Shape-selective alkylation reaction catalyst as well as preparation method and application thereof

Abstract

The invention provides a shape-selective alkylation reaction catalyst as well as a preparation method and application thereof. The preparation method of the shape-selective alkylation reaction catalyst comprises the following steps: step 1, preparing hydrogen-type mordenite; step 2, preparing water vapor dealuminated mordenite; and 3, carrying out outer surface modification on the obtained water vapor dealuminated mordenite by using lanthanide metal nitrate to obtain the lanthanide metal modified water vapor dealuminated mordenite, namely the shape-selective alkylation reaction catalyst. According to the method, the catalyst is modified through an impregnation method, and surface acid sites of the mordenite catalyst are occupied, so that side reactions are inhibited, the shape selectivity of the catalyst is improved, and the service life of the catalyst is prolonged. When the naphthalene alkylation catalyst prepared by the method disclosed by the invention is used for carrying out naphthalene diisopropylation reaction and a reaction for preparing 2, 6-diisopropylnaphthalene, the selectivity of the prepared 2, 6-diisopropylnaphthalene can reach 42% or above, and a relatively good technical effect is achieved.

Description

Technical Field

[0001] The invention is mainly applied to the field of chemical synthesis, and specifically is a shape-selective alkylation reaction catalyst and a preparation method and application thereof. Background Art

[0002] As a new type of high-performance polyester material, polyethylene naphthalate (PEN) has great application potential and market space. In terms of physical properties, compared with polyethylene terephthalate (PET), PEN's mechanical properties, impact strength and heat resistance are better than PET, especially in high temperature environments, PEN's performance is more superior; PEN has good chemical stability, especially in barrier properties, and its barrier effect on oxygen, carbon dioxide and other gases is better than PET, which makes PEN very suitable for packaging materials for food, beverages and cosmetics. In addition, PEN's good hydrolysis resistance, insulation and processing properties make it widely used in industries such as pharmaceutical packaging, electronic products and instrumentation.

[0003] However, the current limitation on large-scale production of PEN is that the preparation process of its raw material 2,6-diisopropylnaphthalene (2,6-DIPN) is relatively complicated and difficult to purify, which makes the production cost high.

[0004] At present, my country has abundant naphthalene and propylene resources with huge output, so the method of alkylation of naphthalene and propylene to prepare high value-added 2,6-diisopropylnaphthalene is a good strategy. However, the isopropylation reaction of naphthalene has many by-products, and there are more than ten isomers of diisopropylnaphthalene alone, and the boiling points of each isomer are relatively close, making purification difficult. Therefore, improving the selectivity of 2,6-diisopropylnaphthalene becomes the key to synthesis.

[0005] At present, the method of preparing 2,6-DIPN using naphthalene and propylene still has the problems of low selectivity and easy catalyst deactivation. The modification direction of the catalyst is mostly focused on adjusting the internal pore size and acidic sites, while there are fewer modification methods for the active sites on the catalyst surface that have reaction activity but no selectivity. Summary of the invention

[0006] In order to solve the problems in the prior art that the catalyst in the naphthalene isopropylation reaction has low selectivity, is easy to deactivate, and is difficult to produce continuously, the present invention provides a method for preparing a shape-selective alkylation reaction catalyst, wherein the catalyst is modified by a lanthanide metal nitrate, and the surface acid sites of the mordenite catalyst are occupied, thereby inhibiting the occurrence of side reactions and improving the shape selectivity and life of the catalyst.

[0007] Another object of the present invention is to provide a shape-selective alkylation catalyst prepared by the above preparation method.

[0008] Another object of the present invention is to provide the use of the above-mentioned shape-selective alkylation catalyst in the preparation of 2,6-diisopropylnaphthalene.

[0009] Another object of the present invention is to provide a method for preparing 2,6-diisopropylnaphthalene, which has high selectivity, is not easy to deactivate the catalyst, and can achieve continuous production of 2,6-diisopropylnaphthalene.

[0010] Existing shape-selective alkylation catalysts control the selectivity of the reaction by regulating the pore size inside the molecular sieve. However, the sites on the catalyst surface also have catalytic activity but lack the selectivity of the internal pores. Therefore, a large number of side reactions occur on the outer surface of the catalyst.

[0011] In view of the deficiencies in the prior art, the present invention discloses:

[0012] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0013] Step 1: Sodium-type mordenite powder (NaM) is subjected to amine exchange and calcination to obtain hydrogen-type mordenite (HM); Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water-gas dealumination, acid washing, water washing to remove chlorine, drying and calcination to obtain water-gas dealuminated mordenite (SDHM); Step 3: The obtained water-gas dealuminated mordenite (SDHM) is surface-modified with lanthanide metal nitrate to obtain lanthanide metal-modified water-gas dealuminated mordenite (RESDHM), i.e., a shape-selective alkylation reaction catalyst.

[0014] Preferably, the amine source for the amine exchange is one of cyclopropylamine, ethylenediamine, triethylamine, piperidine, hexamethyleneimine, triethylenediamine and tetrabutylammonium bromide or a mixture in any proportion; preferably one of ethylenediamine, triethylamine and piperidine or a mixture in any proportion; those skilled in the art can understand that the specific operations of amine exchange and calcination (such as the number of operations) are not restrictive, and those skilled in the art can set them according to the actual prepared catalyst and the reaction conditions of the application.

[0015] Preferably, in step 2, the water vapor dealumination temperature is 420-540°C, preferably 460-490°C;

[0016] Preferably, in step 2, the pickling refers to washing away aluminum hydroxide in the pores with a dilute hydrochloric acid solution; the roasting temperature is 430-540° C., preferably 470-500° C.;

[0017] Preferably, the lanthanide metal nitrate comprises La(NO3)3 . H2O、Nd(NO3)3 . 5H2O and Sm(NO3)3 .6H2O or a mixture in any proportion.

[0018] In the above technical solution, step 3 specifically includes the following steps:

[0019] S1: weigh a certain amount of dried steam-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh a lanthanide metal nitrate according to a ratio and dissolve it in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the mass of the lanthanide metal nitrate is 1-3%wt of the mass of the steam-dealuminized mordenite (SDHM); preferably 2-3%wt;

[0020] S2: pouring the obtained lanthanide metal nitrate solution into a mortar filled with the water vapor dealuminated mordenite (SDHM) to submerge the water vapor dealuminated mordenite (SDHM);

[0021] S3: Grind continuously under an infrared lamp until the moisture is driven out and the product becomes dry, then put into an oven for drying and calcine in a muffle furnace; the calcination temperature in the muffle furnace is 430-540°C, preferably 470-500°C.

[0022] Another aspect of the present invention is the shape-selective alkylation catalyst obtained by the above preparation method.

[0023] Another aspect of the present invention is the use of the above-mentioned shape-selective alkylation catalyst in alkylation reactions, such as methylation, ethylation, diisopropylation, etc.

[0024] Another aspect of the present invention is a method for preparing 2,6-DIPN. Propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene in the presence of a shape-selective alkylation catalyst to obtain 2,6-DIPN.

[0025] In the above technical scheme, first, the shape-selective alkylation reaction catalyst is activated;

[0026] Then, the activated shape-selective alkylation catalyst is loaded into the reactor;

[0027] Finally, propylene and liquid naphthalene are introduced to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0028] In the above technical solution, the amount of the shape-selective alkylation catalyst used is 4%-10% of the mass of naphthalene; preferably 7%-10%.

[0029] The molar ratio of naphthalene to propylene is 1:(1-10), preferably 1:(1.9-3.3); the diisopropylation reaction temperature is 190-310°C, preferably 230-260°C; the diisopropylation reaction pressure is 0.6-4.0MPa, preferably 0.6-1.0MPa; the preheating temperature of liquid naphthalene is 60-280°C, preferably 70-120°C.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. The shape-selective alkylation reaction catalyst provided by the present invention is modified by a lanthanide metal nitrate to occupy the surface acid sites of the mordenite catalyst, thereby inhibiting the occurrence of side reactions and improving the shape selectivity and life of the catalyst. Compared with the unmodified catalyst, the selectivity of the catalytic naphthalene diisopropylation reaction is improved.

[0032] 2. The method for preparing 2,6-diisopropylnaphthalene provided by the present invention adopts the naphthalene alkylation catalyst prepared by the present invention to carry out the naphthalene diisopropylation reaction. In the reaction for preparing 2,6-diisopropylnaphthalene, the selectivity of the prepared 2,6-diisopropylnaphthalene is significantly improved, and a good technical effect is achieved. DETAILED DESCRIPTION

[0033] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below, and preferred embodiments of the present invention are given. However, it should be understood that these embodiments are only used for more detailed description and should not be understood as limiting the present invention in any form, i.e., not intended to limit the scope of protection of the present invention.

[0034] The sodium-type mordenite (NaM) used in the embodiment of the present invention can be purchased from the market.

[0035] Example 1

[0036] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0037] Step 1: Sodium mordenite (NaM) powder is used as a raw material, and hydrogen mordenite (HM) is prepared by amine exchange and calcination; the amine source of the amine exchange is triethylamine. The amine exchange and calcination conditions are prior art and will not be described in detail here.

[0038] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 420° C., aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 430° C. to obtain water vapor dealumination mordenite (SDHM);

[0039] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide La(NO3)3 . H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the La(NO3)3 .The mass of H2O is 2%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 430°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as LaHM2.0.

[0040] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0041] Firstly, the obtained shape-selective alkylation catalyst LaHM2.0 was activated in a muffle furnace at an activation temperature of 270°C and an activation time of 5 h.

[0042] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0043] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 70°C. Naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:1.9. The reaction temperature was controlled to be 190±5°C, the reaction pressure was 0.6 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0044] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 84.7% and the selectivity of 2,6-diisopropylnaphthalene was 35%.

[0045] Comparative Example 1

[0046] Based on the preparation method of the shape-selective alkylation catalyst shown in Example 1, the water-dealuminized mordenite (SDHM) prepared in this comparative example was not subjected to La(NO3)3 . Immersed in H2O solution, marked as SDHM0.

[0047] Based on the preparation method of 2,6-DIPN shown in Example 1, propylene and liquid naphthalene are subjected to diisopropylation reaction of naphthalene under the action of SDHMO catalyst to obtain 2,6-DIPN. A small amount of sample is taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction are determined by gas chromatography. The gas phase results show that the conversion rate of naphthalene is 86% and the selectivity of 2,6-diisopropylnaphthalene is 24%.

[0048] Example 2

[0049] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0050] Step 1: Sodium mordenite (NaM) powder is used as a raw material, and hydrogen mordenite (HM) is obtained by amine exchange and calcination; the amine source of the amine exchange is ethylenediamine. The amine exchange and calcination conditions are prior art and are not described in detail here.

[0051] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 490°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 540°C to obtain water vapor dealumination mordenite (SDHM);

[0052] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide Nd(NO3)3 . 5H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the Nd(NO3)3 . The mass of 5H2O is 3%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 540°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as NdHM3.0.

[0053] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0054] Firstly, the obtained shape-selective alkylation catalyst NdHM3.0 was activated in a muffle furnace at an activation temperature of 450°C and an activation time of 6 hours;

[0055] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0056] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 90°C. Naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:3.3. The reaction temperature was controlled to be 310±5°C, the reaction pressure was 2.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0057] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 97.5% and the selectivity of 2,6-diisopropylnaphthalene was 40.1%.

[0058] Comparative Example 2

[0059] Based on the preparation method of the shape-selective alkylation catalyst shown in Example 2, the water-dealuminized mordenite (SDHM) prepared in this comparative example was not subjected to Nd(NO3)3 . 5H2O solution impregnation, marked as NdHM0.

[0060] Based on a preparation method of 2,6-DIPN shown in Example 2, propylene and liquid naphthalene are subjected to diisopropylation of naphthalene under the action of NdHMO catalyst to obtain 2,6-DIPN. A small amount of sample is taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction are determined by gas chromatography. The gas phase results show that the conversion rate of naphthalene is 98.1% and the selectivity of 2,6-diisopropylnaphthalene is 21%.

[0061] Example 3

[0062] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0063] Step 1: using sodium mordenite (NaM) powder as a raw material, and subjecting it to amine exchange and calcination to obtain hydrogen mordenite (HM); the amine source for the amine exchange is piperidine.

[0064] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 485°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 500°C to obtain water vapor dealumination mordenite (SDHM);

[0065] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide Sm(NO3)3 . 6H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the Sm(NO3)3 . The mass of 6H2O is 3%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dried, then put into an oven for drying and calcined in a muffle furnace; the calcination temperature in the muffle furnace is 500°C, and the obtained product is rare earth modified SDHM (RESDHM), which is marked as SmHM3.0.

[0066] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0067] Firstly, the obtained shape-selective alkylation catalyst SmHM3.0 was activated in a muffle furnace at an activation temperature of 450°C and an activation time of 7 h.

[0068] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0069] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 120°C. Naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:2.3. The reaction temperature was controlled to be 255±5°C, the reaction pressure was 1.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0070] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 99.5% and the selectivity of 2,6-diisopropylnaphthalene was 42%.

[0071] Comparative Example 3

[0072] Based on the preparation method of the shape-selective alkylation catalyst shown in Example 3, the water-dealuminized mordenite (SDHM) prepared in this comparative example was not subjected to Sm(NO3)3 . 6H2O solution impregnation, marked as SmHM0.

[0073] Based on a preparation method of 2,6-DIPN shown in Example 2, propylene and liquid naphthalene are subjected to diisopropylation of naphthalene under the action of SmHMO catalyst to obtain 2,6-DIPN. A small amount of sample is taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction are determined by gas chromatography. The gas phase results show that the conversion rate of naphthalene is 99.5%, and the selectivity of 2,6-diisopropylnaphthalene is 27.1%.

[0074] Example 4

[0075] The difference between this embodiment and embodiment 3 is that the reaction temperature of the diisopropylation reaction is different.

[0076] Specifically,

[0077] A method for preparing 2,6-DIPN,

[0078] First, the shape-selective alkylation catalyst SmHM3.0 obtained in Example 3 was activated in a muffle furnace at an activation temperature of 450° C. for 7 h.

[0079] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0080] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 120°C, and naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:2.3. The reaction temperature was controlled to be 310±5°C, the reaction pressure was 1.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0081] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 100% and the selectivity of 2,6-diisopropylnaphthalene was 32.6%.

[0082] Example 5

[0083] This example is based on the preparation method of the catalyst for the shape-selective alkylation of naphthalene and the preparation method of 2,6-DIPN in Example 3. Compared with Example 3, the difference is that in step 3 of the preparation process of the catalyst for the shape-selective alkylation of naphthalene, the Sm(NO3)3 . The mass of 6H2O is 2%wt of the mass of SDHM. The obtained product is marked as SmHM2.0.

[0084] According to the same preparation method of 2,6-DIPN as in Example 3, after the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 99.5%, and the selectivity of 2,6-diisopropylnaphthalene was 36.2%.

[0085] Example 6

[0086] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0087] Step 1: Using sodium mordenite (NaM) powder as a raw material, undergoing amine exchange and calcination to obtain hydrogen mordenite (HM); the amine source for the amine exchange is triethylamine.

[0088] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 420°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 480°C to obtain water vapor dealumination mordenite (SDHM);

[0089] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide La(NO3)3 . H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the La(NO3)3 . The mass of H2O is 1%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 480°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as LaHM1.0.

[0090] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0091] Firstly, the obtained shape-selective alkylation catalyst LaHM1.0 was activated in a muffle furnace at an activation temperature of 450°C and an activation time of 5 h.

[0092] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0093] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 70°C, and naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:4. The reaction temperature was controlled to be 220±5°C, the reaction pressure was 1.5 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0094] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 87% and the selectivity of 2,6-diisopropylnaphthalene was 26.3%.

[0095] Example 7

[0096] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0097] Step 1: Sodium mordenite (NaM) powder is used as a raw material, and hydrogen mordenite (HM) is prepared through amine exchange and calcination; the amine source of the amine exchange is ethylenediamine.

[0098] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 490°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 530°C to obtain water vapor dealumination mordenite (SDHM);

[0099] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide metal nitrate Nd(NO3)3 . 5H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the Nd(NO3)3 . The mass of 5H2O is 1%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 530°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as NdHM1.0.

[0100] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0101] Firstly, the obtained shape-selective alkylation catalyst NdHM1.0 was activated in a muffle furnace at an activation temperature of 440°C and an activation time of 6 h.

[0102] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0103] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 90°C. Naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:3.3. The reaction temperature was controlled to be 310±5°C, the reaction pressure was 2.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0104] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 97.2% and the selectivity of 2,6-diisopropylnaphthalene was 30.4%.

[0105] Example 8

[0106] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0107] Step 1: using sodium mordenite (NaM) powder as a raw material, and subjecting it to amine exchange and calcination to obtain hydrogen mordenite (HM); the amine source for the amine exchange is piperidine.

[0108] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 465°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 480°C to obtain water vapor dealumination mordenite (SDHM);

[0109] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide metal nitrate Sm(NO3)3 . 6H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the Sm(NO3)3 . The mass of 6H2O is 1%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 480°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as SmHM1.0.

[0110] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0111] Firstly, the obtained shape-selective alkylation catalyst SmHM1.0 was activated in a muffle furnace at an activation temperature of 460°C and an activation time of 7 h.

[0112] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0113] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 120°C, and naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:2.3. The reaction temperature was controlled to be 300±5°C, the reaction pressure was 1.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0114] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 99.7% and the selectivity of 2,6-diisopropylnaphthalene was 32%.

[0115] Example 9

[0116] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0117] Step 1: Using sodium mordenite (NaM) powder as a raw material, undergoing amine exchange and calcination to obtain hydrogen mordenite (HM); the amine source for the amine exchange is triethylamine.

[0118] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 420°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 480°C to obtain water vapor dealumination mordenite (SDHM);

[0119] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide metal salt La(NO3)3 . H2O、Nd(NO3)3 . 5H2O and Sm(NO3)3 . 6H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the La(NO3)3 . The mass of H2O is 1%wt of the mass of SDHM, and the Nd(NO3)3 . The mass of 5H2O is 1%wt of the mass of water-dealuminized mordenite (SDHM), and the Sm(NO3)3 . The mass of 6H2O is 1%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 480°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as La-Nd-SmHM1.0.

[0120] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0121] Firstly, the obtained shape-selective alkylation catalyst La-Nd-SmHM1.0 was activated in a muffle furnace at an activation temperature of 450°C and an activation time of 5 h.

[0122] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0123] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 70°C, and naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:4. The reaction temperature was controlled to be 220±5°C, the reaction pressure was 1.5 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0124] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 87.3% and the selectivity of 2,6-diisopropylnaphthalene was 28.8%.

[0125] Example 10

[0126] A method for preparing a shape-selective alkylation reaction catalyst comprises the following steps:

[0127] Step 1: Using sodium mordenite (NaM) powder as a raw material, undergoing amine exchange and calcination to obtain hydrogen mordenite (HM); the amine source for the amine exchange is triethylamine.

[0128] Step 2: The obtained hydrogen-type mordenite (HM) is subjected to water vapor dealumination at 420°C, aluminum hydroxide in the pores is washed out with a dilute hydrochloric acid solution, chlorine is removed by water washing, drying and calcining at 480°C to obtain water vapor dealumination mordenite (SDHM);

[0129] Step 3: Weigh 20 g of dried water-dealuminized mordenite (SDHM) in a mortar; at the same time, weigh lanthanide metal salt Nd(NO3)3 . 5H2O and Sm(NO3)3 . 6H2O and dissolved in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the Nd(NO3)3 . The mass of 5H2O is 3%wt of the mass of the water-dealuminized mordenite (SDHM), and the Sm(NO3)3 . The mass of 6H2O is 1%wt of the mass of SDHM. Pour the obtained lanthanide metal nitrate solution into a mortar filled with SDHM to immerse the SDHM. Grind continuously under an infrared lamp until the water is completely removed and dry, then put it into an oven for drying and muffle furnace calcination; the muffle furnace calcination temperature is 480°C, and the obtained product is rare earth modified SDHM (RESDHM), marked as Nd-SmHM.

[0130] A method for preparing 2,6-DIPN, wherein propylene and liquid naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of a shape-selective alkylation catalyst to obtain 2,6-DIPN. Specifically, the method comprises the following steps:

[0131] Firstly, the obtained shape-selective alkylation catalyst Nd-SmHM was activated in a muffle furnace at an activation temperature of 460°C and an activation time of 7 h.

[0132] Then, the activated shape-selective alkylation catalyst is loaded into a fixed bed reactor, the fixed bed reactor has a tube inner diameter of 6 mm and a tube length of 20 cm;

[0133] Finally, nitrogen was replaced three times to exhaust the air, and then naphthalene was preheated to 120°C, and naphthalene and propylene gases were introduced into the reactor at a molar ratio of 1:2.3. The reaction temperature was controlled to be 300±5°C, the reaction pressure was 1.0 MPa, and the reaction residence time was 6 s to carry out diisopropylation of naphthalene to obtain 2,6-DIPN.

[0134] After the reaction was completed, a small amount of sample was taken out through the tail sampling valve, dissolved in dichloromethane, and the selectivity and conversion rate of the reaction were determined by gas chromatography. The gas phase results showed that the conversion rate of naphthalene was 98.9% and the selectivity of 2,6-diisopropylnaphthalene was 31.4%.

[0135] The condition parameters in the above embodiment are summarized as shown in the following table:

[0136]

[0137]

[0138] By comparing Example 1 with Comparative Example 1, it is shown that La(NO3)3 . The modification of H2O is beneficial to the improvement of the selectivity of the alkylation reaction.

[0139] By comparing Example 2 and Comparative Example 2, it is shown that Nd(NO3)3 . The modification of 5H2O is beneficial to the improvement of the selectivity of the alkylation reaction.

[0140] By comparing Example 3 and Comparative Example 3, it is shown that Sm(NO3)3 . The modification of 6H2O is beneficial to the improvement of the selectivity of the alkylation reaction.

[0141] By comparing Example 3 with Example 2, it is shown that Sm(NO3)3 . 6H2O vs Nd(NO3)3 . The modification of 5H2O is more effective and the alkylation reaction is more selective.

[0142] By comparing Example 3 and Example 4, it is shown that Sm(NO3)3 . The selectivity of the 6H2O modified catalyst decreases at a higher reaction temperature. The preferred reaction temperature range of the present invention is 230-260°C.

[0143] By comparing Example 2 and Example 7, it is shown that Nd(NO3)3 . 5H2O modification is beneficial to the improvement of alkylation selectivity. . As the amount of 5H2O added increased, the conversion rate of the alkylation reaction remained unchanged while the selectivity increased.

[0144] By comparing Example 3, Example 5 and Example 8, it is shown that adding 3%wt of Sm(NO3)3 . 6H2O is more effective in catalyst modification, and the selectivity of the reaction is higher. The selectivity of the alkylation reaction increases with the increase of Sm(NO3)3 . The selectivity increases with the increase of 6H2O addition, and can reach 42%.

[0145] By comparing Example 1 and Example 5, it is shown that Sm(NO3)3 . 6H2O vs La(NO3)3 . The modification with H2O is more effective and the alkylation reaction is more selective.

[0146] By comparing Example 1 and Example 6, it is shown that with the increase of La(NO3)3 . As the amount of H2O added increased, the conversion rate of the alkylation reaction decreased slightly, while the selectivity increased.

[0147] By comparing Example 4 and Example 8, it is shown that with the increase of Sm(NO3)3 . The conversion rate and selectivity of the alkylation reaction did not change significantly with the increase of the addition amount of 6H2O.

[0148] By comparing Example 9 with Example 6, it is shown that La(NO3)3 . H2O、Nd(NO3)3 . 5H2O and Sm(NO3)3 . The mixed addition modification of 6H2O has little effect on the conversion rate of the alkylation reaction, and the selectivity is slightly improved.

[0149] By comparing Example 10 with Example 8 and Example 2, it is shown that Nd(NO3)3 . 5H2O and Sm(NO3)3 . The mixed addition of 6H2O reduced the selectivity of the alkylation reaction.

[0150] It should be noted that the above contents are further detailed descriptions of the present invention in combination with specific implementation methods, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions; the dimensional data of this embodiment does not necessarily limit the technical solution, but only shows one of the specific working conditions. For ordinary technicians in the technical field to which the present invention belongs, several simple improvements and modifications can be made without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. A method for preparing a shape-selective alkylation catalyst, characterized in that: The following steps are involved: Step 1: sodium-type mordenite powder is subjected to amine exchange and calcination to obtain hydrogen-type mordenite; Step 2: The obtained hydrogen-type mordenite is subjected to water vapor dealuminization, acid washing, water washing to remove chlorine, drying and roasting to obtain water vapor dealuminized mordenite; Step 3: Modify the outer surface of the obtained water-gas dealuminated mordenite with lanthanide metal nitrate to obtain lanthanide metal-modified water-gas dealuminated mordenite, i.e., shape-selective alkylation reaction catalyst.

2. The preparation method according to claim 1, characterized in that In step 1, the amine source for amine exchange is one of cyclopropylamine, ethylenediamine, triethylamine, piperidine, hexamethyleneimine, triethylenediamine and tetrabutylammonium bromide or a mixture thereof in any proportion; preferably one of ethylenediamine, triethylamine and piperidine or a mixture thereof in any proportion.

3. The preparation method according to claim 1, characterized in that: In step 2, the water vapor dealumination temperature is 420-540°C, preferably 460-490°C; The pickling refers to washing away aluminum hydroxide in the pores with a dilute hydrochloric acid solution; The calcination temperature is 430-540°C, preferably 470-500°C.

4. The preparation method according to claim 1, characterized in that: The lanthanide metal nitrate is La(NO3)3 . H2O、Nd(NO3)3 . 5H2O and Sm(NO3)3 . 6H2O or a mixture in any proportion.

5. The preparation method according to claim 1, characterized in that: Step 3 specifically includes the following steps: S1: weigh a certain amount of dried water-dealuminized mordenite in a mortar; weigh a lanthanide metal nitrate according to a ratio and dissolve it in an appropriate amount of distilled water to obtain a lanthanide metal nitrate solution; the mass of the lanthanide metal nitrate is 1-3%wt of the mass of the water-dealuminized mordenite; preferably 2-3%wt; S2: pouring the obtained lanthanide metal nitrate solution into a mortar containing the water vapor dealuminated mordenite to submerge the water vapor dealuminated mordenite; S3: Grind continuously under an infrared lamp until the moisture is driven out and the product becomes dry, then put into an oven for drying and calcine in a muffle furnace; the calcination temperature in the muffle furnace is 430-540°C, preferably 470-500°C.

6. The shape-selective alkylation reaction catalyst prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the shape-selective alkylation reaction catalyst as claimed in claim 6 in an alkylation reaction.

8. A method for preparing 2,6-diisopropylnaphthalene, characterized in that: Propylene and naphthalene are subjected to a diisopropylation reaction of naphthalene under the action of the shape-selective alkylation catalyst as claimed in claim 6 to obtain 2,6-diisopropylnaphthalene.

9. The method for preparing 2,6-diisopropylnaphthalene according to claim 8, characterized in that: First, the shape-selective alkylation catalyst is activated; Then, the activated shape-selective alkylation catalyst is loaded into the reactor; Finally, propylene and naphthalene materials are introduced to carry out diisopropylation reaction of naphthalene to obtain 2,6-diisopropylnaphthalene.

10. The method for preparing 2,6-diisopropylnaphthalene according to claim 8, characterized in that: The amount of the shape-selective alkylation catalyst used is 4%-10% of the mass of naphthalene; preferably 7%-10%; The molar ratio of naphthalene to propylene is 1:(1-10), preferably 1:(1.9-3.3); The diisopropylation reaction temperature is 190-310°C, preferably 230-260°C; The diisopropylation reaction pressure is 0.6-4.0 MPa, preferably 0.6-1.0 MPa; The preheating temperature of naphthalene is 60-280°C, preferably 70-120°C.

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