dynamically crystallized at 140-200°C for 24-192h to hydrothermally synthesize ZSM-5 / ZSM-11 co-crystalline molecular sieve.

[0079] 3) The reaction kettle is cooled with tap water, and the solid product is obtained by centrifugation or filtration. The solid product is washed and dried to obtain ZSM-5 / ZSM-11 co-crystalline molecular sieve raw powder.

[0080] 4) Slowly heat the raw molecular sieve powder under a flowing air atmosphere (20-200 mL / min, 5 g of raw molecular sieve powder) to 460-600 °C at a rate of 0.5-3 °C / min and maintain for 2-20 h to remove the cyclohexylamine template.

[0081] 5) Exchange with oxalic acid, hydrochloric acid, ammonium chloride, ammonium nitrate solution at 60-80 °C, and dry at 80-130 °C after exchange.

[0082] 6) Slowly heat the dried sample under a flowing air atmosphere (20-200 mL / min, 5 g of raw molecular sieve powder) to 460-600 °C at a rate of 0.5-3 °C / min and maintain for 2-20 h to obtain a hydrogen-type molecular sieve catalyst.

[0083] 7) Perform the hydration of cyclohexene at 90-160 °C, 0.1-2.0 MPa, a molar ratio of water to cyclohexene of (0.6-2): 1, and a mass ratio of catalyst to cyclohexene of (0.03-0.30): 1, and stop the reaction after 0.5-6 h to obtain a cyclohexanol product.

[0084] The beneficial effects that can be produced by the present application include:

[0085] The present application develops a new preparation method of ZSM-5 / ZSM-11 co-crystallized molecular sieve catalyst, which has a higher conversion rate of cyclohexene in the hydration of cyclohexene compared with the ZSM-5 / ZSM-11 co-crystallized molecular sieve catalyst synthesized by a conventional system. BRIEF DESCRIPTION OF DRAWINGS

[0086] Figure 1 X-ray diffraction pattern of the ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained in Example 1.

[0087] Figure 2 Scanning electron microscope image of the ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained in Example 1.

[0088] Figure 3 X-ray diffraction pattern of the ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained in Example 2.

[0089] Figure 4 Scanning electron microscope image of the ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained in Example 2.

[0090] Figure 5 X-ray diffraction pattern of the ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained in Comparative Example 1.

[0091] Figure 6Scanning electron microscope picture of ZSM-5 / ZSM-11 co-crystallized molecular sieve obtained for Comparative Example 1. DETAILED DESCRIPTION

[0092] The present application will be described in detail below with reference to Examples, but the present application is not limited to these Examples.

[0093] The raw materials in the Examples of the present application were all purchased through commercial channels unless otherwise specified.

[0094] The analytical methods in the Examples of the present application were as follows:

[0095] X-ray diffraction analysis was performed using an X-ray diffractometer of X'Pert Pro type from the Netherlands Panaek Company, and scanning electron microscope analysis was performed using a scanning electron microscope of JSM-7800F type.

[0096] The conversion rate and selectivity in the Examples of the present application were calculated as follows:

[0097] Conversion rate of cyclohexene:

[0098]

[0099] Selectivity of cyclohexanol:

[0100]

[0101] Selectivity of cyclohexene dimer:

[0102]

[0103] Example 1

[0104] The raw materials used were as follows:

[0105] A. Silica sol (31.09 wt.% Si02, 0.35 wt.% Na20, 0.14 wt.% Al203, 68.42 wt.% H20);

[0106] B. Solid sodium metaaluminate (NaAl02, 53.50 wt.% Al203, 43.50 wt.% Na20, 3.00 wt.% H20):

[0107] C. Sodium hydroxide solution (0.10 g / ml);

[0108] D. Cyclohexylamine (CHA, C6H 13 N, purity ≥ 98 wt.%);

[0109] E. Deionized water;

[0110] Under stirring, 297.32 g of silica sol, 4.06 g of solid sodium metaaluminate, 21.00 ml of sodium hydroxide solution (0.10 g / ml), 30.51 g of cyclohexylamine, 384.69 g of deionized water were added into a reactor in turn. The molar composition of the raw material mixture was: SiO2 / Al2O3= 60.6, Na + / SiO2= 0.093, OH- / SiO2= 0.093, CHA / SiO2= 0.20, H2O / SiO2= 22. After stirring for 30 min, the mixture was mixed uniformly and the reactor was sealed. The reactor was crystallized at 178 °C for 140 h under dynamic conditions at 30 rpm. The reaction was quenched with tap water and the solid product was separated by centrifugation. The product was washed with deionized water until neutral. The ZSM-5 / ZSM-11 co-crystalline molecular sieve crude powder was dried at 120 °C overnight. Figure 1 The powder X-ray diffraction pattern of the obtained ZSM-5 / ZSM-11 co-crystalline molecular sieve crude powder is shown in Figure 1. Figure 1 It can be seen that it is a pure phase ZSM-5 / ZSM-11 co-crystalline molecular sieve. Figure 2 The scanning electron microscope photograph of the ZSM-5 / ZSM-11 co-crystalline molecular sieve crude powder is shown in Figure 2. Figure 2 It can be seen that the micro-morphology of the ZSM-5 / ZSM-11 co-crystalline molecular sieve obtained in Example 1 is rod-shaped, with a size of 0.3-1 micron.

[0111] Example 2

[0112] The raw materials used are as follows:

[0113] A. silica gel (dry basis 98 wt.%);

[0114] B. aluminum sulfate [Al2(SO4)3-18H2O, purity > 98 wt.%];

[0115] C. sodium hydroxide solution (1.0 g / ml);

[0116] D. cyclohexylamine (CHA, C6H 13 N, purity > 98 wt.%);

[0117] E. deionized water;

[0118] F. ZSM-5 / ZSM-11 seed;

[0119] Under stirring, 43.79 g of solid silica gel, 15.71 g of aluminum sulfate, 4.55 ml of sodium hydroxide solution (1.0 g / ml), 35.42 g of cyclohexylamine, 634.99 g of deionized water, 2.27 g of ZSM-5 / ZSM-11 seed were added into a reactor in turn. The molar composition of the raw material mixture was: SiO2 / Al2O3= 30.3, Na+ / SiO2= 0.15, OH- / SiO2= 0.15, CHA / SiO2= 0.5, H2O / SiO2= 50, Seed / SiO2= 5%. Stirring for 30 min, make it mix well, seal the synthesis kettle. The reaction mixture is crystallized at 155°C for 100 h with 100 rpm dynamic crystallization. Quench the reaction with tap water, centrifugal separation to get solid product. Wash with deionized water until neutral. Dry at 120°C overnight to get ZSM-5 / ZSM-11 co-crystalline molecular sieve raw powder. Figure 3 The powder X-ray diffraction pattern of the obtained ZSM-5 / ZSM-11 co-crystalline molecular sieve raw powder is shown in Figure 2. Figure 3 It can be seen that it is pure phase ZSM-5 / ZSM-11 co-crystalline molecular sieve. Figure 4 The scanning electron microscope photo of the obtained ZSM-5 / ZSM-11 co-crystalline molecular sieve raw powder is shown in Figure 3. Figure 4 It can be seen that the ZSM-5 / ZSM-11 co-crystalline molecular sieve obtained in Example 2 has rod-like morphology in microstructure, with a size of 0.2-0.8 microns.

[0120] Example 3

[0121] The raw materials used are as follows:

[0122] A. Silica sol (30.19 wt.% SiO2, 0.29 wt.% Na2O, 0.23 wt.% Al2O3, 69.29 wt.% H2O);

[0123] B. Pseudo-boehmite (72 wt.% Al2O3)

[0124] C. Sodium hydroxide solid (96 wt.%)

[0125] D. Sodium hydroxide solution (0.10 g / ml);

[0126] E. Cyclohexylamine (CHA, C6H 13 N, purity ≥98 wt.%);

[0127] F. Deionized water;

[0128] G. ZSM-11 Seed;

[0129] Under stirring conditions, 4.39 g pseudo-boehmite, 4.90 g sodium hydroxide solid, 9.53 g deionized water were added into a reaction kettle, which was treated at 162°C for 7.5 h and then cooled to room temperature. Then 398.04 g silica sol, 0.43 ml of sodium hydroxide solution (0.10 g / ml), 59.50 g cyclohexylamine, 288.23 g deionized water, 1.24 g ZSM-11 Seed were added into the reaction kettle in sequence. The molar composition of the starting mixture was: SiO2 / Al2O3= 50.0, Na + / SiO2= 0.078, OH- / SiO2= 0.078, CHA / SiO2= 0.3, H2O / SiO2= 16, Seed / SiO2= 1%. The mixture was stirred for 30 min to ensure homogeneity and the synthesis kettle was sealed. The initial gel was crystallized at 162°C for 84 h at 80 rpm. The reaction was quenched with tap water and the solid product was isolated by centrifugation. The product was washed with deionized water until neutral. The ZSM-5 / ZSM-11 co-crystalline molecular sieve was dried at 120°C overnight. The XRD pattern was similar to that of ZSM-5 / ZSM-11 co-crystalline molecular sieve. Figure 1 The product was determined to be ZSM-5 / ZSM-11 co-crystalline molecular sieve.

[0130] Example 4

[0131] The starting materials used were as follows:

[0132] A. tetraethyl orthosilicate (28.4 wt.% SiO2);

[0133] B. aluminum sulfate [Al2(SO4)3-18H2O, purity > 98 wt.%];

[0134] C. potassium hydroxide solution (0.10 g / ml);

[0135] D. cyclohexylamine (CHA, C6H 13 N, purity > 98 wt.%);

[0136] E. deionized water;

[0137] F. ZSM-5 Seed;

[0138] Under stirring conditions, 103.98 g tetraethyl orthosilicate, 25.20 ml of 0.10 g / ml potassium hydroxide solution and 227 ml deionized water were mixed, and after hydrolysis at 80°C, the evaporated water was supplemented, and 4.12 g aluminum sulfate, 58.31 g cyclohexylamine, 290.68 g deionized water, 5.34 g ZSM-5 molecular sieve seed were added. The molar composition of the starting mixture was: SiO2 / Al2O3= 80, K + / SiO2= 0.09, OH - / SiO2 = 0.09, CHA / SiO2 = 1.2, H2O / SiO2 = 58, Seed / SiO2 = 18%. Stirring for 30 min, make it fully mixed, seal the reactor. Initial gel at 170°C, 150 rpm dynamic crystallization for 60 h. Quench the reaction with tap water, centrifugal separation to get solid product. Wash with deionized water until neutral. Dry at 120°C overnight to get ZSM-5 / ZSM-11 co-crystalline molecular sieve raw powder. The XRD pattern is similar to Figure 1 The product is determined to be ZSM-5 / ZSM-11 co-crystalline molecular sieve.

[0139] Comparative Example 1

[0140] The raw materials used are as follows:

[0141] A. Solid silica gel (98.0 wt.% SiO2);

[0142] B. Aluminum sulfate [Al2(SO4)3-18H2O, purity ≥ 98.0 wt.%];

[0143] C. Sodium hydroxide (99.0 wt.%);

[0144] D. 1,6-hexanediamine (HMDA, C6H 16 N2, purity ≥ 99.0 wt.%);

[0145] E. Deionized water;

[0146] Under stirring conditions, 51.10 g of solid silica gel, 9.30 g of aluminum sulfate octadecahydrate, 3.50 g of sodium hydroxide, 39.10 g of 1,6-hexanediamine, and 145.60 g of deionized water were sequentially added to the reactor. The molar composition of the raw material mixture was: SiO2 / Al2O3 = 60, Na2O / SiO2 = 0.05, HMDA / SiO2 = 0.4, H2O / SiO2 = 10. Stirring for 30 min, make it fully mixed, seal the reactor, and heat to 150°C, 150 rpm dynamic crystallization for 60 h. Quench the reaction with tap water, centrifugal separation to get solid product. Wash with deionized water until neutral. Dry at 120°C overnight to get molecular sieve raw powder. Figure 5 The XRD pattern of the molecular sieve is shown in Figure 1, which is similar to Figure 5 The product is determined to be ZSM-5 / ZSM-11 co-crystalline molecular sieve. Figure 6 The scanning electron microscope image of the molecular sieve is shown in Figure 2, which is a scanning electron microscope image of the molecular sieve. Figure 6 As can be seen, the micro-morphology of the molecular sieve obtained in Comparative Example 1 is irregular block-shaped, with a size of 0.3-1 microns.

[0147] Comparative Example 2

[0148] The ZSM-5 / ZSM-11 co-crystallized molecular sieve with a Si / Al ratio of 55 synthesized by using commercially purchased tetrabutylammonium bromide as a template agent.

[0149] Example 5

[0150] The ZSM-5 / ZSM-11 co-crystallized molecular sieve powder obtained in Example 1 was calcined under a flowing air atmosphere (60 mL / min, 5 g of the ZSM-5 / ZSM-11 co-crystallized molecular sieve powder) at a temperature increasing rate of 1.5 ℃ / min to 550 ℃ and maintained for 6 h to remove the organic amine template agent. Then, the calcined sample was exchanged with 20 mL of a 0.8 mol / L ammonium chloride solution at 80 ℃ for three times, with each single exchange time being 1 h; and then washed with deionized water for three times, and dried at 120 ℃ for 6 h, and then calcined at a temperature increasing rate of 1.5 ℃ / min to 550 ℃ and maintained for 3 h. After being cooled to room temperature, a hydrogen type catalyst A was obtained.

[0151] The ZSM-5 / ZSM-11 co-crystallized molecular sieves obtained in Examples 2 to 4 and Comparative Examples 1 to 2 were prepared into hydrogen type catalysts by using the same method (except that the molecular sieves were different, and other process parameters were the same), and the numbers of the hydrogen type catalysts were B, C, D, E, F and G, respectively.

[0152] Example 6

[0153] The reaction performance evaluation was carried out in a 1.0 L capacity micro high-pressure reaction kettle. 10 g of the catalyst (hydrogen type catalysts A, B, C, D, E, F and G in turn) was placed in the reaction kettle, 50 g of cyclohexene and 100 g of water were used, the reaction conditions were as follows: temperature 125 ℃, pressure 0.5 MPa, rotation speed 750 rpm, and reaction time 2 h. The materials before and after the reaction were analyzed for composition by using an Agilent 7890A chromatographic system, an OV-1 capillary column and a hydrogen flame ionization detector. The percentages used in the present application were all weight percentages. The conversion rate of cyclohexene and the selectivity of cyclohexanol were shown in Table 1.

[0154] As shown in Table 1, when the ZSM-5 / ZSM-11 co-crystallized molecular sieve catalysts obtained by different methods were applied to the hydration reaction of cyclohexene, the selectivity of the cyclohexanol product was relatively close, all being greater than 96.5%, but the conversion rates were quite different. The conversion rate of cyclohexene on the ZSM-5 / ZSM-11 catalyst E synthesized by using 1,6-hexanediamine was 4.2%, the conversion rate of cyclohexene on the ZSM-5 / ZSM-11 catalyst F synthesized by using commercially purchased tetrabutylammonium bromide as a template agent was 5.6%, and the conversion rate of cyclohexene on the ZSM-5 / ZSM-11 co-crystallized molecular sieve catalysts A, B, C and D synthesized by using cyclohexylamine in the present application was not less than 9.4%. It can be seen that the ZSM-5 / ZSM-11 co-crystallized molecular sieve catalysts obtained in the present application have more excellent catalytic performance in the hydration reaction of cyclohexene.

[0155] Table 1 Performance of cyclohexene hydration reaction over molecular sieve catalysts

[0156] Catalyst Cyclohexene conversion (%) Cyclohexanol selectivity (%) Cyclohexene dimer selectivity (%) A 10.3 98.4 1.6 B 9.4 97.6 2.4 C 10.1 98.2 1.8 D 9.7 96.8 3.2 E 4.2 97.0 3.0 F 5.6 97.6 2.4

[0157] The above merely describes several embodiments of the present application, and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the disclosed technical contents without departing from the scope of the present application, and the equivalent embodiments are equivalent to the equivalent embodiments, which are within the scope of the technical solutions.

Claims

1. A method for preparing cyclohexanol by hydrating cyclohexene, characterized in that, a raw material containing cyclohexene, water and a catalyst is reacted to obtain a product containing cyclohexanol; wherein the catalyst is a hydrogen type molecular sieve catalyst; the preparation method of the hydrogen type molecular sieve catalyst comprises: calcining I, ion exchange and calcining II of ZSM-5 / ZSM-11 co-crystalline molecular sieve to obtain the hydrogen type molecular sieve catalyst; the preparation method of the ZSM-5 / ZSM-11 co-crystalline molecular sieve comprises the following steps: mixing raw materials containing a silicon source, an aluminum source, an alkali source, cyclohexylamine and water, and performing dynamic crystallization to obtain the ZSM-5 / ZSM-11 co-crystalline molecular sieve; wherein the dynamic crystallization is performed under the condition that the rotation speed is 5-200 rpm; the micro-morphology of the ZSM-5 / ZSM-11 co-crystalline molecular sieve is rod structure; the molar ratio of the silicon source to the aluminum source is 20-120; the molar ratio of the water to the silicon source is 12-60; the molar ratio of the alkali source to the silicon source is 0.03-0.20; the molar ratio of the cyclohexylamine to the silicon source is 0.01-2.0; the molar number of the silicon source is based on the molar number of SiO2 contained therein; the molar number of the aluminum source is based on the molar number of Al2O3 contained therein; the molar number of the water is based on the molar number of itself; the molar number of the alkali source is based on the molar number of alkali metal ions contained therein; the molar number of the cyclohexylamine is based on the molar number of itself. 2.The method according to claim 1, characterized in that, the silicon source is selected from at least one of solid silica gel, silica sol, tetraethyl orthosilicate or white carbon black; the aluminum source is selected from at least one of sodium metaaluminate, aluminum sulfate, aluminum hydroxide or pseudo-boehmite; the alkali source is selected from at least one of sodium hydroxide or potassium hydroxide. 3.The method according to claim 1, characterized in that, the raw material further comprises seed crystals; the seed crystals are selected from at least one of ZSM-5, ZSM-11 and ZSM-5 / ZSM-11. 4.The method according to claim 3, characterized in that, the mass of the seed crystals is 0-20% of the mass of the silicon source, not including the end point value 0, wherein the mass of the silicon source is based on the mass of SiO2 contained therein; the crystallization temperature of the dynamic crystallization is 140-200 ℃, and the crystallization time is 24-192 h. 5.The method according to claim 1, characterized in that, the calcining I is performed under the condition that the calcination temperature is 460-600 ℃, the calcination time is 2-20 h, the heating rate is 0.5-3 ℃ / min, and the calcination atmosphere is air atmosphere; the calcining II is performed under the condition that the calcination temperature is 460-600 ℃, the calcination time is 2-20 h, the heating rate is 0.5-3 ℃ / min, and the calcination atmosphere is air atmosphere. 6.The method according to claim 1, characterized in that, the ion exchange comprises at least one of ammonium exchange and acid exchange; the ammonium exchange agent used in the ammonium exchange is selected from at least one of ammonium chloride and ammonium nitrate. The acid exchange reagent used in the acid exchange is selected from at least one of oxalic acid and hydrochloric acid; The ion exchange is carried out at 60-80 DEG C, and the exchange is carried out for 3 times, and the single exchange time is 1h, and the weight ratio of the ZSM-5 / ZSM-11 co-crystallized molecular sieve to the ion exchange reagent is 1:3-5; The ion exchange is further dried, the drying temperature is 80-130 DEG C, and the drying time is 5-10h.

7. The method of claim 1, wherein, The specific conditions of the raw material reaction containing cyclohexene, water and catalyst are as follows: The mass ratio of the water to the cyclohexene is (0.6-2):1; The mass ratio of the catalyst to the cyclohexene is (0.03-0.30):1; The reaction temperature is 90-160 DEG C; The reaction is carried out at a rotation speed of 500-800r / min; The reaction pressure is 0.1-2.0 MPa; The reaction time is 0.5-6h.

Images