CN112661587A - Process for preparing 2, 6-dialkylnaphthalene - Google Patents
Process for preparing 2, 6-dialkylnaphthalene Download PDFInfo
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Abstract
The invention relates to the technical field of dialkyl naphthalene, and discloses a preparation method of 2, 6-dialkyl naphthalene. The method comprises the following steps: (1) under the condition of a first alkylation reaction and in the presence of a first solid acid catalyst, naphthalene is in first contact with an alkylating agent to obtain an alkylated product; (2) under the isomerization reaction condition and in the presence of a second solid acid catalyst, carrying out second contact on the alkylation product to obtain an isomerization product; (3) and (3) carrying out third contact on the isomerization product and an alkylating agent under the condition of second alkylation reaction and in the presence of a third solid acid catalyst to obtain the 2, 6-dialkyl naphthalene. The conversion rate of the naphthalene prepared by the method provided by the invention is up to 48%, the selectivity of the 2, 6-dialkyl naphthalene is up to 61%, and the content of heavy components (substances with molecular weight not less than trialkyl naphthalene) in the product is lower than 0.8 wt%.
Description
Technical Field
The invention relates to the technical field of dialkyl naphthalene, in particular to a preparation method of 2, 6-dialkyl naphthalene.
Background
The production capacity of tar naphthalene, ethylene tar and petroleum naphthalene extracted from C9 aromatic hydrocarbon in coal tar in China is considerable. In 2013, the yield of the tar naphthalene, the ethylene tar and the petroleum naphthalene extracted from the C9 aromatic hydrocarbon in the coal tar in China reaches 130 ten thousand t/a. Therefore, the development of the downstream high value-added product of naphthalene is of great significance. Naphthalene alkylation can produce many products, of which 2, 6-dialkylnaphthalene has the greatest practical value.
The early synthesis of Diisopropylnaphthalene (DIPN) was carried out by liquid phase method using amorphous SiO2-A12O3Or an anhydrous aluminum trichloride catalyst. The method has high activity, but the defects are also obvious: namely, DIPN is synthesized on catalysts such as anhydrous aluminum trichloride and the like, reaction products are complex, namely isopropyl naphthalene (IPN) and a plurality of dialkyl naphthalenes are obtained, the dialkyl naphthalenes can further react to form a plurality of substituted products, the by-products are more, the yield of 2, 6-diisopropyl naphthalene (2,6-DIPN) is low, the separation is difficult, and the production cost is high. And the catalyst has high corrosivity and serious environmental pollution.
Catalytica also uses naphthalene and propylene as raw materials, and first SiO2-A12O3Reacting on catalyst to balance, then making the balance component undergo the process of alkylation reaction on mordenite to obtain 2,6-DIPN whose content is 43%, purity can be up to 99.5% of the total weight of the composition. But SiO2-A12O32,6-DIPN has no shape selectivity, so the process flow is complex, the energy consumption is large, the product separation is difficult, the equipment investment is large, and the cost is high.
CN1660726B discloses a method for preparing 2, 6-dimethylnaphthalene by disproportionation of beta-methylnaphthalene under the catalysis of ionic liquid, which comprises the following steps: mixing beta-methylnaphthalene and a solvent in a molar ratio of 1: 4-7, adding an ionic liquid catalyst accounting for 8-17 percent of the total weight of the mixed solution into the mixed solution, carrying out disproportionation reaction at the temperature of 120-160 ℃ under the protection of inert gas, and finishing the reaction after 2-4h to obtain the 2, 6-dimethylnaphthalene.
CN1362392B discloses a method for preparing 2, 6-dimethylnaphthalene, under the critical reaction condition, using naphthalene or 2-methylnaphthalene or mixed methylnaphthalene as raw material a, using methanol as raw material B, using inert solvent as raw material C, mixing the raw materials a, B and C in the ratio of a: b: c is 1: 0.5-3: 1-4 at a reaction temperature of 370-550 ℃ and a reaction pressure of 3.1-12.0MPa for 0.1-2h-1The reaction space velocity of (2) is passed through catalyst bed layer, and alkylation reaction is implemented to synthesize 2, 6-dimethylnaphthalene.
CN107262140A discloses a catalyst for preparing 2, 6-dimethylnaphthalene by alkylation of 2-methylnaphthalene, firstly, filling a superfine nano CuHZSM-5 molecular sieve catalyst into a fixed bed reactor, and carrying out primary taste activation pretreatment on the catalyst for 1-3h at 500-600 ℃ in a nitrogen atmosphere on a reaction device before reaction; uniformly mixing 2-methylnaphthalene, an alkylating reagent and a solvent to obtain a raw material solution, and carrying out contact reaction on the raw material and a catalyst by using a metering pump; wherein the grain size catalyzed by the CuHZSM-5 molecular sieve is between 10 and 100 nm.
Disclosure of Invention
The invention aims to provide a novel preparation method of 2, 6-dialkyl naphthalene, which has the characteristics of high selectivity of the 2, 6-dialkyl naphthalene and low content of heavy components in a product.
In order to achieve the above object, the present invention provides a method for producing 2, 6-dialkylnaphthalene, comprising:
(1) under the condition of a first alkylation reaction and in the presence of a first solid acid catalyst, naphthalene is in first contact with an alkylating agent to obtain an alkylated product;
(2) under the isomerization reaction condition and in the presence of a second solid acid catalyst, carrying out second contact on the alkylation product to obtain an isomerization product;
(3) and (3) carrying out third contact on the isomerization product and an alkylating agent under the condition of second alkylation reaction and in the presence of a third solid acid catalyst to obtain the 2, 6-dialkyl naphthalene.
Preferably, the 2, 6-dialkylnaphthalene is 2, 6-dimethylnaphthalene or 2, 6-diisopropylnaphthalene.
Preferably, the alkylating agent is methanol or propylene.
Preferably, the Hammett functions of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) are each in the range of-10 to-1.
Preferably, the second solid acid catalyst in step (2) has a Hammett function in the range of-14 to-2.5.
Preferably, the difference between the Hammett functions of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) is within. + -. 5%.
Preferably, the absolute value of the hamilter function of the second solid acid catalyst in step (2) is more than 15% higher than the absolute value of the hamilter function of the first solid acid catalyst in step (1).
Preferably, the absolute value of the hamilter function of the second solid acid catalyst in step (2) is more than 15% higher than the absolute value of the hamilter function of the third solid acid catalyst in step (3).
Through the technical scheme, compared with the prior art, the preparation method of the 2, 6-dialkyl naphthalene provided by the invention has the following advantages:
(1) the alkylation reagent and the solid acid catalyst used in the invention have low price and low raw material cost; the reaction condition is mild, easy to control and high in safety;
(2) a fixed bed reactor is adopted for carrying out solid-liquid phase catalytic reaction and isomerization reaction, the separation is simple and convenient, and the production is continuous;
(3) the conversion rate of the naphthalene prepared by the method provided by the invention is up to 48%, the selectivity of the 2, 6-dialkyl naphthalene is higher than 61%, and the content of heavy components (substances with molecular weight not less than trialkyl naphthalene) in the product is lower than 0.8 wt%.
Drawings
FIG. 1 is a process flow diagram of 2, 6-diisopropylnaphthalene of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
All pressures mentioned in this specification are, unless explicitly stated, gauge pressures.
In the context of this specification, the reaction temperature refers to the catalyst bed hot spot temperature, which refers to the highest temperature within the catalyst bed.
In the invention, the Hamilt function H0 refers to an acid strength index of a catalyst, and a specific calculation formula is as follows:
H0＝-lg[H+]＝-lgKBH+－lg{[BH+]/[B]}，
wherein, KBH+Is the ionization constant of the conjugate acid of the indicator, which can be determined by the usual methods for determining the equilibrium constant, and [ BH+]/[B]Is the ionization ratio of the indicator and can be determined by UV-visible spectrophotometry (specific measurement method: Lawrence J. Henderson. centering the relationship between the acids and the efficiency to the predetermined selectivity. am. J. Physiol.1908,21, 173. F. 179.).
The invention provides a preparation method of 2, 6-dialkyl naphthalene, which comprises the following steps:
(1) under the condition of a first alkylation reaction and in the presence of a first solid acid catalyst, naphthalene is in first contact with an alkylating agent to obtain an alkylated product;
(2) under the isomerization reaction condition and in the presence of a second solid acid catalyst, carrying out second contact on the alkylation product to obtain an isomerization product;
(3) and (3) carrying out third contact on the isomerization product and an alkylating agent under the condition of second alkylation reaction and in the presence of a third solid acid catalyst to obtain the 2, 6-dialkyl naphthalene.
The inventor of the invention finds in research that: performing a first alkylation reaction on naphthalene and an alkylating agent, and controlling the molar ratio of the naphthalene to the alkylating agent to obtain an alkylation product, namely a mixture of 1-alkyl naphthalene and 2-alkyl naphthalene; carrying out isomerization reaction on 1-alkyl naphthalene in the alkylation product to obtain an isomerization product; and then carrying out a second alkylation reaction on the isomerization product and an alkylating agent, and controlling the molar ratio of the isomerization product to the alkylating agent to improve the selectivity of the 2, 6-dialkyl naphthalene and reduce the content of heavy components (substances with molecular weight not less than that of the third alkyl naphthalene) in the product.
The present invention combines a first alkylation, isomerization and a second alkylation to reduce byproduct production.
According to the present invention, the 2, 6-dialkylnaphthalene is not particularly limited. The two alkyl groups in the 2, 6-dialkylnaphthalene may be the same or different, and specifically, the 2, 6-dialkylnaphthalene is preferably at least one selected from the group consisting of 2, 6-dimethylnaphthalene, 2, 6-diethylnaphthalene, 2, 6-dipropylnaphthalene, 2, 6-diisopropylnaphthalene, 2, 6-di-n-butylnaphthalene, 2, 6-diisobutylnaphthalene and 2, 6-di-tert-butylnaphthalene, and is preferably 2, 6-dimethylnaphthalene or 2, 6-isopropylnaphthalene.
According to the invention, the alkylating reagents in step (1) and step (3) may be the same or different, depending on the desired 2, 6-dialkylnaphthalene. The alkylating agent is not particularly limited in the present invention. Specifically, the alkylating agent is selected from at least one of a low olefin and a low alkyl alcohol. In the present invention, the term "low" means that the number of carbon atoms is not more than 4, for example, low olefins means olefins having not more than 4 carbon atoms, for example, the low olefins are selected from at least one of ethylene, propylene, n-butene and isobutylene, and preferably propylene; for example, the lower alkyl alcohol refers to an alkyl alcohol having not more than 4 carbon atoms, and is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
In the present invention, preferably, in step (1), the molar ratio of said naphthalene to said alkylating agent is from 4 to 10: 1, more preferably 4 to 8: 1. that is, the naphthalene is used in an amount of 4 moles, 6 moles, 8 moles, 10 moles, and any value within a range of any two of these points, based on 1 mole of the alkylating agent. The preferred molar ratio of naphthalene to alkylating agent used in the present invention is more favorable to increase the selectivity of 2-alkylnaphthalene in the alkylated product.
In the present invention, preferably, in step (3), the molar ratio of the isomerized product to the alkylating agent is from 4 to 10: 1, more preferably 4 to 8: 1. that is, the amount of the isomerized product is 4 moles, 6 moles, 8 moles, 10 moles, and any value within the range of any two of these points, based on 1 mole of the alkylating agent. The preferred molar ratio of isomerization product to alkylating agent used in the present invention is more favorable for increasing the selectivity of 2, 6-dialkylnaphthalene.
According to the present invention, it is preferred that the Hammett function of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) each be in the range of-10 to-1, for example, -10, -8, -6, -4, -1, and any value in the range formed by any two of these points, preferably in the range of-6.6 to-3.5, in order to further improve the selectivity of 2, 6-dialkylnaphthalene.
According to the present invention, it is preferred that the Hammett function of the second solid acid catalyst in step (2) is in the range of-14 to-2.5, for example, -14, -11, -8, -5, -2.5, and any value within the range formed by any two of these values, preferably in the range of-10 to-8, in order to further improve the selectivity of 2, 6-dialkylnaphthalene.
In the present invention, it is preferable that the difference between the Hammett functions of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) is within. + -. 5%.
According to the present invention, the Hammett function of the second solid acid catalyst is closely related to the Hammett function of the first solid acid catalyst and the Hammett function of the third solid acid catalyst, and in order to further improve the selectivity of 2, 6-dialkylnaphthalene and reduce heavy component impurities, the absolute value of the Hammett function of the second solid acid catalyst in step (2) is more than 15% higher, more preferably 60 to 80% higher, than the absolute value of the Hammett function of the first solid acid catalyst in step (1), and/or the absolute value of the Hammett function of the second solid acid catalyst in step (2) is more than 15% higher, more preferably 60 to 80% higher, than the absolute value of the Hammett function of the third solid acid catalyst in step (3).
In the present invention, the first solid acid catalyst, the second solid acid catalyst and the third solid acid catalyst all refer to catalysts that are acidic in a solid state. According to the present invention, the first solid acid catalyst, the second solid acid catalyst, and the third solid acid catalyst are not particularly limited.
Specifically, the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) are the same or different and each is selected from at least one of an MFI-configuration molecular sieve, an MTT-configuration molecular sieve, an MWW-configuration molecular sieve and a solid super acid, preferably an MWW-configuration molecular sieve; the second solid acid catalyst in the step (2) is the same as or different from the first solid acid catalyst in the step (1), and the second solid acid catalyst is at least one selected from the group consisting of a molecular sieve of MTT configuration, a molecular sieve of BEA configuration, a molecular sieve of MWW configuration, a molecular sieve of MFI configuration and a solid super acid, and is preferably a molecular sieve of BEA configuration. The MWW-configuration molecular sieve and the BEA-configuration molecular sieve which are preferred by the invention are more favorable for improving the selectivity of the 2, 6-dialkyl naphthalene.
Preferably, the MWW configuration molecular sieve is selected from at least one of MCM-22 molecular sieve, MCM-56 molecular sieve, MP-01 molecular sieve, MP-02 molecular sieve, MP-03 molecular sieve and MP-04 molecular sieve, and the first solid acid catalyst is preferably MCM-56 molecular sieve; the third solid acid catalyst is preferably an MCM-22 molecular sieve.
The BEA configuration molecular sieve is at least one selected from BTA-01 molecular sieve, BTA-02 molecular sieve, BTA-03 molecular sieve, BTA-04 molecular sieve and ZSM-5 molecular sieve, and the second solid acid catalyst is preferably ZSM-5 molecular sieve.
According to a preferred embodiment of the present invention, the first solid acid catalyst is preferably an MCM-56 molecular sieve, the second solid acid catalyst is preferably a ZSM-5 molecular sieve, and the third solid acid catalyst is preferably an MCM-22 molecular sieve. With this preferred embodiment, the conversion of naphthalene and the selectivity of 2, 6-dialkylnaphthalene can be further improved.
According to the present invention, the first contact, the second contact, and the third contact are not particularly limited. In particular, the first contacting, the second contacting and the third contacting are all carried out in a liquid-solid phase reactor, preferably the liquid-solid phase reactor is selected from at least one of a fixed bed reactor, a fluidized bed reactor, a moving bed reactor and a trickle bed reactor, preferably a fixed bed reactor.
In the present invention, the first alkylation reaction conditions include: the reaction temperature is 200-260 ℃, preferably 220-230 ℃; the reaction pressure is 1-5MPa, preferably 2.5-3.5 MPa; the mass space velocity of naphthalene is 0.1-2h-1Preferably 0.5-0.8h-1. The use of the preferred first alkylation reaction conditions is more advantageous in increasing the selectivity of the 2-alkylnaphthalene.
In the present invention, the isomerization reaction conditions include: the reaction temperature is 250-320 ℃, and preferably 270-290 ℃; the reaction pressure is 1 to 5MPa, preferably 2.5 to 3.5 MPa. The preferred alkylation reaction conditions are more favorable for improving the selectivity of converting 1-alkyl naphthalene into 2-alkyl naphthalene.
In the present invention, the second alkylation reaction conditions include: the reaction temperature is 200-260 ℃, preferably 220-230 ℃; the reaction pressure is 1-5MPa, preferably 2.5-3.5 MPa; the mass space velocity of the isomerization product is 0.1-2h-1Preferably 0.5-0.8h-1. The use of the preferred second alkylation reaction conditions is more advantageous for increasing the 2, 6-dialkylnaphthaleneSelectivity of (2).
In the present invention, it is preferable that the first alkylation reaction product is entirely fed into the isomerization reactor to undergo isomerization reaction and the isomerization reaction product is entirely fed into the second alkylation reactor to undergo reaction, so that the mass space velocities of the alkylation product and the isomerization product are considered to be 0.1 to 2 hours, respectively, based on the mass space velocity of naphthalene-1Preferably 0.5-0.8h-1。
Preferably, the loading weight ratio of the first alkylation catalyst, the isomerization catalyst and the second alkylation catalyst is 1: 0.6-1.5: 0.6-1.5.
For the sake of understanding, the present invention will be further described below by way of examples.
In the examples and comparative examples of the present invention, the calculation formula of the Hammett function H0 is as follows: h0 ═ lg [ H+]＝-lgKBH+－lg{[BH+]/[B]}，
Wherein, KBH+Is the ionization constant of the conjugate acid of the indicator, which can be determined by the usual methods for determining the equilibrium constant, and [ BH+]/[B]Is the ionization ratio of the indicator and can be determined by uv-vis spectrophotometry.
Specifically, the measurement is carried out by the method disclosed in Lawrence J.Henderson.Concerning the relationship between the acids and the capacity to the prior probability distribution. am.J.Physiol.1908,21, 173-.
In the embodiment and the comparative example of the invention, the reactors are fixed bed reactors, and the heavy component refers to a substance with the molecular weight being more than or equal to triisopropylnaphthalene.
In the examples and comparative examples, the MCM-22 molecular sieve, the MCM-56 molecular sieve and the ZSM-5 molecular sieve were all commercially available from Mobil oil Co., USA; BTA-01 molecular sieve, BTA-02 molecular sieve, BTA-03 molecular sieve, BTA-04 molecular sieve, MP-01 molecular sieve, MP-02 molecular sieve, MP-03 molecular sieve and MP-04 molecular sieve are all commercially available products from Shanghai Petroleum chemical institute of China petrochemical industry, Inc.
Example 1
(1) Naphthalene and propylene were mixed at a ratio of 4: 1 is fed to the first alkylation reactionReactor, naphthalene feed 12.2g/h, to obtain an alkylation product, wherein the first alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.6h-1The reactor is filled with 20-mesh MCM-56 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
(2) feeding the alkylation product into an isomerization reactor to obtain an isomerization product, wherein the isomerization reaction conditions comprise: the reaction temperature is 280 ℃, the reaction pressure is 3MPa, a ZSM-5 molecular sieve with 20 meshes is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-8.1;
(3) the isomerized product and propylene are mixed in a ratio of 4: 1 to obtain 2, 6-diisopropyl naphthalene, wherein the second alkylation reaction conditions comprise: the reaction temperature is 240 ℃, the reaction pressure is 3MPa, a 20-mesh MCM-22 molecular sieve is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-4.8.
The filling weight ratio of the MCM-56 molecular sieve, the ZSM-5 molecular sieve and the MCM-22 molecular sieve is 1: 1: 1.
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Comparative example 1
Naphthalene and propylene were mixed at a ratio of 2: 1, and feeding naphthalene with the feeding amount of 12.2g/h to obtain 2, 6-diisopropyl naphthalene, wherein the alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.6h-1The reactor is filled with a 20-mesh MCM-22 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 2
(1) Naphthalene and methanol were mixed at 8: 1 is fed into the first alkylation reactor with a naphthalene feed rate of 12.2g/h to obtain the alkaneA alkylation product, wherein the first alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.6h-1The reactor is filled with 30-mesh MCM-56 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
(2) feeding the alkylation product into an isomerization reactor to obtain an isomerization product, wherein the isomerization reaction conditions comprise: the reaction temperature is 280 ℃, the reaction pressure is 3MPa, a ZSM-5 molecular sieve with 30 meshes is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-8.1;
(3) the isomerized product and methanol were combined in a 8: 1 to a second alkylation reactor to obtain 2, 6-dimethylnaphthalene, wherein the second alkylation reaction conditions comprise: the reaction temperature is 240 ℃, the reaction pressure is 3MPa, a 30-mesh MCM-22 molecular sieve is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-4.8;
the filling weight ratio of the MCM-56 molecular sieve, the ZSM-5 molecular sieve and the MCM-22 molecular sieve is 1: 1: 1.
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Comparative example 2
Naphthalene and methanol were mixed at a ratio of 4: 1, and feeding naphthalene with the feeding amount of 12.2g/h to obtain 2, 6-dimethylnaphthalene, wherein the alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.6h-1The reactor is filled with 30-mesh MCM-22 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 3
(1) Naphthalene and isopropanol were mixed at 8: 1, to a first alkylation reactor with a naphthalene feed rate of 12.2g/h to obtain an alkylation product, wherein the first alkylation reactionThe conditions include: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.8h-1The reactor is filled with a 40-mesh MCM-56 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
(2) feeding the alkylation product into an isomerization reactor to obtain an isomerization product, wherein the isomerization reaction conditions comprise: the reaction temperature is 280 ℃, the reaction pressure is 3MPa, a ZSM-5 molecular sieve with 40 meshes is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-8.1;
(3) the isomerized product and isopropanol were mixed in a 8: 1 to obtain 2, 6-diisopropyl naphthalene, wherein the second alkylation reaction conditions comprise: the reaction temperature is 240 ℃, the reaction pressure is 3MPa, a 40-mesh MCM-22 molecular sieve is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-4.8;
the filling weight ratio of the MCM-56 molecular sieve, the ZSM-5 molecular sieve and the MCM-22 molecular sieve is 1: 0.8: 0.9.
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Comparative example 3
Naphthalene and isopropanol were mixed at a ratio of 4: 1, and feeding naphthalene with the feeding amount of 12.2g/h to obtain 2, 6-diisopropyl naphthalene, wherein the alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.8h-1The reactor is filled with a 40-mesh MCM-22 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 4
(1) Naphthalene and tert-butanol were mixed at a ratio of 4: 1, to a first alkylation reactor at a naphthalene feed rate of 12.2g/h to provide an alkylation product, wherein the first alkylation reaction conditions comprise: reaction temperatureThe reaction pressure is 3MPa at 230 ℃, and the mass space velocity of naphthalene is 0.7h-1The reactor is filled with 20-mesh MCM-56 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
(2) feeding the alkylation product into an isomerization reactor to obtain an isomerization product, wherein the isomerization reaction conditions comprise: the reaction temperature is 280 ℃, the reaction pressure is 3MPa, a ZSM-5 molecular sieve with 20 meshes is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-8.1;
(3) mixing the isomerized product and tert-butyl alcohol in a ratio of 4: 1 to a second alkylation reactor to obtain 2, 6-di-tert-butylnaphthalene, wherein the second alkylation reaction conditions comprise: the reaction temperature is 240 ℃, the reaction pressure is 3MPa, a 20-mesh MCM-22 molecular sieve is filled in the reactor, and the Hamilt function H0 of the molecular sieve is-4.8;
the filling weight ratio of the MCM-56 molecular sieve, the ZSM-5 molecular sieve and the MCM-22 molecular sieve is 1: 0.9: 1.1.
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Comparative example 4
Naphthalene and tert-butanol were mixed at a ratio of 2: 1, and feeding naphthalene with the feeding amount of 12.2g/h to obtain 2, 6-di-tert-butylnaphthalene, wherein the alkylation reaction conditions comprise: the reaction temperature is 230 ℃, the reaction pressure is 3MPa, and the mass space velocity of naphthalene is 0.7h-1The reactor is filled with a 20-mesh MCM-22 molecular sieve, and the Hamilt function H0 of the molecular sieve is-4.8;
the product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 5
2, 6-di-tert-butylnaphthalene was prepared according to the method of example 4, except that the first solid acid was an MCM-22 molecular sieve having a Hammett function of-5.4, the second solid acid was a BTA-01 molecular sieve having a Hammett function of-6, and the third solid acid was an MCM-22 molecular sieve having a Hammett function of-5.4.
The product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 6
2, 6-di-tert-butylnaphthalene was prepared according to the method of example 4, except that the first solid acid catalyst used was an MP-01 molecular sieve having a Hammett function of-6.6, the second solid acid catalyst used was a BTA-02 molecular sieve having a Hammett function of-10, and the third solid acid catalyst used was an MP-01 molecular sieve having a Hammett function of-6.6.
The product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 7
2, 6-di-tert-butylnaphthalene was prepared according to the method of example 4, except that the first solid acid was an MP-02 molecular sieve having a Hammett function of-3.5, the second solid acid was a BTA-03 molecular sieve having a Hammett function of-8, and the third solid acid was an MP-02 molecular sieve having a Hammett function of-3.5.
The product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
Example 8
2, 6-di-tert-butylnaphthalene was prepared according to the method of example 4, except that the first solid acid was an MP-03 molecular sieve having a Hammett function of-10, the second solid acid was a BTA-04 molecular sieve having a Hammett function of-14, and the third solid acid was an MP-04 molecular sieve having a Hammett function of-9.5.
The product of the alkylation reactor was subjected to rectification, crystallization and gas chromatography, and the results of the naphthalene conversion, the selectivity of 2, 6-dialkylnaphthalene and the heavy component content, which were measured after 1 hour of reaction and 24 hours of reaction, are shown in table 1.
TABLE 1
As can be seen from Table 1, the conversion rate of the naphthalene prepared by the method provided by the invention is up to 48%, the selectivity of the 2, 6-dialkyl naphthalene is up to 61%, and the content of heavy components (substances with molecular weight being more than or equal to that of trialkyl naphthalene) in the product is lower than 0.8 wt%; the device is operated for 24 hours, the conversion rate of naphthalene is up to 49 percent, the selectivity of 2, 6-dialkyl naphthalene is up to 61 percent, and the content of heavy components (substances with molecular weight not less than trialkyl naphthalene) in the product is lower than 0.8 percent by weight.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for producing a 2, 6-dialkylnaphthalene, the process comprising:
(1) under the condition of a first alkylation reaction and in the presence of a first solid acid catalyst, naphthalene is in first contact with an alkylating agent to obtain an alkylated product;
(2) under the isomerization reaction condition and in the presence of a second solid acid catalyst, carrying out second contact on the alkylation product to obtain an isomerization product;
(3) and (3) carrying out third contact on the isomerization product and an alkylating agent under the condition of second alkylation reaction and in the presence of a third solid acid catalyst to obtain the 2, 6-dialkyl naphthalene.
2. The method according to claim 1, wherein the 2, 6-dialkylnaphthalene is selected from at least one of 2, 6-dimethylnaphthalene, 2, 6-diethylnaphthalene, 2, 6-dipropylnaphthalene, 2, 6-diisopropylnaphthalene, 2, 6-di-n-butylnaphthalene, 2, 6-diisobutylnaphthalene and 2, 6-di-tert-butylnaphthalene, preferably 2, 6-dimethylnaphthalene or 2, 6-isopropylnaphthalene.
3. The process of claim 1 or 2, wherein the alkylating agent is selected from at least one of a low olefin and a low alkyl alcohol;
preferably, the low olefin is selected from at least one of ethylene, propylene, n-butene and isobutene, preferably propylene;
preferably, the lower alkyl alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
4. The process according to any one of claims 1 to 3, wherein in step (1), the molar ratio of the naphthalene to the alkylating agent is from 4 to 10: 1, preferably 4 to 8: 1;
in the step (3), the molar ratio of the isomerization product to the alkylating reagent is 4-10: 1, preferably 4 to 8: 1.
5. the process according to any one of claims 1 to 4, wherein the Hammett functions of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) are each in the range of-10 to-1, preferably in the range of-6.6 to-3.5;
the Hammett function of the second solid acid catalyst in the step (2) is in the range of-14 to-2.5, preferably in the range of-10 to-8.
6. The process of claim 5, wherein the difference between the Hammett functions of the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) is within ± 5%;
preferably, the absolute value of the Hammett function of the second solid acid catalyst in step (2) is more than 15%, preferably 60 to 80% higher than the absolute value of the Hammett function of the first solid acid catalyst in step (1), and/or the absolute value of the Hammett function of the second solid acid catalyst in step (2) is more than 15%, preferably 60 to 80% higher than the absolute value of the Hammett function of the third solid acid catalyst in step (3).
7. The process according to any one of claims 1 to 6, wherein the first solid acid catalyst in step (1) and the third solid acid catalyst in step (3) are the same or different and each is selected from at least one of an MFI-configured molecular sieve, an MTT-configured molecular sieve, an MWW-configured molecular sieve and a solid superacid, preferably an MWW-configured molecular sieve;
the second solid acid catalyst in the step (2) is the same as or different from the first solid acid catalyst in the step (1), and the second solid acid catalyst is at least one selected from the group consisting of a molecular sieve of MTT configuration, a molecular sieve of BEA configuration, a molecular sieve of MWW configuration, a molecular sieve of MFI configuration and a solid super acid, and is preferably a molecular sieve of BEA configuration.
8. The process according to claim 7, wherein the MWW configured molecular sieve is selected from at least one of MCM-22 molecular sieve, MCM-56 molecular sieve, MP-01 molecular sieve, MP-02 molecular sieve, MP-03 molecular sieve and MP-04 molecular sieve, the first solid acid catalyst is preferably MCM-56 molecular sieve; the third solid acid catalyst is preferably an MCM-22 molecular sieve;
the BEA configuration molecular sieve is at least one selected from BTA-01 molecular sieve, BTA-02 molecular sieve, BTA-03 molecular sieve, BTA-04 molecular sieve and ZSM-5 molecular sieve, and the second solid acid catalyst is preferably ZSM-5 molecular sieve.
9. The process of any of claims 1-8, wherein the first contacting, the second contacting, and the third contacting are all performed in a liquid-solid phase reactor selected from at least one of a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, and a trickle bed reactor, preferably a fixed bed reactor.
10. The process of any one of claims 1-9, wherein the first alkylation reaction conditions comprise: the reaction temperature is 200-260 ℃, preferably 220-230 ℃; the reaction pressure is 1-5MPa, preferably 2.5-3.5 MPa; the mass space velocity of naphthalene is 0.1-2h-1Preferably 0.5-0.8h-1；
The isomerization reaction conditions include: the reaction temperature is 250-320 ℃, and preferably 270-290 ℃; the reaction pressure is 1-5MPa, preferably 2.5-3.5 MPa;
the second alkylation reaction conditions include: the reaction temperature is 200-260 ℃, preferably 220-230 ℃; the reaction pressure is 1 to 5MPa, preferably 2.5 to 3.5 MPa.
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| CN114478157A (en) * | 2022-01-06 | 2022-05-13 | 常州大学 | Preparation method of long-chain dialkyl naphthalene type lubricating oil base oil |
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| JPH0288531A (en) * | 1988-09-26 | 1990-03-28 | Chiyoda Corp | Production of isopropylated naphthalenes |
| JPH11158087A (en) * | 1997-07-02 | 1999-06-15 | Kobe Steel Ltd | Production of dialkylnaphthalene |
| CN105294377A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Method for nathphalene alkylation |
| CN109574781A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The preparation method of multi-methylnaphthalene |
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| JPH0288531A (en) * | 1988-09-26 | 1990-03-28 | Chiyoda Corp | Production of isopropylated naphthalenes |
| JPH11158087A (en) * | 1997-07-02 | 1999-06-15 | Kobe Steel Ltd | Production of dialkylnaphthalene |
| CN105294377A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Method for nathphalene alkylation |
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