CN109433253B - Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof - Google Patents

Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof Download PDF

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CN109433253B
CN109433253B CN201811459890.7A CN201811459890A CN109433253B CN 109433253 B CN109433253 B CN 109433253B CN 201811459890 A CN201811459890 A CN 201811459890A CN 109433253 B CN109433253 B CN 109433253B
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CN109433253A (en
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许磊
黄治华
袁扬扬
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract

The invention discloses a catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation, a preparation method and application thereof, wherein the catalyst is an HEMT molecular sieve modified by metal and siloxane compounds. The catalyst is applied to naphthalene tert-butylation reaction, and has higher activity and product selectivity.

Description

Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation and a preparation method and application thereof, belonging to the field of chemical engineering.
Background
Polyethylene naphthalate (PEN) is a high-performance polyester material with great potential and application prospect, has better heat resistance, mechanical property, gas barrier property, chemical stability, radiation resistance and the like compared with polybutylene terephthalate (PET), and can be widely applied to the manufacturing industries of electronic elements, instruments, insulating materials, films for food packaging, beer bottles, aerospace and the like. However, the bottleneck of limiting the large-scale introduction of PEN into the market at present is that the preparation process of the key raw material 2, 6-dialkyl naphthalene (2,6-DAN) is complicated and the production cost is high.
The naphthalene resource is rich in China, and cheap and rich naphthalene is synthesized into 2,6-DAN through alkylation reaction, so that the raw material source can be widened, the additional value of the naphthalene is improved, the process route is shortened, and the method is an ideal route for preparing the 2, 6-DAN. However, 2,6-DAN has ten isomers, and the boiling points of the isomers are similar, and the separation is very difficult, for example, the boiling points of 2, 6-dimethylnaphthalene (2,6-DMN) and 2, 7-dimethylnaphthalene (2,7-DMN) are only different by 0.3 ℃, so how to improve the selectivity of 2,6-DAN is the key to realizing the preparation of 2,6-DAN by the naphthalene one-step method.
Based on the steric hindrance effect of alkyl substituent groups, the use of larger alkyl substituent groups can reduce the product isomers and improve the selectivity of the target product, for example, 2, 6-dimethylnaphthalene, 2, 6-diisopropylnaphthalene and 2, 6-di-tert-butylnaphthalene are synthesized according to different alkyl substituent groups, the product selectivity is sequentially improved, and meanwhile, in view of the characteristic that the literature (W.Gump, Journal of the American Chemical Society,53(1931) 380. 381.) reports that 2, 6-di-tert-butylnaphthalene (2,6-DTBN) and 2, 7-di-tert-butylnaphthalene (2,7-DTBN) can be separated by crystallization in low-alcohol, separation and purification are facilitated, and the energy consumption and cost for separation are reduced. Therefore, the method is a route with application prospect for synthesizing 2,6-DAN and naphthalene tert-butylation.
In recent years, catalysts for catalyzing naphthalene tertiary butyl esterification are mainly large pore molecular sieves containing 12-membered rings and above, including molecular sieves with topological structures such as MOR, AFI, ATS, IFR, SSY, FAU, BEA, CON, and MSE having 12-membered rings, and molecular sieves with topological structures such as CFI, DON, and SFH having 14-membered rings.
The literature (Liu Z, Chemical Communications,23(1996)2653-2654.) reports that the highest ratio of 2,6-/2,7-DTBN on HY molecular sieves is 5.9, and the conversion is 52.4%. After stepwise acid-base treatment of HY molecular sieve, 2,6-/2,7-DTBN increased from 4.16 to 6.11 but conversion decreased from 83.4% before unmodified to 45.7% (Wang Y, Catalysis Communications,9.10(2008) 1982-. Currently, the highest 2,6-DTBN is shown on MOR zeolite with 2,6-/2,7-DTBN values up to 50, but with lower naphthalene conversion, poorer catalyst activity and lifetime compared to HY molecular sieves (K Smith, Organic & biologicalaclearchemistry, 1.9(2003) 1552-. Patents CN 101417234 a and CN 101417922A describe the results of acid treatment of Y zeolite molecular sieves to dealuminate and naphthalene tertiary butylation to make 2, 6-DTBN. Patent CN 105601459A describes the preparation of 2-methyl-6-tert-butylnaphthalene by alkylation of 2-methylnaphthalene with tert-butanol or isobutylene using a siloxane-based compound modified zeolite molecular sieve. Patent CN 105268471A reports a method for synthesizing 2, 6-diisopropyl naphthalene by using alkaline earth metal ion exchange zeolite molecular sieve as a catalyst to catalyze the alkylation reaction of naphthalene and propylene, and the selectivity of 2, 6-diisopropyl naphthalene is 41%.
In a word, the method has great space for improving the conversion rate of naphthalene and the selectivity of the product 2,6-DAN, selects a molecular sieve with a proper pore structure, and has practical value and innovative significance for carrying out pore structure modification and acidic modification on the molecular sieve on the basis.
Disclosure of Invention
According to one aspect of the invention, the catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation is provided, and the catalyst is applied to naphthalene tert-butyl reaction and has higher activity and product selectivity.
The catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation is characterized in that the Si/MeHEMT catalyst is an HEMT molecular sieve modified by metal and siloxane compounds.
The catalyst is a Si/MeHEMT catalyst prepared by metal modification and siloxane compound modification of an HEMT molecular sieve. The metal ions supported on the catalyst can be supported by a hydrothermal synthesis method or an ion exchange method. The siloxane-based compound modification refers to silanization modification on the outer surface of the HEMT molecular sieve. The catalyst is a Si/MeHEMT molecular sieve catalyst. Me is a metal.
In another aspect of the present invention, a method for preparing a Si/MeHEMT catalyst is provided, comprising the steps of: performing metal ion exchange on the HEMT molecular sieve to obtain a metal modified HEMT molecular sieve (MeHEMT);
and then modifying the MeHEMT by a siloxane compound to obtain the Si/MeHEMT catalyst.
In the Si/MeHEMT catalyst, the mass ratio of the metal element Me is 1-20 wt%, and the mass ratio of the Si element is 39.1-45.5 wt%.
Preferably, the mass ratio of the metal element Me is 2.5-5.7%; the mass ratio of the metal element Me in the Si/MeHEMT catalyst can be 2.5 wt%, 2.6 wt%, 5.7 wt% and 3.1 wt%; the Si element may be contained in an amount of 43.5 wt%, 43.3 wt%, 39.1 wt%, 41.4 wt%, or 45.5 wt%.
Optionally, the metal ion Me is at least one of lanthanide metal ions.
Optionally, the metal ion exchange step is performed by ion exchange with a solution containing a metal salt selected from at least one of lanthanide metal nitrate and lanthanide metal halide;
the concentration of metal ions in the solution containing the metal salt is 0.05-0.5 mol/L;
the solid-liquid weight ratio of the HEMT molecular sieve to the solution containing the metal salt is (0.02-0.1): 1.0;
even more preferably, the concentration of the metal ions in the solution containing the metal salt is 0.05-0.2 mol/L.
Alternatively, the lower limit of the metal ion concentration range in the lanthanide metal salt solution is selected from 0.05mol/L and the upper limit is selected from 0.1mol/L and 0.2 mol/L.
Preferably, the solid-liquid weight ratio of the HEMT molecular sieve to the solution containing the metal salt is (0.03-0.09): 1.0.
alternatively, the lower limit of the solid-liquid weight ratio range of the HEMT molecular sieve to the metal salt-containing solution is selected from the group consisting of 0.04:1, 0.05: 1, the upper limit is selected from 0.06:1, 0.08:1 or 0.09: 1.
The ion exchange conditions can be selected by the skilled person as desired, preferably the ion exchange conditions are: ion exchange is carried out for 1 to 6 times at the temperature of between 30 and 80 ℃, and the ion exchange time is 1.0 to 12.0 hours each time.
Optionally, the siloxane-based compound is selected from at least one of ethyl orthosilicate, isobutyltriethoxysilane, phenyltriethoxysilane, octyltrichlorosilane, dodecyltrichlorosilane, or hexadecyltrichlorosilane.
Optionally, the siloxane-based compound is used in an amount of: modifying each gram of the metal modified HEMT molecular sieve by adopting 0.5-20.0 mmol of siloxane compound;
more preferably, the siloxane-based compound is used in an amount of: and modifying each gram of the metal modified HEMT molecular sieve by adopting 0.5-10.0 mmol of siloxane compound.
Alternatively, the lower limit of the amount of silylating agent used in the step of silylating the outer surface is selected from 0.5mmol or 4mmol, and the upper limit is selected from 6mmol or 10 mmol.
Optionally, the step of silanizing the outer surface is to dissolve a silanization reagent in toluene, and silanization treatment is performed by heating in a water bath, refluxing and stirring to obtain the catalyst.
The skilled person can select the parameters in the external surface silanization step as desired, preferably, said step c) is: dissolving a siloxane compound in toluene, heating in a water bath, refluxing and stirring for silanization treatment to obtain the Si/MeHEMT catalyst;
preferably, the silylation temperature in the step of modifying the siloxane-based compound is 60-90 ℃ and the time is 2-24 hours.
The siloxane-based compound in the step c) is selected from at least one of ethyl orthosilicate, isobutyl triethoxysilane, phenyl triethoxysilane, octyl trichlorosilane, dodecyl trichlorosilane and hexadecyl trichlorosilane.
More preferably, the silylating agent is selected from any one of phenyltriethoxysilane, isobutyltriethoxysilane, dodecyltrichlorosilane or hexadecyltrichlorosilane.
The invention also provides an application of the Si/MeHEMT catalyst in naphthalene shape-selective alkylation reaction, the Si/MeHEMT catalyst is activated for 2 hours at 400-600 ℃ in nitrogen atmosphere before reaction, then the catalyst, solvent and alkylating reagent are mixed uniformly and placed in a stainless steel high-pressure reaction kettle for reaction, and after the reaction is finished, the catalyst and liquid product are separated.
The alkylating agent is tert-butyl alcohol and/or isobutene.
The invention also provides a preparation method of 2, 6-di-tert-butyl naphthalene, which comprises the following steps:
the starting material containing naphthalene and alkylating agent is contacted with the Si/MeHEMT catalyst as described above to obtain 2, 6-di-tert-butylnaphthalene.
Optionally, the alkylating agent is tert-butanol and/or isobutylene;
alternatively, an autoclave batch reaction is employed;
before reaction, activating the Si/MeHEMT catalyst for 2-4 hours at 500-600 ℃, then cooling the system to 200 ℃ for later use, adding naphthalene and cyclohexane into a polytetrafluoroethylene lining of an autoclave, and then adding the catalyst and an alkylating agent for reaction to prepare 2, 6-di-tert-butylnaphthalene;
the reaction temperature is 100-350 ℃, and the reaction time is 0.5-4 hours.
In one embodiment, the method for preparing 2, 6-di-tert-butylnaphthalene comprises the following steps:
an autoclave batch reaction is adopted, before the reaction, the catalyst is activated for 2 to 4 hours at the temperature of 500 ℃ and 600 ℃ in the nitrogen atmosphere, then the temperature is reduced to 200 ℃, the naphthalene and the cyclohexane are added into a polytetrafluoroethylene lining of the autoclave, the catalyst is added, and the alkylating reagent is added (introduced). The reaction temperature is 100 ℃ and 350 ℃, and the reaction time is 0.5-4 hours.
In one embodiment, the alkylating agent may be introduced after the reaction temperature is reached, or the temperature may be raised to the reaction temperature after the introduction.
The invention can produce the beneficial effects that:
1) the catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation is a Si/MeHEMT catalyst prepared by metal modification and siloxane compound modification of an HEMT molecular sieve. The catalyst is applied to the naphthalene alkylation reaction and has the advantages of high catalytic activity and good selectivity of DTBN and 2, 6-DTBN.
2) According to the catalyst for preparing 2, 6-di-tert-butylnaphthalene by naphthalene shape-selective alkylation, provided by the invention, an HEMT molecular sieve is taken as a precursor, the acidity of the HEMT molecular sieve is changed by ion exchange of the EMT molecular sieve, the acid strength of a strong acid site is reduced, and the HEMT molecular sieve is favorable for the generation of 2,6-DTBN, and meanwhile, the acid site on the outer surface is passivated by using a silanization technology, so that the generated 2,6-DTBN is further inhibited from secondary side reaction, and the selectivity of a product is effectively improved.
3) The preparation method of 2, 6-di-tert-butylnaphthalene provided by the invention uses the catalyst in naphthalene tert-butylation reaction, the naphthalene conversion rate can reach more than 80%, and the 2,6-/2,7-DTBN ratio can reach more than 8.0. In the optimal result, the 2,6/2,7-DTBN can reach 9.1; the naphthalene conversion can still be maintained at 94.1%.
4) The preparation method of the catalyst provided by the invention is simple to operate, has mild reaction conditions, and has a huge industrial application prospect.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present invention were all commercially available, and the HEMT molecular sieve had a Si/Al ratio of 3.9.
In the embodiment of the invention, the gas chromatograph is Agilent 7890A chromatographic on-line analysis. The hydrocarbon components were analyzed on an Agilent HP-530 m.times.32 μm.times.0.25 μm capillary column and detected on a FID detector.
In the examples of the present invention, the mass percentage of each substance in the obtained product was measured by using a Magix 2424X-ray fluorescence analyzer (XRF) from Philips.
In the embodiment of the present invention, the first and second substrates,
Figure BDA0001888438160000061
Figure BDA0001888438160000062
EXAMPLE 1 preparation of catalyst sample NTC-1
1) Taking 5g of HEMT molecular sieve powder, adding La (NO) containing 0.1mol/L3)3The aqueous solution was ion exchanged three times at 80 ℃ for 4 hours each time.
2) The solid obtained in the above step was washed, dried and calcined at 550 ℃ for 6 hours, and 4.0g of the obtained sample was put into a toluene solution containing 24.0mmol of phenyltriethoxysilane, and then silanized by stirring at 90 ℃ under reflux for 12 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder, which is named as NTC-1.
The catalyst sample NTC-1 obtained contained the metal element La in an amount of 2.5 wt% and the Si in an amount of 43.5 wt%.
EXAMPLE 2 preparation of catalyst sample NTC-2
1) Taking 5g of HEMT molecular sieve powder, adding 0.1mol/L Pr (NO)3)3The aqueous solution was ion exchanged three times at 80 ℃ for 4 hours each time.
2) The solid obtained in the above step was washed, dried and calcined at 550 ℃ for 6 hours, and 4.0g of the obtained sample was put into a toluene solution containing 24.0mmol of phenyltriethoxysilane, and then silanized by stirring at 90 ℃ under reflux for 12 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder, which is named as NTC-2.
The mass ratio of the metal element Pr in the obtained catalyst sample NTC-2 was 2.6 wt%, and the mass ratio of the Si element was 43.3 wt%.
EXAMPLE 3 preparation of catalyst sample NTC-3
1) Taking 5g of HEMT molecular sieve powder, adding 0.2mol/L Ce (NO)3)3The aqueous solution was ion exchanged six times at 80 ℃ for 8 hours each.
2) The solid obtained in the above step was washed, dried and calcined at 550 ℃ for 6 hours, and 4.0g of the obtained sample was put into a toluene solution containing 2.0mmol of phenyltriethoxysilane, and then silanized by stirring under reflux at 90 ℃ for 12 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder, which is named as NTC-3.
The mass ratio of the metal element Ce in the obtained catalyst sample NTC-3 was 5.7 wt%. The mass ratio of the Si element was 39.1 wt%.
EXAMPLE 4 preparation of NTC-4 catalyst sample
1) Taking 5g of HEMT molecular sieve powder, adding La (NO) containing 0.1mol/L3)3The aqueous solution was ion exchanged four times at 80 ℃ for 4 hours each time.
2) The solid obtained in the above step was washed, dried and calcined at 550 ℃ for 6 hours, and 4.0g of the obtained sample was put into a toluene solution containing 16.0mml of isobutyltriethoxysilane, and subjected to reflux stirring at 90 ℃ for silylation for 24 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder which is named as NTC-4.
The catalyst sample NTC-4 obtained contained 3.1 wt% of La as the metal element and 41.4 wt% of Si as the element.
EXAMPLE 5 preparation of catalyst sample NTC-5
1) 5g of HEMT molecular sieve powder is taken and ion-exchanged four times by using 0.1mol/L La (NO3)3 aqueous solution, the temperature is 80 ℃, and each time is 4 hours.
2) The solid obtained in the previous step is taken, washed, dried and roasted at 550 ℃ for 6 hours, 4.0g of the obtained sample is taken and put into a toluene solution containing 40.0mml of dodecyl trichlorosilane, and the mixture is stirred under reflux at 90 ℃ for silanization for 24 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder, which is named as NTC-5.
The catalyst sample NTC-5 obtained contained 3.1 wt% of La as the metal element and 45.5 wt% of Si as the element.
EXAMPLE 6 preparation of catalyst sample NTC-6
1) Taking 5g of HEMT molecular sieve powder, adding La (NO) containing 0.1mol/L3)3The aqueous solution was ion exchanged four times at 80 ℃ for 4 hours each time.
2) The solid obtained in the above step was washed, dried and calcined at 550 ℃ for 6 hours, and 4.0g of the obtained sample was put into a toluene solution containing 40.0mml of hexadecyltrichlorosilane, and then silanized by stirring under reflux at 90 ℃ for 24 hours. Filtering, drying and roasting at 550 ℃ for 6 hours to obtain finished catalyst powder, which is named as NTC-6.
The catalyst sample NTC-6 obtained contained 3.1 wt% of La as the metal element and 45.1 wt% of Si as the element.
Example 7
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of HEMT was activated in a muffle furnace for 4 hours in an air atmosphere at 550 ℃ and then cooled to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 130 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 8
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-1 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 9
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-2 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 10
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-3 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 11
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-4 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 12
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-5 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added. Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 13
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-6 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use. 1.28g of naphthalene and 33.66g of cyclohexane were mixed, the catalyst was added and stirred, and finally 2.22g of tert-butanol were added.
Before the reaction was heated, the air in the autoclave was replaced with nitrogen gas 3 times, and then the autoclave was pressurized to 2.0 MPa. The reaction temperature was 160 ℃ for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
Example 14
Naphthalene tert-butylation reactions were carried out on autoclave reactors, lined with 100mL volume of polytetrafluoroethylene. Before the reaction, 1.0g of NTC-1 was activated in a muffle furnace for 4 hours in an air atmosphere at a temperature of 550 ℃ and then the temperature was lowered to 200 ℃ for further use.
1.28g of naphthalene and 33.66g of cyclohexane were mixed, added to the mixture, and stirred.
The air in the autoclave was replaced with nitrogen 3 times before the reaction was heated. After the reaction temperature reaches 160 ℃, introducing isobutene gas, and maintaining the reaction pressure at 1.0MPa for 2 hours. After the reaction, the product was centrifuged and analyzed by gas chromatography, and the reaction results are shown in table 1.
TABLE 1 catalytic reaction performance of different catalysts for preparation of 2, 6-di-tert-butylnaphthalene by naphthalene tert-butylation (reaction 2h)
Figure BDA0001888438160000111
Wt% is mass percentage content.
As shown in Table 1, when the catalyst provided by the invention is used for catalyzing naphthalene shape-selective alkylation to prepare 2, 6-di-tert-butylnaphthalene, 2,6/2,7-DTBN can reach 9.1; the naphthalene conversion can still be maintained at 94.1%.
The above description is only for the purpose of illustrating the present invention and is not intended to limit the present invention in any way, and the present invention is not limited to the above description, but rather should be construed as being limited to the scope of the present invention.

Claims (5)

1. A preparation method of 2, 6-di-tert-butylnaphthalene is characterized by comprising the following steps:
contacting a raw material containing naphthalene and an alkylating agent with a Si/MeHEMT catalyst to obtain 2, 6-di-tert-butylnaphthalene;
the method specifically comprises the following steps: before reaction, activating the Si/MeHEMT catalyst for 2-4 hours at 500-600 ℃, then cooling the system to 200 ℃ for later use, adding naphthalene and cyclohexane into a polytetrafluoroethylene lining of an autoclave, and then adding the catalyst and an alkylating agent for reaction to prepare 2, 6-di-tert-butylnaphthalene;
the reaction temperature is 100-350 ℃, and the reaction time is 0.5-4 hours;
the alkylating agent is tert-butyl alcohol and/or isobutene;
the Si/MeHEMT catalyst is an HEMT molecular sieve modified by metal and siloxane compounds;
the metal is at least one of lanthanide metals;
in the Si/MeHEMT catalyst, the mass proportion of a metal element Me is 1-20 wt%; the mass ratio of the Si element is 39.1-45.5 wt%; the siloxane-based compound is selected from at least one of ethyl orthosilicate, isobutyl triethoxysilane, phenyl triethoxysilane, octyl trichlorosilane, dodecyl trichlorosilane or hexadecyl trichlorosilane.
2. The method of claim 1, wherein the method of preparing the Si/MeHEMT catalyst comprises the steps of:
performing metal ion exchange on the HEMT molecular sieve to obtain a metal modified HEMT molecular sieve;
and then modifying the metal modified HEMT molecular sieve by a siloxane compound to obtain the Si/MeHEMT catalyst.
3. The method for producing 2, 6-di-tert-butylnaphthalene according to claim 2, wherein the metal ion exchange step is carried out by ion exchange with a solution containing a metal salt selected from at least one of lanthanide metal nitrates or lanthanide metal halides.
4. The method for producing 2, 6-di-tert-butylnaphthalene according to claim 3, wherein the concentration of metal ions in the solution containing a metal salt is 0.05 to 0.5 mol/L.
5. The method of claim 1, wherein the siloxane-based compound is used in an amount of: and modifying each gram of the metal modified HEMT molecular sieve by adopting 0.5-20.0 mmol of siloxane compound.
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