A process for the preparation of a dialkyl arene compound

Abstract

The application discloses a preparation method of a dialkyl arene compound, which comprises the following steps: an optional step (1), alkylating an arene compound with an olefin to obtain an alkyl arene, and a step (2), disproportionating the alkyl arene in a disproportionation rectifying tower in the presence of optional hydrogen to obtain the dialkyl arene compound, wherein the disproportionation rectifying tower is filled with a disproportionation catalyst for catalyzing the disproportionation reaction. The application particularly discloses a preparation method of diisopropyl benzene and diisopropyl naphthalene. When the corresponding dialkyl arene compound is prepared by adopting the method, the selectivity is high, the yield is greatly improved, the occurrence of a side reaction is reduced, and the service life of a catalyst is prolonged.

Description

Technical Field

[0001] This invention belongs to the field of alkyl aromatic compound synthesis technology, specifically relating to a method for preparing dialkyl aromatic compounds, particularly diisopropylbenzene and diisopropylnaphthalene. Background Technology

[0002] Among dialkyl aromatic compounds, diisopropylbenzene and diisopropylnaphthalene are of significant industrial value. Diisopropylbenzene is an important fine chemical product, mainly used in the production of hydroquinone, which is a high-performance polymer additive and an important dye auxiliary agent.

[0003] Currently, methods for preparing diisopropylbenzene include benzene and propylene alkylation and cumene disproportionation. The benzene and propylene alkylation method for preparing diisopropylbenzene has low selectivity, and the product is mainly a byproduct of the cumene production unit. The cumene disproportionation method uses cumene as its raw material, and its raw material source depends on the cumene production unit. Moreover, the cumene disproportionation method generally suffers from low selectivity and a high proportion of heavy components in the byproducts.

[0004] Chinese patent CN1721379A describes a technique for preparing p-diisopropylbenzene from propylene and cumene. This patent uses a special-configuration silica-alumina zeolite molecular sieve as a catalyst and employs an alkylation reaction to prepare p-diisopropylbenzene. The cumene raw material in this method relies on an cumene production unit, and the selectivity of diisopropylbenzene is 99%.

[0005] Diisopropylnaphthalene is an important fine chemical product, mainly used for the separation and extraction of 2,6-diisopropylnaphthalene, which is a crucial monomer for the preparation of the high-performance polymer polyethylene naphthalate (PEN). Simultaneously, the remaining diisopropylnaphthalene after the extraction of 2,6-diisopropylnaphthalene can also be used as a high-quality high-temperature heat transfer oil.

[0006] Currently, methods for preparing diisopropylnaphthalene include alkylation of naphthalene and propylene, and alkylation of naphthalene and isopropanol. The equipment used includes liquid-phase alkylation fixed-bed reactors, which have short catalyst lifetimes, low selectivity for diisopropylnaphthalene during the reaction, and a large amount of heavy components are generated.

[0007] Chinese patent CN100364941C describes a method for preparing 2,6-diisopropylnaphthalene by hydroisopropylation of refined naphthalene. The patent relates to a batch reactor, in which refined naphthalene and isopropanol are alkylated under quasi-hydrogen conditions. The resulting product is then separated, purified, and recycled to obtain 2,6-diisopropylnaphthalene with a purity ≥99%.

[0008] In summary, current methods for preparing diisopropylbenzene and diisopropylnaphthalene suffer from low selectivity and complex processes. Summary of the Invention

[0009] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing dialkyl aromatic compounds, especially diisopropylbenzene and diisopropylnaphthalene. The method of the present invention has high selectivity in preparing dialkyl aromatic compounds, greatly improves the yield, reduces the occurrence of side reactions, and extends the service life of catalysts.

[0010] Therefore, the present invention provides a method for preparing dialkyl aromatic compounds, which includes the following steps:

[0011] Optional step (1): Alkylating an aromatic compound with an olefin to obtain an alkyl aromatic compound;

[0012] Step (2): The alkyl aromatic hydrocarbon is disproportionated in a disproportionation distillation column in the optional presence of hydrogen to obtain the dialkyl aromatic hydrocarbon compound.

[0013] The disproportionation distillation column is filled with a disproportionation catalyst that catalyzes the disproportionation reaction.

[0014] In this invention, the term "aromatic hydrocarbon" in "dialkyl aromatic hydrocarbon compound", "aromatic hydrocarbon compound", and "alkyl aromatic hydrocarbon" does not include those aromatic hydrocarbon compounds in the common sense in which the hydrogen on the benzene ring is replaced by any other substituent. That is, in the aromatic hydrocarbons described in this invention, the hydrogen on the benzene ring is not replaced by any substituent.

[0015] According to some embodiments of the present invention, the aromatic compound has 1-3 benzene rings, preferably benzene.

[0016] According to some embodiments of the present invention, the olefin is a C2-C5 olefin, preferably propylene.

[0017] According to some embodiments of the present invention, the alkyl group is a C2-C5 alkyl group, preferably isopropyl.

[0018] According to some embodiments of the present invention, the alkyl aromatic hydrocarbon is isopropylbenzene or isopropylnaphthalene.

[0019] According to some embodiments of the present invention, the dialkyl aromatic compound is diisopropylbenzene or diisopropylnaphthalene.

[0020] Those skilled in the art will understand that the dialkyl aromatic compounds obtained in the preparation method of the present invention are directly related to the raw materials used in the preparation steps. For example, alkylating benzene with propylene will generate a compound containing isopropylbenzene, and further disproportionation reaction can generate diisopropylbenzene; while disproportionation reaction of isopropylnaphthalene in the presence of hydrogen can generate diisopropylnaphthalene.

[0021] According to some embodiments of the present invention, the disproportionation catalyst is a solid acid catalyst.

[0022] According to some embodiments of the present invention, the Hammit function H0 of the disproportionation catalyst is in the range of -28 to -3.5, preferably -23 to -5.6.

[0023] According to the present invention, specific examples of the disproportionation catalyst include, but are not limited to, MWW-configured molecular sieve catalysts, BEA-configured molecular sieve catalysts, MTW-configured molecular sieve catalysts, MFI-configured molecular sieve catalysts, sulfuric acid-supported zirconia-type solid acid catalysts, and sulfuric acid-supported zirconia and titanium dioxide solid acid catalysts.

[0024] According to the present invention, the amount of the disproportionation catalyst used is relatively wide, as long as it can catalyze the disproportionation reaction. In some preferred embodiments, when a feedstock containing isopropylbenzene is prepared by alkylation of benzene and propylene, and then disproportionated to prepare diisopropylbenzene, the amount of disproportionation catalyst used is 2.0 h. -1 -8.0h -1 (Catalyst mass hourly space velocity relative to benzene). The amount of disproportionation catalyst used to prepare diisopropylnaphthalene via disproportionation under hydrogen-induced conditions is 1.0 h⁻¹. -1 -5.0h -1 (Mass hourly space velocity of catalyst relative to isopropylnaphthalene).

[0025] According to some preferred embodiments of the present invention, when a raw material containing isopropylbenzene is prepared by alkylation reaction of benzene and propylene, and then further subjected to disproportionation reaction to prepare diisopropylbenzene, the Hammitt function H0 of the disproportionation catalyst is preferably -28 to -3.5, preferably -9 to -7. Preferred examples include, but are not limited to, MTW configuration molecular sieve catalysts, MFI configuration molecular sieve catalysts, sulfuric acid supported zirconium oxide solid acid catalysts, sulfuric acid supported zirconium oxide and titanium oxide solid acid catalysts, such as ZSM-12, ZSM-5, etc.

[0026] According to some preferred embodiments of the present invention, when isopropylnaphthalene is used as a raw material to prepare diisopropylnaphthalene by disproportionation reaction, the Hammit function H0 of the disproportionation catalyst is -23 to -5.6, preferably -8 to -6. Preferred examples include, but are not limited to, at least one selected from MWW configuration molecular sieve catalysts, BEA configuration molecular sieve catalysts, and sulfuric acid supported zirconia type solid acid catalysts.

[0027] According to some embodiments of the present invention, the bottom temperature of the disproportionation distillation column in the disproportionation reaction is 220–300°C.

[0028] According to some embodiments of the present invention, the top pressure of the disproportionation distillation column in the disproportionation reaction is 0.02 MPa-1 MPa.

[0029] According to some embodiments of the present invention, the temperature of the catalyst-filled section of the disproportionation distillation column in the disproportionation reaction is 150–230°C.

[0030] According to some embodiments of the present invention, when a raw material containing isopropylbenzene is prepared by alkylation reaction of benzene and propylene and then subjected to disproportionation reaction (without ortho-hydrogen) to prepare diisopropylbenzene, the disproportionation distillation column is a pressurized distillation column, and the top pressure of the disproportionation distillation column is 0.2 MPa to 1.0 MPa, preferably 0.3 MPa to 0.5 MPa.

[0031] According to some preferred embodiments of the present invention, when a raw material containing isopropylbenzene is prepared by alkylation reaction of benzene and propylene and then subjected to disproportionation reaction (without ortho-hydrogen) to prepare diisopropylbenzene, the bottom temperature of the disproportionation distillation column is 220-300°C, preferably 230-250°C.

[0032] According to some preferred embodiments of the present invention, when a raw material containing isopropylbenzene is prepared by alkylation reaction of benzene and propylene and then subjected to disproportionation reaction (without ortho-hydrogen) to prepare diisopropylbenzene, the temperature of the catalyst packing section of the disproportionation distillation column is 150-200°C, preferably 160-180°C.

[0033] According to some embodiments of the present invention, when isopropylnaphthalene is used as raw material to prepare diisopropylnaphthalene by disproportionation reaction (under ortho-hydrogen conditions), the disproportionation distillation column is a vacuum distillation column, and the top pressure of the disproportionation distillation column is 0.03 MPa to 0.07 MPa, preferably 0.05 MPa to 0.06 MPa.

[0034] According to some embodiments of the present invention, when isopropylnaphthalene is used as raw material to prepare diisopropylnaphthalene through a disproportionation reaction (under ortho-hydrogen conditions), the bottom temperature of the disproportionation distillation column is 250–300°C, preferably 260–280°C.

[0035] According to some embodiments of the present invention, when isopropylnaphthalene is used as a raw material to prepare diisopropylnaphthalene through a disproportionation reaction (under ortho-hydrogen conditions), the temperature of the catalyst-filled section of the disproportionation distillation column is 190–230°C, preferably 200–210°C.

[0036] According to some embodiments of the present invention, the disproportionation distillation column has a theoretical plate number of 25-80.

[0037] According to some embodiments of the present invention, the disproportionating catalyst is filled in the disproportionating distillation column at a distance of more than 10 theoretical plates from the bottom of the disproportionating distillation column, preferably the disproportionating catalyst is filled in the middle section of the disproportionating distillation column.

[0038] According to some embodiments of the present invention, the alkylation reaction in step (1) is a liquid-phase alkylation reaction, preferably the alkylation reaction is carried out in a fixed-bed reactor.

[0039] According to some embodiments of the present invention, the temperature of the alkylation reaction is 100-200°C, preferably 130-150°C.

[0040] According to some embodiments of the present invention, the pressure of the alkylation reaction is 2.5 MPa to 4.0 MPa, preferably 33.0 to 3.5 MPa.

[0041] According to some embodiments of the present invention, the alkylation reaction is carried out in the presence of a solid acid catalyst, wherein the Hammitt function H0 of the solid acid catalyst is in the range of -25 to -3, preferably -7 to -5.

[0042] According to the present invention, examples of catalysts for the alkylation reaction include, but are not limited to, at least one of MWW, BEA, MOR and Y-configuration molecular sieve catalysts.

[0043] According to the present invention, the amount of catalyst used in the alkylation reaction is relatively wide, as long as it is sufficient to catalyze the alkylation reaction. In some embodiments, when benzene and propylene are used for the alkylation reaction, the amount of catalyst used in the alkylation reaction is 1.0 h. -1 -10.0h -1 (Mass hourly space velocity of catalyst relative to benzene).

[0044] According to some embodiments of the present invention, step (1) further includes passing the reaction product obtained from the alkylation reaction through a light component removal tower to remove the light components from the reaction product. In particular, when the alkylation reaction is carried out using benzene and propylene as raw materials, the reaction product obtained from the alkylation reaction is passed through a light component removal tower to remove the light components from the reaction product.

[0045] According to some embodiments of the present invention, the light-light removal column is an atmospheric distillation column, and the bottom temperature of the light-light removal column is 80-150°C, preferably 90-100°C.

[0046] According to some embodiments of the present invention, step (2) further includes feeding the disproportionation distillation column bottom feed into the product column.

[0047] According to some embodiments of the present invention, when diisopropylnaphthalene is prepared by disproportionation reaction of isopropylnaphthalene under quasi-hydrogen conditions, the bottom feed of the disproportionation distillation column is passed into the product column to separate diisopropylnaphthalene. Preferably, the product column is an atmospheric distillation column, and preferably the bottom temperature of the product column is 300-330°C, more preferably 310-320°C.

[0048] According to some embodiments of the present invention, when preparing diisopropylnaphthalene by disproportionation reaction of isopropylnaphthalene under quasi-hydrogen conditions, the bottom feed of the product tower is further passed into a deweighting tower to remove heavy components. The deweighting tower is an atmospheric distillation tower, and preferably the bottom temperature of the deweighting tower is 340-370°C, more preferably 350-360°C.

[0049] According to some embodiments of the present invention, in step (2), the molar ratio of hydrogen to alkyl aromatic hydrocarbon is 0.5 to 5, preferably 1.0 to 2.0.

[0050] According to the present invention, a method for preparing diisopropylbenzene is provided, comprising:

[0051] A) Alkylating benzene with propylene yields a reaction product containing isopropylbenzene;

[0052] B) The resulting reaction product is passed through a light component removal tower to remove light components and then fed into a disproportionation distillation tower for disproportionation reaction. The disproportionation distillation tower is filled with a disproportionation catalyst that catalyzes the disproportionation reaction.

[0053] According to some embodiments of the present invention, the alkylation reaction in step (A) is a liquid-phase alkylation reaction, preferably the alkylation reaction is carried out in a fixed-bed reactor.

[0054] According to some embodiments of the present invention, the temperature of the alkylation reaction is 100-200°C, preferably 130-150°C.

[0055] According to some embodiments of the present invention, the pressure of the alkylation reaction is 2.5 MPa to 4.0 MPa, preferably 33.0 to 3.5 MPa.

[0056] According to some embodiments of the present invention, the alkylation reaction is carried out in the presence of a solid acid catalyst, wherein the Hammitt function H0 of the solid acid catalyst is in the range of -25 to -3, preferably -7 to -5, and examples of the catalyst for the alkylation reaction include, but are not limited to, at least one of MWW, BEA, MOR and Y-configuration molecular sieve catalysts.

[0057] According to some embodiments of the present invention, the light-light removal column is an atmospheric distillation column, and the bottom temperature of the light-light removal column is 80-150°C, preferably 90-100°C.

[0058] According to some embodiments of the present invention, the Hammit function H0 of the disproportionation catalyst used in step B) is -25 to -3, preferably -9 to -7. Preferred examples include, but are not limited to, MTW configuration molecular sieve catalysts, MFI configuration molecular sieve catalysts, sulfuric acid supported zirconium oxide solid acid catalysts, sulfuric acid supported zirconium oxide and titanium oxide solid acid catalysts, such as ZSM-12, ZSM-5, etc.

[0059] According to some embodiments of the present invention, the disproportionation distillation column in step B) is a pressurized distillation column, and the top pressure of the disproportionation distillation column is 0.2MPa to 1.0MPa, preferably 0.3MPa to 0.5MPa.

[0060] According to some embodiments of the present invention, the bottom temperature of the disproportionation distillation column is 220-300°C, preferably 230-250°C.

[0061] According to some embodiments of the present invention, the temperature of the catalyst-filled section of the disproportionation distillation column is 150–200°C, preferably 160–180°C.

[0062] According to some embodiments of the present invention, step B) further includes feeding the bottom component into the product column and removing the heavy component from the system. Specifically, diisopropylbenzene product is collected from the top of the column, and the heavy component is collected from the bottom of the column and removed from the system.

[0063] According to the present invention, the method for preparing diisopropylbenzene provided by the present invention solves the following problems existing in the traditional process: 1) low conversion rate of cumene disproportionation reaction; 2) low selectivity of diisopropylbenzene; 3) a large number of heavy components resulting from side reactions.

[0064] According to the present invention, a method for preparing diisopropylnaphthalene is provided, comprising:

[0065] a) Isopropylnaphthalene is subjected to a disproportionation reaction in the presence of hydrogen in a disproportionation distillation column, wherein the disproportionation distillation column is filled with a disproportionation catalyst that catalyzes the disproportionation reaction.

[0066] b) Naphthalene is discharged from the top of the disproportionation distillation column after the reaction, and the bottom feed of the disproportionation distillation column enters the product column. The product product, diisopropylnaphthalene, is collected from the top of the product column, and the bottom feed of the product column enters the deweighting column to remove heavy components.

[0067] According to some embodiments of the present invention, the Hammit function H0 of the disproportionation catalyst in step a) is -23 to -5.6, preferably -8 to -6, wherein preferred examples include, but are not limited to, at least one selected from MWW configuration molecular sieve catalysts, BEA configuration molecular sieve catalysts, and sulfuric acid supported zirconia type solid acid catalysts.

[0068] According to some embodiments of the present invention, the disproportionation distillation column in step a) is a vacuum distillation column, and the top pressure of the disproportionation distillation column is 0.03MPa to 0.07MPa, preferably 0.05MPa to 0.06MPa.

[0069] According to some embodiments of the present invention, the bottom temperature of the disproportionation distillation column in step a) is 250-300°C, preferably 260-280°C.

[0070] According to some embodiments of the present invention, the temperature of the catalyst-filled section of the disproportionation distillation column in step a) is 190–230°C, preferably 200–210°C.

[0071] According to some embodiments of the present invention, the product column is an atmospheric distillation column, and preferably the bottom temperature of the product column is 300-330°C, more preferably 310-320°C.

[0072] According to some embodiments of the present invention, the deweighting tower is an atmospheric distillation tower, and preferably the bottom temperature of the deweighting tower is 340-370°C, more preferably 350-360°C.

[0073] According to some embodiments of the present invention, the method further includes: feeding the top product of the deweighting tower and the isopropylnaphthalene feed together into a disproportionation distillation tower, and discharging the heavy components from the bottom of the deweighting tower into the system.

[0074] According to some embodiments of the present invention, in step b), the molar ratio of hydrogen to alkyl aromatic hydrocarbon is 0.5 to 5, preferably 1.0 to 2.0.

[0075] According to the present invention, the method for preparing diisopropylnaphthalene provided by the present invention solves the following problems existing in the traditional process: 1) low conversion rate of isopropylnaphthalene disproportionation reaction; 2) low selectivity of diisopropylnaphthalene; 3) a large number of heavy components brought about by side reactions; 4) short catalyst lifetime.

[0076] The present invention has the following beneficial effects: The method of the present invention overcomes the problems of low reaction conversion rate, low product selectivity and a large number of heavy components caused by side reactions when producing dialkyl aromatics in the prior art. The method described above has high selectivity, greatly improves the yield, reduces the occurrence of side reactions, and extends the service life of the catalyst when preparing the corresponding dialkyl aromatic compounds. Attached Figure Description

[0077] Figure 1 This is a schematic diagram of the process for preparing diisopropylbenzene according to an embodiment of the present invention.

[0078] Figure 2 This is a schematic diagram of the process for preparing diisopropylbenzene in a comparative example of the present invention.

[0079] Figure 3 This is a schematic diagram of the process for preparing diisopropylnaphthalene according to an embodiment of the present invention. Detailed Implementation

[0080] To make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments and accompanying drawings. These embodiments are for illustrative purposes only and should not be considered as limiting the scope of the present invention. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Unless otherwise stated, all raw materials involved in the embodiments are commercially available or products that can be obtained by known methods.

[0081] In this invention, "optional" means either present or absent, added or not added, or contained or not contained.

[0082] Unless otherwise specified, all pressures mentioned in this manual refer to gauge pressure.

[0083] This invention can be adopted as follows Figure 1 The process diagram shown illustrates the production of diisopropylbenzene. The specific steps are as follows: Benzene and propylene undergo an alkylation reaction in an alkylation reactor to obtain a reaction product containing isopropylbenzene; the resulting reaction product is then passed through a light component removal column to remove light components, and the product is discharged from the top of the column. The bottom product enters a disproportionation distillation column packed with a disproportionation catalyst in the middle section for disproportionation reaction. By controlling the reaction conditions, the top of the disproportionation distillation column yields a material mainly composed of benzene (which can be reused as raw material), while the bottom component of the disproportionation distillation column enters a product column, and the heavy components are discharged from the system. Specifically, diisopropylbenzene is collected from the top of the column, and the heavy components are collected from the bottom and discharged from the system.

[0084] This invention can be adopted as follows Figure 1 The process diagram shown illustrates the production of diisopropylnaphthalene. The specific steps are as follows: Isopropylnaphthalene and hydrogen are introduced into a disproportionation distillation column packed with a disproportionation catalyst in the middle section for a disproportionation reaction. By controlling the conditions in the disproportionation distillation column, naphthalene and hydrogen are discharged from the top of the column. The bottom feed of the disproportionation distillation column enters the product column. The conditions in the product column are controlled, and diisopropylnaphthalene is collected from the top of the product column. The bottom feed of the product column enters a deweighting column to remove heavy components and is discharged from the bottom of the column. The top product from the deweighting column (e.g., triisopropylnaphthalene) is then fed into the disproportionation distillation column along with the isopropylnaphthalene feed for a second reaction.

[0085] Examples of preparation of diisopropylbenzene are as follows:

[0086] Example 1

[0087] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1The process flow diagram shown illustrates the reaction process. The alkylation reactor is filled with 10 grams of MWW-type molecular sieve catalyst (MP-02, produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.5. The middle section of the disproportionation distillation column is filled with 30 grams of MTW-type molecular sieve catalyst ZSM-12, with a corresponding Hammitt function H0 = -7.8. The propylene flow rate is 8.0 g / h, and the benzene flow rate is 7.5 g / h. The alkylation reactor is controlled at a temperature of 140℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, the temperature of the middle section (catalyst-filled section) is 170℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates in this disproportionation distillation column is 30.

[0088] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.6% and a heavy component content (triisopropylbenzene and components with larger molecular weights than triisopropylbenzene) of 0.4%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 99.9% and a cumene content of 0.1%. This disproportionation distillation column achieved a cumene disproportionation conversion rate of 99.9%.

[0089] The final diisopropylbenzene product output was 15.4 g / hour, and the heavy component output was 0.1 g / hour.

[0090] Example 2

[0091] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction process. The alkylation reactor is filled with 10 grams of MWW-type molecular sieve catalyst (MP-02, produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.5. The middle section of the disproportionation distillation column is filled with 30 grams of MTW-type molecular sieve catalyst ZSM-12, with a corresponding Hammitt function H0 = -7.8. The propylene flow rate is 8.0 g / h, and the benzene flow rate is 7.5 g / h. The alkylation reactor is controlled at a temperature of 140℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, and the temperature of the middle section (catalyst-filled section) is 170℃. The top pressure of the disproportionation distillation column is atmospheric pressure, and the theoretical number of plates for this disproportionation distillation column is 30.

[0092] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 95.3% and a heavy component content of 4.7%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 89.1% and an isopropylbenzene content of 11.9%. The disproportionation distillation column achieved an isopropylbenzene disproportionation conversion rate of 88.1%.

[0093] The final diisopropylbenzene product output was 14.7 g / h, which was less than that in Example 1, while the heavy component output was 0.7 g / h, which was greater than that in Example 1.

[0094] Example 3

[0095] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction process. The alkylation reactor is filled with 10 grams of MWW-type molecular sieve catalyst (MP-02, produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.5. The middle section of the disproportionation distillation column is filled with 30 grams of MTW-type molecular sieve catalyst ZSM-12, with a corresponding Hammitt function H0 = -7.8. The propylene flow rate is 8.0 g / h, and the benzene flow rate is 7.5 g / h. The alkylation reactor is controlled at a temperature of 140℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, the temperature of the middle section (catalyst-filled section) is 220℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates in this disproportionation distillation column is 30.

[0096] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.6% and a heavy component content of 0.4%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 76.6% and an isopropylbenzene content of 23.4%. The disproportionation distillation column achieved a cumene disproportionation conversion rate of 76.6%.

[0097] The final diisopropylbenzene product output was 15.1 g / h, which was less than that in Example 1, while the heavy component output was 0.4 g / h, which was greater than that in Example 1.

[0098] Example 4

[0099] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction process. The alkylation reactor is packed with 25 grams of BEA-type molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.9. The middle section of the disproportionation distillation column is packed with 40 grams of MFI-type molecular sieve catalyst ZSM-5, with a corresponding Hammitt function H0 = -7.1. The propylene flow rate is 8.6 g / h, and the benzene flow rate is 8 g / h. The alkylation reactor is controlled at a temperature of 150℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, the temperature of the middle section (catalyst-packed section) is 180℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates for this disproportionation distillation column is 40.

[0100] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.7% and a heavy component content of 0.3%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 99.9% and an isopropylbenzene content of 0.1%. This disproportionation distillation column achieved a 99.9% conversion rate in the cumene disproportionation reaction.

[0101] The final diisopropylbenzene product output was 16.5 g / hour, and the heavy component output was 0.1 g / hour.

[0102] Example 5

[0103] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction process. The alkylation reactor is packed with 25 grams of BEA-type molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.9. The middle section of the disproportionation distillation column is packed with 40 grams of MFI-type molecular sieve catalyst ZSM-5, with a corresponding Hammitt function H0 = -7.1. The propylene flow rate is 8.6 g / h, and the benzene flow rate is 8 g / h. The alkylation reactor is controlled at a temperature of 150℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, and the temperature of the middle section (catalyst-packed section) is 180℃. The top pressure of the disproportionation distillation column is atmospheric pressure, and the theoretical number of plates for this disproportionation distillation column is 40.

[0104] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 93.8% and a heavy component content of 6.2%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 86.1% and an isopropylbenzene content of 13.9%. The disproportionation distillation column achieved an isopropylbenzene disproportionation conversion rate of 86.1%.

[0105] The final diisopropylbenzene product output was 15.6 g / h, which was less than that in Example 4, while the output of the heavy component was 1 g / h, which was greater than that in Example 4.

[0106] Example 6

[0107] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1The process flow diagram shown illustrates the reaction process. The alkylation reactor is packed with 25 grams of BEA-type molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammitt function H0 = -6.9. The middle section of the disproportionation distillation column is packed with 40 grams of MFI-type molecular sieve catalyst ZSM-5, with a corresponding Hammitt function H0 = -7.1. The propylene flow rate is 8.6 g / h, and the benzene flow rate is 8 g / h. The alkylation reactor is controlled at a temperature of 150℃ and a pressure of 3.0 MPa; the bottom temperature of the light component removal column is 95℃; the bottom temperature of the disproportionation distillation column is 240℃, the temperature of the middle section (catalyst-packed section) is 210℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates in this disproportionation distillation column is 40.

[0108] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.6% and a heavy component content of 0.4%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 76.4% and an isopropylbenzene content of 23.6%. The disproportionation distillation column achieved a cumene disproportionation conversion rate of 76.4%.

[0109] The final diisopropylbenzene product output was 16.1 g / h, which was less than that in Example 4, while the heavy component output was 0.5 g / h, which was greater than that in Example 4.

[0110] Example 7

[0111] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction process. The alkylation reactor is filled with 31 g of MOR-configured molecular sieve catalyst, corresponding to a Hammitt function H0 = -6.3. The middle section of the disproportionation distillation column is filled with 28 g of sulfuric acid-supported zirconium oxide superacid solid catalyst (preparation method: first, zirconium hydroxide solid is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain sulfuric acid-supported zirconium oxide superacid solid catalyst), corresponding to a Hammitt function H0 = -8.5. The propylene flow rate is 8.9 g / h, and the benzene flow rate is 8.3 g / h. The alkylation reactor temperature is controlled at 155℃ and the pressure at 3.2 MPa; the bottom temperature of the light component removal column is 90℃; the bottom temperature of the disproportionation distillation column is 245℃, the temperature of the middle section (catalyst-filled section) is 175℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates for this disproportionation distillation column is 30.

[0112] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.8% and a heavy component content of 0.2%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 99.9% and an isopropylbenzene content of 0.1%. This disproportionation distillation column achieved a 99.9% conversion rate in the cumene disproportionation reaction.

[0113] The final diisopropylbenzene product output was 17.1 g / hour, and the heavy component output was 0.1 g / hour.

[0114] Example 8

[0115] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction. The alkylation reactor is filled with 31 g of MOR-configured molecular sieve catalyst, corresponding to a Hammitt function H0 = -6.3. The middle section of the disproportionation distillation column is filled with 28 g of sulfuric acid-supported zirconium oxide superacid solid catalyst (preparation method: first, zirconium hydroxide solid is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain sulfuric acid-supported zirconium oxide superacid solid catalyst), corresponding to a Hammitt function H0 = -8.5. The propylene flow rate is 8.9 g / h, and the benzene flow rate is 8.3 g / h. The alkylation reactor temperature is controlled at 155℃ and the pressure at 3.2 MPa; the bottom temperature of the light component removal column is 90℃; the bottom temperature of the disproportionation distillation column is 245℃, and the temperature of the middle section (catalyst-filled section) is 175℃. The top pressure of the disproportionation distillation column is atmospheric pressure, and the theoretical number of plates for this disproportionation distillation column is 30.

[0116] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 91.8% and a heavy component content of 8.2%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 81.2% and an isopropylbenzene content of 18.8%. The disproportionation distillation column achieved an isopropylbenzene disproportionation conversion rate of 81.2%.

[0117] The final diisopropylbenzene product output was 15.7 g / h, which was less than that in Example 7, while the heavy component output was 1.5 g / h, which was greater than that in Example 7.

[0118] Example 9

[0119] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1The process flow diagram shown illustrates the reaction. The alkylation reactor is filled with 31 g of MOR-configured molecular sieve catalyst, corresponding to a Hammitt function H0 = -6.3. The middle section of the disproportionation distillation column is filled with 28 g of sulfuric acid-supported zirconium oxide superacid solid catalyst (preparation method: first, zirconium hydroxide solid is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain sulfuric acid-supported zirconium oxide superacid solid catalyst), corresponding to a Hammitt function H0 = -8.5. The propylene flow rate is 8.9 g / h, and the benzene flow rate is 8.3 g / h. The alkylation reactor temperature is controlled at 155℃ and the pressure at 3.2 MPa; the bottom temperature of the light component removal column is 90℃; the bottom temperature of the disproportionation distillation column is 245℃, the temperature of the middle section (catalyst-filled section) is 220℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates for this disproportionation distillation column is 30.

[0120] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.3% and a heavy component content of 0.7%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 83.1% and an isopropylbenzene content of 16.9%. The disproportionation distillation column achieved an isopropylbenzene disproportionation conversion rate of 83.1%.

[0121] The final diisopropylbenzene product output was 16.5 g / h, which was less than that in Example 7, while the heavy component output was 0.7 g / h, which was greater than that in Example 7.

[0122] Example 10

[0123] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 1 The process flow diagram shown illustrates the reaction. The alkylation reactor is filled with 29 g of Y-configuration molecular sieve catalyst, with a corresponding Hammitt function H0 = -6.8. The middle section of the disproportionation distillation column is filled with 26 g of sulfuric acid-supported zirconium oxide and titanium oxide superacid solid catalyst, with a corresponding Hammitt function H0 = -8.8. Preparation method: First, titanium hydroxide solid is prepared by hydrolysis of titanium tetrachloride, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported titanium oxide superacid solid catalyst. The propylene flow rate is 8.6 g / h, and the benzene flow rate is 8.0 g / h. The alkylation reactor temperature is controlled at 160℃ and the pressure at 3.2 MPa; the bottom temperature of the light component removal column is 90℃; the bottom temperature of the disproportionation distillation column is 245℃, the temperature of the middle section (catalyst-filled section) is 180℃, and the top pressure of the disproportionation distillation column is 0.4 MPa. The theoretical number of plates in this disproportionation distillation column is 40.

[0124] Analysis of the bottom product from the disproportionation distillation column revealed a diisopropylbenzene content of 99.6% and a heavy component content of 0.4%. Simultaneously, analysis of the top product from the disproportionation distillation column showed a benzene content of 99.8% and an isopropylbenzene content of 0.2%. This disproportionation distillation column achieved a 99.8% conversion rate for the isopropylbenzene disproportionation reaction.

[0125] The final diisopropylbenzene product output was 16.5 g / hour, and the heavy component output was 0.1 g / hour.

[0126] Comparative Example 1

[0127] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 2 The process flow diagram shown differs from that of Example 10 in that the reaction proceeds as described. Figure 2 Will Figure 1 The disproportionation distillation column was replaced with a single distillation column, the middle section of which was not filled with catalyst but only with distillation packing. The alkylation reactor was filled with 29 g of Y-configuration molecular sieve catalyst, corresponding to a Hammett function H0 = -6.8, with a propylene flow rate of 8.6 g / h and a benzene flow rate of 8.0 g / h. The alkylation reactor was controlled at a temperature of 160°C and a pressure of 3.2 MPa; the bottom temperature of the light component removal column was 90°C; the bottom temperature of the distillation column was 245°C; the middle section, i.e., the catalyst-packed section in Example 10, had a temperature of 180°C; the top pressure of the distillation column was 0.4 MPa; and the theoretical number of plates for this distillation column was 40.

[0128] Analysis of the bottom product from the distillation column revealed a diisopropylbenzene content of 99.5% and a heavy component content of 0.5%. Simultaneously, analysis of the top product from the distillation column showed a benzene content of 73.6% and an isopropylbenzene content of 26.4%. This distillation column did not participate in the disproportionation reaction; the benzene and isopropylbenzene were returned to the feed system of the alkylation reactor.

[0129] The final diisopropylbenzene product output was 15.3 g / h, which was less than that in Example 10, while the heavy component output was 1.3 g / h, which was greater than that in Example 4.

[0130] Comparative Example 2

[0131] Using high-purity propylene (99.99%) and benzene (99.99%) as raw materials, according to... Figure 2 The process flow diagram shown differs from that of Example 10 in that the reaction proceeds as described. Figure 2 Will Figure 1The disproportionation distillation column was replaced with a single distillation column, the middle section of which was not filled with catalyst but only with distillation packing. The alkylation reactor was filled with 29 g of MWW-configured molecular sieve catalyst, corresponding to a Hammett function H0 = -6.8. The propylene flow rate was 8.6 g / h, and the benzene flow rate was 8.0 g / h. The alkylation reactor was controlled at a temperature of 160℃ and a pressure of 3.2 MPa; the bottom temperature of the light component removal column was 90℃; the bottom temperature of the distillation column was 245℃; the temperature of the middle section (catalyst-packed section) was 180℃; the top pressure of the disproportionation distillation column was 0.4 MPa; and the theoretical number of plates for this distillation column was 40.

[0132] Analysis of the bottom product from the distillation column revealed a diisopropylbenzene content of 99.6% and a heavy component content of 0.4%. Simultaneously, analysis of the top product from the distillation column showed a benzene content of 72.6% and an isopropylbenzene content of 27.4%. This distillation column did not participate in the disproportionation reaction; the benzene and isopropylbenzene were returned to the feed system of the alkylation reactor.

[0133] The final diisopropylbenzene product output was 14.3 g / h, which was less than that in Example 10, while the heavy component output was 2.3 g / h, which was greater than that in Example 10.

[0134] Examples of preparation of diisopropylnaphthalene are as follows:

[0135] Example 11

[0136] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 12 kg of MP-02 (produced by Shanghai Research Institute of Petrochemical Technology) MWW molecular sieve catalyst, with a corresponding Hammett function H0 = -6.8. The isopropylnaphthalene feedstock flow rate is 10 kg / h, and hydrogen gas is simultaneously introduced at a rate of 0.12 kg / h. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The disproportionation distillation column has 40 theoretical plates. The product column is an atmospheric pressure distillation column with 30 theoretical plates, and its bottom temperature is controlled at 310℃. The heavy removal column is also an atmospheric pressure distillation column with 28 theoretical plates, and its bottom temperature is controlled at 360℃.

[0137] The bottom product of the disproportionation distillation column was analyzed. It contained 99.6% diisopropylnaphthalene and 0.4% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 99.1% naphthalene and 0.9% isopropylnaphthalene. This disproportionation distillation column achieved a 99.4% conversion rate for the isopropylnaphthalene disproportionation reaction.

[0138] The final output of diisopropylnaphthalene was 6.2 kg / hour, the output of naphthalene was 3.7 kg / hour, the output of heavy components was 0.1 kg / hour, and the content of diisopropylnaphthalene in the diisopropylnaphthalene product was 99%.

[0139] Example 12

[0140] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 12 kg of MP-02 (produced by Shanghai Research Institute of Petrochemical Technology) MWW molecular sieve catalyst, with a corresponding Hammett function H0 = -6.8. The isopropylnaphthalene feedstock flow rate is 10 kg / h, and hydrogen gas is simultaneously introduced at a rate of 0.12 kg / h. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure is atmospheric pressure, and the intermediate catalyst section temperature is controlled at 210℃. The disproportionation distillation column has 40 theoretical plates. The product column is an atmospheric pressure distillation column with 30 theoretical plates, and its bottom temperature is controlled at 310℃. The heavy removal column is an atmospheric pressure distillation column with 28 theoretical plates, and its bottom temperature is controlled at 360℃.

[0141] The bottom product of the disproportionation distillation column was analyzed. It contained 34.1% isopropylnaphthalene, 65.8% diisopropylnaphthalene, and 0.1% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 99.2% naphthalene and 0.8% isopropylnaphthalene. The isopropylnaphthalene disproportionation conversion rate of this disproportionation distillation column was 65.1%, which is lower than the isopropylnaphthalene conversion rate corresponding to Example 1.

[0142] The final diisopropylnaphthalene product had a diisopropylnaphthalene yield of 5.3 kg / h, a naphthalene yield of 1.2 kg / h, and a heavy component yield of 0.1 kg / h. The diisopropylnaphthalene yield was less than that in Example 11, and the diisopropylnaphthalene content in the obtained product was 61%, which was also less than the diisopropylnaphthalene content in Example 11.

[0143] Example 13

[0144] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 12 kg of MP-02 (produced by Shanghai Research Institute of Petrochemical Technology) MWW molecular sieve catalyst, with a corresponding Hammett function H0 = -6.8. The isopropylnaphthalene feedstock flow rate is 10 kg / h, and hydrogen gas is simultaneously introduced at a rate of 0.12 kg / h. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure is 0.3 MPa, and the intermediate catalyst section temperature is controlled at 210℃. The disproportionation distillation column has 40 theoretical plates. The product column is an atmospheric pressure distillation column with 30 theoretical plates, and its bottom temperature is controlled at 310℃. The heavy removal column is also an atmospheric pressure distillation column with 28 theoretical plates, and its bottom temperature is controlled at 360℃.

[0145] The bottom product of the disproportionation distillation column was analyzed. It contained 31.6% isopropylnaphthalene, 68.3% diisopropylnaphthalene, and 0.1% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 99.3% naphthalene and 0.7% isopropylnaphthalene. The disproportionation conversion rate of isopropylnaphthalene in this disproportionation distillation column was 68.4%, which is lower than the isopropylnaphthalene conversion rate corresponding to Example 1.

[0146] The final diisopropylnaphthalene product had a diisopropylnaphthalene output of 5.1 kg / h, a naphthalene output of 1.3 kg / h, and a heavy component output of 0.1 kg / h. The diisopropylnaphthalene product output was less than that of Example 11, and the diisopropylnaphthalene content in the product was 60%, which was also less than the diisopropylnaphthalene content of Example 11.

[0147] Example 14

[0148] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 10.2 kg of BEA-configuration molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammett function H0 = -7.5. The isopropylnaphthalene feed flow rate is 8.5 kg / h, and hydrogen gas is introduced at a rate of 0.1 kg / h. The bottom temperature of the disproportionation distillation column is controlled at 270℃, the top pressure is controlled at 0.06 MPa, and the intermediate catalyst section temperature is controlled at 205℃. The disproportionation distillation column has 45 theoretical plates. The product column is an atmospheric pressure distillation column with 40 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 30 theoretical plates and a bottom temperature controlled at 355℃.

[0149] The bottom product of the disproportionation distillation column was analyzed. It contained 99.5% diisopropylnaphthalene and 0.6% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 99% naphthalene and 1% isopropylnaphthalene. This disproportionation distillation column achieved a 99.5% conversion rate for the isopropylnaphthalene disproportionation reaction.

[0150] The final output of diisopropylnaphthalene was 5.2 kg / hour, the output of naphthalene was 3.2 kg / hour, the output of heavy components was 0.1 kg / hour, and the content of diisopropylnaphthalene in the diisopropylnaphthalene product was 99%.

[0151] Example 15

[0152] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 10.2 kg of BEA-configuration molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammett function H0 = -7.5. The isopropylnaphthalene feed flow rate is 8.5 kg / h, and hydrogen gas is introduced at a rate of 0.1 kg / h. The bottom temperature of the disproportionation distillation column is controlled at 270℃, the top is at atmospheric pressure, and the intermediate catalyst section temperature is controlled at 205℃. The disproportionation distillation column has 45 theoretical plates. The product column is an atmospheric pressure distillation column with 40 theoretical plates, and the bottom temperature is controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 30 theoretical plates, and the bottom temperature is controlled at 355℃.

[0153] The bottom product of the disproportionation distillation column was analyzed. It contained 34.6% isopropylnaphthalene, 65.3% diisopropylnaphthalene, and 0.1% heavy components (tetraisopropylnaphthalene and above). Simultaneously, the top product of the disproportionation distillation column was analyzed, containing 99% naphthalene and 1% isopropylnaphthalene. This disproportionation distillation column achieved a 65% conversion rate for isopropylnaphthalene disproportionation, which is lower than the isopropylnaphthalene conversion rate corresponding to Example 14.

[0154] The final diisopropylnaphthalene product had a diisopropylnaphthalene output of 4.3 kg / hour, a naphthalene output of 1.0 kg / hour, and a heavy component output of 0.1 kg / hour. The diisopropylnaphthalene content in the product was 59%, which was less than the diisopropylnaphthalene content corresponding to Example 14.

[0155] Example 16

[0156] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 10.2 kg of BEA-configuration molecular sieve catalyst (produced by Shanghai Research Institute of Petrochemical Technology), with a corresponding Hammett function H0 = -7.5. The isopropylnaphthalene feedstock flow rate is 8.5 kg / h, and hydrogen gas is simultaneously introduced at a rate of 0.1 kg / h. The disproportionation distillation column bottom temperature is controlled at 270℃, the top pressure at 0.5 MPa, and the intermediate catalyst section temperature at 205℃. The disproportionation distillation column has 45 theoretical plates. The product column is an atmospheric pressure distillation column with 40 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is also an atmospheric pressure distillation column with 30 theoretical plates and a bottom temperature controlled at 355℃.

[0157] The bottom product of the disproportionation distillation column was analyzed. It contained 29.8% isopropylnaphthalene, 70.1% diisopropylnaphthalene, and 0.1% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 99% naphthalene and 1% isopropylnaphthalene. This disproportionation distillation column achieved a 65% conversion rate for isopropylnaphthalene disproportionation, which is lower than the isopropylnaphthalene conversion rate corresponding to Example 14.

[0158] The final diisopropylnaphthalene product had a diisopropylnaphthalene output of 5.2 kg / hour, a naphthalene output of 0.9 kg / hour, and a heavy component output of 0.1 kg / hour. The diisopropylnaphthalene content in the product was 70%, which was less than the diisopropylnaphthalene content corresponding to Example 14.

[0159] Example 17

[0160] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 1 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -7.8. The isopropylnaphthalene feed flow rate is 8.4 kg / h, with 0.1 kg / h of hydrogen gas introduced simultaneously. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The disproportionation distillation column has 50 theoretical plates. The product column is an atmospheric pressure distillation column with 45 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 30 theoretical plates and a bottom temperature controlled at 355℃.

[0161] The bottom product of the disproportionation distillation column was analyzed. It contained 99.1% diisopropylnaphthalene and 0.9% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 98.5% naphthalene and 1.5% isopropylnaphthalene. This disproportionation distillation column achieved a 99.9% conversion rate for the isopropylnaphthalene disproportionation reaction.

[0162] The final output of diisopropylnaphthalene was 5.1 kg / hour, the output of naphthalene was 3.2 kg / hour, the output of heavy components was 0.1 kg / hour, and the content of diisopropylnaphthalene in the diisopropylnaphthalene product was 99%.

[0163] Example 18

[0164] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 2 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -34. The isopropylnaphthalene feed flow rate is 8.4 kg / h, with 0.1 kg / h of hydrogen gas introduced simultaneously. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The disproportionation distillation column has 50 theoretical plates. The product column is an atmospheric pressure distillation column with 45 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 30 theoretical plates and a bottom temperature controlled at 355℃.

[0165] The bottom product of the disproportionation distillation column was analyzed. It contained 90.1% diisopropylnaphthalene and 9.9% heavy components (tetraisopropylnaphthalene and above). The top product of the disproportionation distillation column was also analyzed, containing 98.8% naphthalene and 1.2% isopropylnaphthalene. This disproportionation distillation column achieved a 99.9% conversion rate for the isopropylnaphthalene disproportionation reaction, consistent with Example 17.

[0166] The final diisopropylnaphthalene product output was 4.6 kg / hour, the naphthalene output was 3.2 kg / hour, and the heavy component output was 0.6 kg / hour. The amount of heavy component generated was greater than that in Example 17.

[0167] Example 19

[0168] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 3 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -2.1. The isopropylnaphthalene feed flow rate is 8.4 kg / h, with 0.1 kg / h of hydrogen gas introduced simultaneously. The disproportionation distillation column bottom temperature is controlled at 260℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The disproportionation distillation column has 50 theoretical plates. The product column is an atmospheric pressure distillation column with 45 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 30 theoretical plates and a bottom temperature controlled at 355℃.

[0169] The bottom product of the disproportionation distillation column was analyzed. It contained 9.8% isopropylnaphthalene, 90.1% diisopropylnaphthalene, and 0.1% heavy components (tetraisopropylnaphthalene and above). Simultaneously, the top product of the disproportionation distillation column was analyzed, containing 98.8% naphthalene and 1.2% isopropylnaphthalene. The isopropylnaphthalene disproportionation conversion rate of this disproportionation distillation column was 90%, which is lower than that of Example 17.

[0170] The final diisopropylnaphthalene product had a diisopropylnaphthalene output of 6.6 kg / hour, a naphthalene output of 0.9 kg / hour, and a heavy component output of 0.1 kg / hour. Furthermore, the diisopropylnaphthalene content in the diisopropylnaphthalene product was 90%, which is less than the diisopropylnaphthalene content corresponding to Example 17.

[0171] Example 20

[0172] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 4 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -7.2. The isopropylnaphthalene feed flow rate is 8.1 kg / h, and hydrogen gas is simultaneously introduced at a rate of 0.09 kg / h. The disproportionation distillation column bottom temperature is controlled at 270℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The theoretical number of trays in the disproportionation distillation column is 47. The disproportionation distillation column has operated stably for over 1000 hours. The product column is an atmospheric pressure distillation column with 41 theoretical trays, and the bottom temperature is controlled at 320℃. The deweight removal column is an atmospheric pressure (atmospheric pressure) distillation column with 32 theoretical plates and a bottom temperature controlled at 355℃.

[0173] The bottom product of the disproportionation distillation column was analyzed. It contained 99.2% diisopropylnaphthalene and 0.8% heavy components (tetraisopropylnaphthalene and above). Simultaneously, the top product of the disproportionation distillation column was analyzed, containing 99% naphthalene and 1% isopropylnaphthalene. This disproportionation distillation column achieved a 99% conversion rate for the isopropylnaphthalene disproportionation reaction.

[0174] The final output of diisopropylnaphthalene product is 5 kg / hour, the output of naphthalene is 3 kg / hour, the output of heavy components is 0.1 kg / hour, and the content of diisopropylnaphthalene in the diisopropylnaphthalene product is 94%.

[0175] Comparative Example 3

[0176] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3 The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 4 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -7.2. The isopropylnaphthalene feed flow rate is 8.1 kg / h, and no hydrogen is introduced. The disproportionation distillation column bottom temperature is controlled at 270℃, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210℃. The theoretical number of plates in the disproportionation distillation column is 47. The product column is an atmospheric pressure distillation column with 41 theoretical plates and a bottom temperature controlled at 320℃. The heavy removal column is an atmospheric pressure distillation column with 32 theoretical plates and a bottom temperature controlled at 355℃.

[0177] Within the first 100 hours, the bottom product of the disproportionation distillation column was analyzed. It contained 95% diisopropylnaphthalene and 5% heavy components (tetraisopropylnaphthalene and above), with the amount of heavy components significantly exceeding that in Example 20. Simultaneously, the top product of the disproportionation distillation column was analyzed, containing 99% naphthalene and 1% isopropylnaphthalene.

[0178] The disproportionation distillation column had a stable operating time of less than 200 hours. After 200 hours, the catalyst was deactivated. Under this operating condition, the catalyst life was significantly shorter than that of Example 20.

[0179] Comparative Example 4

[0180] Using isopropyl naphthalene (95% isopropyl naphthalene, 4% other naphthalene, and 1% diisopropyl naphthalene) as raw material, according to... Figure 3The process flow diagram shown illustrates the reaction. The disproportionation distillation column is filled with 8.5 kg of sulfuric acid-supported zirconia-type solid superacid catalyst No. 4 (preparation method: first, solid zirconium hydroxide is prepared by co-precipitation, then impregnated with dilute sulfuric acid, followed by filtration, calcination, tableting, and molding to obtain the sulfuric acid-supported zirconia superacid solid catalyst), with a corresponding Hammett function H0 = -7.2. The isopropylnaphthalene feed flow rate is 8.1 kg / h, with 0.09 kg / h of hydrogen gas introduced simultaneously. The disproportionation distillation column bottom temperature is controlled at 270°C, the top pressure at 0.05 MPa, and the intermediate catalyst section temperature at 210°C. The theoretical number of plates in the disproportionation distillation column is 47. The product column is an atmospheric pressure distillation column with 41 theoretical plates and a bottom temperature controlled at 290°C, lower than the 320°C in Example 20. The heavy removal column is an atmospheric pressure distillation column with 32 theoretical plates and a bottom temperature controlled at 355°C.

[0181] The bottom product of the disproportionation distillation column was analyzed. It contained 5.1% isopropylnaphthalene, 94.1% diisopropylnaphthalene, and 0.8% heavy components (tetraisopropylnaphthalene and above). Simultaneously, the top product of the disproportionation distillation column was analyzed, containing 99% naphthalene and 1% isopropylnaphthalene. The isopropylnaphthalene disproportionation conversion rate of this disproportionation distillation column (94%) is lower than the isopropylnaphthalene conversion rate corresponding to Example 20.

[0182] The final diisopropylnaphthalene product output was 4.7 kg / hour, the naphthalene output was 3 kg / hour, and the heavy component output was 0.1 kg / hour. The diisopropylnaphthalene content in the diisopropylnaphthalene product was 94%, which is less than the diisopropylnaphthalene content corresponding to Example 20.

[0183] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0184] Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0185] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application’s filing, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0186] In the context of this specification, except where expressly stated, any matters or issues not mentioned herein shall apply directly to those known in the art without any modification. Furthermore, any implementation described herein may be freely combined with one or more other implementations described herein, and any resulting technical solutions or concepts shall be considered part of the original disclosure or original record of this invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider such combination to be clearly unreasonable.

[0187] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A method for preparing a dialkyl arene compound, comprising the following steps: optionally, step (1) : subjecting an arene compound to an alkylation reaction with an olefin to obtain an alkyl arene; step (2) : subjecting the alkyl arene to a disproportionation reaction in a disproportionation rectifying column in the presence of optional hydrogen to obtain the dialkyl arene compound, wherein the disproportionation rectifying column is filled with a disproportionation catalyst catalyzing the disproportionation reaction; the alkyl arene is cumene, and the dialkyl arene compound is diisopropyl benzene; the disproportionation rectifying column is a pressurized rectifying column, the top pressure of the disproportionation rectifying column is 0.2-0.5 MPa, and the temperature of the catalyst-filled section of the disproportionation rectifying column is 160-180 ℃; or the alkyl arene is isopropyl naphthalene, the dialkyl arene compound is diisopropyl naphthalene, and the disproportionation rectifying column is a reduced-pressure rectifying column, the top pressure of the disproportionation rectifying column is 0.03-0.07 MPa, and the temperature of the catalyst-filled section of the disproportionation rectifying column is 200-210 ℃; the disproportionation catalyst is at least one selected from the group consisting of a MWW-configuration molecular sieve catalyst, a BEA-configuration molecular sieve catalyst, a MTW-configuration molecular sieve catalyst, a MFI-configuration molecular sieve catalyst, a solid acid catalyst of zirconium oxide supported by sulfuric acid, and a solid acid catalyst of zirconium oxide and titanium oxide supported by sulfuric acid; the Hammett function H 0 of the disproportionation catalyst ranges from-28 to-3.5; the Hammett function H 0 of the disproportionation catalyst ranges from-23 to-5.6; when cumene is used as the raw material to prepare diisopropyl benzene by disproportionation reaction, the Hammett function H 0 of the disproportionation catalyst ranges from-9 to-7; when isopropyl naphthalene is used as the raw material to prepare diisopropyl naphthalene by disproportionation reaction, the Hammett function H 0 of the disproportionation catalyst ranges from-8 to-6; the disproportionation rectifying column is a pressurized rectifying column, the bottom temperature of the disproportionation rectifying column is 220-300 ℃; and / or the top pressure of the disproportionation rectifying column is 0.3-0.5 MPa; and / or the temperature of the catalyst-filled section of the disproportionation rectifying column is 160-180 ℃; and / or the arene compound is benzene, the olefin is propylene, and the amount of hydrogen is 0; the disproportionation rectifying column is a pressurized rectifying column, and the bottom temperature of the disproportionation rectifying column is 230-250 ℃; the disproportionation rectifying column is a reduced-pressure rectifying column, the top pressure of the disproportionation rectifying column is 0.05-0.06 MPa; and / or the bottom temperature of the disproportionation rectifying column is 250-300 ℃; and / or the temperature of the catalyst-filled section of the disproportionation rectifying column is 200-210 ℃; and / or the method does not perform step (1), the alkyl arene is isopropyl naphthalene, and the amount of hydrogen is not 0; the disproportionation rectifying column is a reduced-pressure rectifying column, and the bottom temperature of the disproportionation rectifying column is 260-280 ℃; the number of theoretical plates of the disproportionation rectifying column is 25-80; the disproportionation catalyst is filled in the disproportionation rectifying column at a position being more than 10 theoretical plates away from the bottom of the disproportionation rectifying column; and / or the filling position of the disproportionation catalyst is in the middle section of the disproportionation rectifying column. ​ ​ ​ ​ ​ ​ ​ 2. The production method according to claim 1, characterized by, ​ 3. The production method according to claim 2, characterized by, ​ 4. The production method according to any one of claims 1 to 3, characterized by, ​ 5. The preparation method according to claim 4, characterized in that, ​ 6. The production method according to any one of claims 1 to 3, characterized by, ​ 7. The preparation method according to claim 6, characterized in that, ​ 8. The production method according to any one of claims 1 to 3, characterized by, ​ 9. The production method according to claim 8, characterized by, ​ 10. The preparation method according to claim 8, characterized in that, ​ 11. The production method according to any one of claims 1 to 3, characterized by, The alkylation reaction in step (1) is a liquid phase alkylation reaction.

12. The production method according to any one of claims 1 to 3, characterized by, The alkylation reaction in step (1) is carried out in a fixed bed reactor.

13. The production method according to any one of claims 1 to 3, characterized by, The temperature of the alkylation reaction in step (1) is 100-200℃, and / or the pressure of the alkylation reaction is 2.5-4.0 MPa.

14. The method of claim 13, wherein, The temperature of the alkylation reaction in step (1) is 130-150℃, and / or the pressure of the alkylation reaction is 3.0-3.5 MPa.

15. The method of any one of claims 1-3, wherein, The alkylation reaction in step (1) is carried out in the presence of a solid acid catalyst, and the Hammett function H0 of the solid acid catalyst ranges from -25 to -3.

16. The method of claim 15, wherein, The alkylation reaction in step (1) is carried out in the presence of a solid acid catalyst, and the Hammett function H0 of the solid acid catalyst ranges from -7 to -5.

17. The preparation method according to claim 15, characterized in that, The alkylation reaction in step (1) is carried out in the presence of a solid acid catalyst selected from at least one of MWW, BEA, MOR and Y configuration molecular sieve catalysts.

18. The method of making of any one of claims 1-3, wherein, Step (1) further comprises passing the reaction product obtained from the alkylation reaction through a light component removal column to remove light components in the reaction product.

19. The method of claim 18, wherein, The light component removal column is an atmospheric distillation column, and the column bottom temperature of the light component removal column is 80-150℃.

20. The method of claim 19, wherein, The column bottom temperature of the light component removal column is 90-100℃.

21. The method of making according to any one of claims 1-3, wherein, Step (2) further comprises passing the column bottom material of the disproportionation distillation column into a product column.

22. The method of claim 21, wherein, When preparing diisopropyl naphthalene by carrying out a disproportionation reaction on isopropyl naphthalene under ortho-hydrogen conditions, the column bottom material of the disproportionation distillation column is passed into a product column to separate diisopropyl naphthalene, and the product column is an atmospheric distillation column.

23. The preparation method according to claim 22, characterized in that, The column bottom temperature of the product column is 300-330℃.

24. The method of claim 22, wherein, The column bottom temperature of the product column is 310-320℃.

25. The method of claim 21, wherein, Step (2) further comprises passing the column bottom material of the product column into a heavy component removal column to remove heavy components, and the heavy component removal column is an atmospheric distillation column.

26. The method of claim 25, wherein, The column bottom temperature of the heavy component removal column is 340-370℃.

27. The preparation method according to claim 25, characterized in that, The column bottom temperature of the heavy component removal column is 350-360℃.

28. The method of making of any one of claims 1-3, wherein, In step (2), the molar ratio of the amount of hydrogen to the amount of alkyl aromatic hydrocarbon is (0.5-5):

1.

29. The method of making of any one of claims 1-3, wherein, In step (2), the molar ratio of the amount of hydrogen to the amount of alkyl aromatic hydrocarbon is (1.0-2.0):1.

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