CN111039741A - Method for preparing mesitylene by isomerizing mesitylene - Google Patents
Method for preparing mesitylene by isomerizing mesitylene Download PDFInfo
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- CN111039741A CN111039741A CN201911346248.2A CN201911346248A CN111039741A CN 111039741 A CN111039741 A CN 111039741A CN 201911346248 A CN201911346248 A CN 201911346248A CN 111039741 A CN111039741 A CN 111039741A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7846—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
Abstract
The invention relates to a method for preparing mesitylene by isomerizing trimethylbenzene, which comprises the following steps of feeding a solvent taking the pseudocumene as a raw material into a fixed bed reactor filled with a catalyst and ceramic balls for reaction, taking hydrogen as a reaction atmosphere, controlling the reaction temperature to be 350-370 ℃, the pressure to be 0.3-0.6 MPa, the mass space velocity to be 2.5-3.5 h < -1 >, and the hydrogen-hydrocarbon ratio to be 500-700v/v, wherein the catalyst comprises the following components in percentage by weight: 1) 45-65 wt% of hydrogen type EUO structure molecular sieve; 2) 30-60% of gamma-Al 2O 3; 3) two metals of group VIII elements; 4) group VIB element is a metal. The invention has strong anti-coking capability and good stability when the mesitylene is prepared by isomerizing the mesitylene; under the action of the catalyst, the invention has the advantages of less front light component of C8, less hydrogen consumption, low reaction pressure and reduced production cost.
Description
Technical Field
The invention relates to an aromatic hydrocarbon isomerization method, in particular to a method for preparing mesitylene by isomerizing trimethylbenzene.
Background
The mesitylene is a precious fine chemical raw material, is used as an organic chemical raw material for preparing synthetic resin, M acid, a mesitylene antioxidant 330, a high-efficiency cornfield herbicide, a polyester resin stabilizer, an alkyd resin plasticizer and the like, can be used for producing dye intermediates such as reactive brilliant blue, K-3R and the like, and has wide market prospect.
The production method of mesitylene can be divided into synthesis method and separation and purification method. The synthesis method mainly comprises a synthesis method of acetone and concentrated sulfuric acid, a gas phase synthesis method of xylene and the like; the separation method comprises a rectification method, a sulfonation method, a cryogenic crystallization method, an HF-BF3 extraction method, an isomerization method, an alkylation method and the like. At present, the domestic industrial production method mainly comprises an alkylation method and a pseudocumene isomerization method.
Isomerization catalysts for the conversion of trimethylbenzene to mesitylene have been reported, the support of which is composed of alumina or silica and one or more zeolites in addition to one or more metal components.
CN1510017A discloses a catalyst for simultaneously preparing mesitylene and durene, which is an acid catalyst of a crystalline metallosilicate containing β zeolite, and under the conditions of temperature of 210 ℃ and 400 ℃, pressure of 1-50 bar and weight space velocity of 0.1-20h < -1 >, mesitylene and durene can be generated by using pseudocumene as the original.
CN102746092A discloses a method for producing mesitylene by hydrocracking and separating heavy aromatic cones, which comprises the steps of taking hydrogen type binder-free ten-membered ring zeolite loaded with platinum or palladium with the mass percentage of 0.005-0.5% as a catalyst, and taking hydrogen and heavy aromatic hydrocarbon as raw materials to carry out hydrocracking treatment, so that the production of the mesitylene by the BTX aromatic cones can be increased and the mesitylene can be separated.
Li Zhong Ming reacts pseudocumene with hydrogen on mordenite catalyst which is lack of aluminium hydrogen and impregnated with aluminium nickel to generate mesitylene, which has been industrially produced in Nanjing oil refinery, but the yield can not reach 200 tons/year of design ability, the scale is small, the production cost is high, and the purity is difficult to reach 98.5%.
The method uses mixed trimethylbenzene as raw material instead of pure pseudotrimethylbenzene as well as nickel-molybdenum mordenite as catalyst to obtain mesitylene product which is close to thermodynamic equilibrium distribution, and the suitable reaction temperature is 320-380 deg.C, pressure is 0.11-1.15MPa, and airspeed is 1.10-2.10 h-1.
Disclosure of Invention
The invention aims to provide a method for preparing mesitylene by isomerizing trimethylbenzene, which aims to realize the technical goals of high selectivity, good stability, long service life of an isomerization reaction and chemical equilibrium composition exceeding of mesitylene concentration in a product, improve the yield of mesitylene and reduce the production cost.
The invention adopts the following technical scheme:
the invention provides a method for preparing mesitylene by isomerizing trimethylbenzene, which comprises the steps of feeding a solvent taking the pseudocumene as a raw material into a fixed bed reactor filled with a catalyst and ceramic balls for reaction, taking hydrogen as a reaction atmosphere, controlling the reaction temperature to be 350-370 ℃, preferably 360 ℃, controlling the pressure to be 0.3-0.6 MPa, preferably 0.5MPa, and controlling the mass space velocity to be 2.5-3.5 h-1,Preferably 3.0h-1The hydrogen-to-hydrocarbon ratio is 500-700v/v, preferably 600 v/v.
The fixed bed reactor is conventional.
The solvent taking trimethylbenzene as a raw material comprises the following components in percentage by mass:
0 to 1 percent of mesitylene
96 to 99 percent of pseudocumene
0 to 1 percent of hemimellitene
0 to 1 percent of C9 aromatic hydrocarbon
The sum of the percentages of the components is 100%.
The catalyst comprises the following components in percentage by weight:
1) 45-65 wt% of hydrogen type EUO structure molecular sieve;
2）30～60%γ-Al2O3；
3) two metals of group VIII elements;
4) group VIB element is a metal.
The molar silicon-aluminum ratio of the hydrogen type EUO structure molecular sieve is preferably within a range of 30-50, the loading range of the VIII group element is preferably within a range of 0.005-0.05%, and the loading range of the VIB group element is preferably within a range of 0.05-0.15%.
In a preferred technical scheme, the group VIII element is two of platinum, palladium, iridium, ruthenium, cobalt or nickel, and platinum and palladium are preferred. The VIB group element is one of chromium and molybdenum, preferably molybdenum.
The preparation method of the catalyst for preparing mesitylene by isomerizing trimethylbenzene comprises the following steps:
(1) mixing hydrogen type raw powder of the EUO structure molecular sieve with gamma-Al 2O3, adding an inorganic binder and kneading;
the inorganic binder is selected from nitric acid or phosphoric acid, preferably nitric acid with the weight concentration of 2% or phosphoric acid with the weight concentration of 2%, and the weight amount of the inorganic binder is as follows:
the EUO structure molecular sieve hydrogen type raw powder is mixed with gamma-Al 2O3 and inorganic binder = 10: 2-5;
(2) then extruding the mixture into strips, drying the strips in the shade for 24 hours, drying the strips for 3 hours at the temperature of 120 ℃, and roasting the strips for 4 hours at the temperature of 530 ℃ and 540 ℃ to obtain a catalyst body;
(3) soaking the catalyst body and a mixed solution of two metals of the VIII group element or other metal salts for 24 hours in an equal volume, and drying for 5 hours at 90-110 ℃;
(4) isovolumetrically impregnating the dried catalyst body in the step (3) with a VIB group element metal or other metal salt solution for 12 hours, and standing for 4 hours at 60 ℃;
(5) drying the catalyst body after standing in the step (4) at 90-110 ℃ for 5 hours, and roasting at 550 ℃ for 4 hours; the catalyst for preparing mesitylene by isomerizing the mesitylene is obtained.
The invention has the beneficial effects that:
(1) the equilibrium achievement rate of the mesitylene is high, namely the mesitylene content in the product exceeds the equilibrium composition, and the mesitylene content in the product can reach 24 percent; good isomerization performance, less side reactions such as transalkylation and the like, and high trimethylbenzene yield reaching 89 percent;
(2) the catalyst prepared by the invention has strong anti-coking capability, good stability and long service life when the mesitylene is prepared by isomerizing the mesitylene;
(3) the metal elements loaded in the catalyst prepared by the method have synergistic effect, the front light component of C8 is less, the hydrogen consumption is low, the reaction pressure is low, and the production cost is reduced.
Detailed Description
The technical scheme of the invention is further explained in detail.
Taking EUO molecular sieve with SiO2/Al2O3 molar ratio of 30 and gamma-Al 2O3 powder according to the weight ratio of 65: 35 on a dry basis and mixing. Adding 2% nitric acid aqueous solution, kneading, extruding into strips,
the adding weight of the nitric acid is as follows: and mixing the EUO structure molecular sieve hydrogen type raw powder with gamma-Al 2O3, nitric acid = 10: 3;
drying in the shade for 24 hours, drying at 120 ℃ for 3 hours, and roasting at 530 ℃ and 540 ℃ for 4 hours. Soaking for 24 hours in an equal volume by using a mixed solution of chloroplatinic acid and palladium chloride, wherein the concentration of the chloroplatinic acid solution is 0.008 percent, the concentration of the palladium chloride solution is 0.05 percent, drying for 5 hours at 90-110 ℃, soaking for 12 hours in an equal volume by using an ammonium molybdate solution, wherein the concentration of the ammonium molybdate solution is 0.1 percent, standing for 4 hours at 60 ℃, drying for 5 hours at 90-110 ℃, and roasting for 4 hours at 550 ℃ to obtain the catalyst A, wherein the composition of the catalyst A is shown in Table 1.
Example 2
A catalyst was prepared as in example 1, except that the EUO molecular sieve having a SiO2/Al2O3 molar ratio of 35 and the gamma-Al 2O3 powder were mixed in the ratio of 60: 40, and obtaining the catalyst B through three metal loading, drying and roasting, wherein the composition is shown in table 1.
Example 3
A catalyst was prepared as in example 1, except that the EUO molecular sieve having a SiO2/Al2O3 molar ratio of 40 and the gamma-Al 2O3 powder were mixed in the ratio of 55: 45, and the catalyst C is obtained by loading, drying and roasting three metals to obtain the catalyst C, wherein the composition of the catalyst C is shown in table 1.
Example 4
A catalyst was prepared as in example 1, except that the EUO molecular sieve having a SiO2/Al2O3 molar ratio of 45 and the gamma-Al 2O3 powder were mixed in the ratio of 50: mixing and molding at a dry basis mass ratio of 50, loading three metals, drying and roasting to obtain the catalyst D, wherein the composition of the catalyst D is shown in Table 1.
Example 5
A catalyst was prepared as in example 1, except that the EUO molecular sieve having a SiO2/Al2O3 molar ratio of 50 and the gamma-Al 2O3 powder were mixed in the ratio of 45: 55, and the catalyst E is obtained by loading, drying and roasting three metals to obtain the catalyst E, wherein the composition of the catalyst E is shown in Table 1.
Examples 6 to 10, evaluation examples
The catalyst A, B, C, D, E prepared in examples 1-5 above was reduced in a hydrogen atmosphere at 500 ℃ for 4 hours. The isomerization reaction was evaluated in a fixed bed reactor using mesitylene as the starting material. The reactor has an internal diameter of 20 mm and a catalyst loading of 25 g. The reaction conditions are as follows: the temperature is 360 ℃, the pressure is 0.5MPa, the hydrogen-hydrocarbon ratio is 600v/v, and the mass space velocity is 3.0h < -1 >. The catalyst, feed oil composition and reaction results used in each example are shown in Table 2.
TABLE 1
TABLE 2
Note:
mesitylene/sigma-mesitylene = mesitylene in product/sigma-mesitylene in product × 100%
In summary, the present invention is only a preferred embodiment, and not intended to limit the scope of the invention, and all equivalent changes and modifications in the shape, structure, characteristics and spirit of the present invention described in the claims should be included in the scope of the present invention.
Claims (9)
1. A method for preparing mesitylene by isomerizing trimethylbenzene is characterized in that a solvent taking the pseudocumene as a raw material is sent into a fixed bed reactor filled with a catalyst and ceramic balls for reaction, hydrogen is taken as a reaction atmosphere, the reaction temperature is 350-370 ℃, the pressure is 0.3-0.6 MPa, the mass space velocity is 2.5-3.5 h < -1 >, the hydrogen-hydrocarbon ratio is 500-,
the catalyst comprises the following components in percentage by weight: 1) 45-65 wt% of hydrogen type EUO structure molecular sieve; 2) 30-60% of gamma-Al 2O 3; 3) two metals of group VIII elements; 4) the metal is a metal of a VIB group element, the VIII group element is platinum, palladium, iridium, ruthenium, cobalt or nickel, and the VIB group element is one of chromium and molybdenum.
2. The method for preparing mesitylene by isomerizing trimethylbenzene according to claim 1, wherein the solvent using trimethylbenzene as a raw material comprises the following components in percentage by mass:
0 to 1 percent of mesitylene
96 to 99 percent of pseudocumene
0 to 1 percent of hemimellitene
0 to 1 percent of C9 aromatic hydrocarbon
The sum of the percentages of the components is 100%.
3. The method for preparing mesitylene by isomerizing trimethylbenzene according to claim 1, wherein the molar silica-alumina ratio of the hydrogen type EUO structure molecular sieve is preferably in the range of 30 to 50 in terms of weight percent of the catalyst.
4. The method for preparing mesitylene by isomerizing trimethylbenzene according to claim 1, wherein the amount of the group VIII element is preferably 0.005-0.05% by weight of the catalyst.
5. The method for preparing mesitylene by isomerizing trimethylbenzene according to claim 1, wherein the supported amount of the group VIB element is preferably 0.05-0.15% by weight of the catalyst.
6. The method of claim 1, wherein the group VIII element is preferably selected from platinum and palladium.
7. The process for isomerizing mesitylene according to claim 1, wherein the group VIB element is preferably molybdenum.
8. The process for preparing a catalyst for the isomerization of mesitylene to mesitylene according to any one of claims 1 to 7, comprising the steps of:
(1) mixing hydrogen type raw powder of the EUO structure molecular sieve with gamma-Al 2O3, adding an inorganic binder and kneading;
(2) then extruding the mixture into strips, drying the strips in the shade for 24 hours, drying the strips for 3 hours at the temperature of 120 ℃, and roasting the strips for 4 hours at the temperature of 530 ℃ and 540 ℃ to obtain a catalyst body;
(3) soaking the catalyst body and a mixed solution of two metals of the VIII group element or other metal salts for 24 hours in an equal volume, and drying for 5 hours at 90-110 ℃;
(4) isovolumetrically impregnating the dried catalyst body in the step (3) with a VIB group element metal or other metal salt solution for 12 hours, and standing for 4 hours at 60 ℃;
(5) drying the catalyst body after standing in the step (4) at 90-110 ℃ for 5 hours, and roasting at 550 ℃ for 4 hours; the catalyst for preparing mesitylene by isomerizing the mesitylene is obtained.
9. The method of claim 8, wherein the inorganic binder is selected from nitric acid or phosphoric acid, preferably nitric acid with a weight concentration of 2% or phosphoric acid with a weight concentration of 2%, and the inorganic binder is used in an amount of:
the EUO structure molecular sieve hydrogen type raw powder is mixed with gamma-Al 2O3 and inorganic binder = 10: 2 to 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115770611A (en) * | 2022-12-12 | 2023-03-10 | 大连龙缘化学有限公司 | Preparation method and application of mesitylene catalyst prepared by isomerizing pseudocumene |
| CN116173963A (en) * | 2023-02-24 | 2023-05-30 | 盐城工学院 | Catalyst for preparing mesitylene by pseudocumene isomerization and preparation method thereof |
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2019
- 2019-12-24 CN CN201911346248.2A patent/CN111039741A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115770611A (en) * | 2022-12-12 | 2023-03-10 | 大连龙缘化学有限公司 | Preparation method and application of mesitylene catalyst prepared by isomerizing pseudocumene |
| CN115770611B (en) * | 2022-12-12 | 2024-02-06 | 大连龙缘化学有限公司 | Preparation method and application of catalyst for preparing mesitylene by pseudocumene isomerization |
| CN116173963A (en) * | 2023-02-24 | 2023-05-30 | 盐城工学院 | Catalyst for preparing mesitylene by pseudocumene isomerization and preparation method thereof |
| CN116173963B (en) * | 2023-02-24 | 2024-01-19 | 盐城工学院 | Catalyst for preparing mesitylene by pseudocumene isomerization and preparation method thereof |
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