Side chain alkylation catalyst as well as preparation method and application thereof

Abstract

The invention discloses a side chain alkylation catalyst and a preparation method and application thereof.The catalyst comprises a carrier and an auxiliary I loaded on the carrier, the carrier comprises a molecular sieve subjected to IA group metal ion exchange treatment, and the auxiliary I is selected from one or more of VIII group metals; an auxiliary agent II is further optionally loaded on the carrier, and the auxiliary agent II is selected from one or more of IIIB group metals. The side-chain alkylation catalyst can be applied to side-chain alkylation of aromatic hydrocarbon, such as side-chain alkylation of toluene and methanol or side-chain alkylation of toluene and propylene.

Description

Technical Field

[0001] This invention belongs to the field of side-chain alkylation technology, and particularly relates to a side-chain alkylation catalyst, its preparation method and application. Background Technology

[0002] Isobutylbenzene (IBB) is a key intermediate in the synthesis of ibuprofen (Profe or Brufen), a human drug used for its anti-inflammatory, antipyretic, and analgesic properties. Since its initial market launch by Boots in the 1970s, ibuprofen has been extremely popular and a top seller in the international market. Almost all of the numerous synthetic routes for ibuprofen require the intermediate isobutylbenzene. To date, there are more than a dozen synthetic routes for isobutylbenzene, but most are laboratory preparation methods. While some can be industrialized, the raw materials are often difficult to obtain.

[0003] In 1950, scientists such as Pines first proposed the use of strong bases to catalyze the side-chain alkylation reaction of alkyl aromatic hydrocarbons with small molecule olefins. The strong base catalyst consists of an alkali metal or alkali metal hydride and a promoter. The promoter can be an aromatic hydrocarbon, phenyl cyanide, pyridine, or chloroalkanes, etc. Its main function is to induce the alkali metal or its oxides to form organometallic compounds, which then attack the alkylbenzene. In the late 1970s, while developing ibuprofen, the Northwest Second Pharmaceutical Factory in my country also began research on the synthesis of isobutylene. During this period, the Shandong Provincial Chemical Research Institute, the Liaoning Provincial Chemical Research Institute, the Ningxia Chemical Research Institute, and the Fushun Chemical Research and Design Institute also began research on isobutylene production technology, successfully developing production technologies using potassium metal as a catalyst, sodium carbonate as a support, and toluene and propylene side-chain alkylation to produce isobutylene.

[0004] US4914251A, US4962254A, US6046130A, US6414207B2, US7148177B2 and other patents disclose current methods for synthesizing isobutylene, all of which use intermittent high-pressure autoclave reactors and catalysts that contain metallic alkali metals. The reactions are carried out under high pressure and anhydrous and oxygen-free conditions, which poses a great safety risk. Summary of the Invention

[0005] To overcome the problems existing in the prior art, the present invention provides a side-chain alkylation catalyst, its preparation method and application. Using this catalyst, the present invention further provides a fixed-bed reaction process for the synthesis of isobutylene by the side-chain alkylation of toluene and propylene. Compared with the traditional batch reaction process, it has the advantages of simple operation and mild process conditions, and can realize continuous isobutylene production.

[0006] One objective of this invention is to provide a side-chain alkylation catalyst comprising a support and an auxiliary agent I supported on the support, wherein the support comprises a molecular sieve treated with group IA metal ion exchange, and the auxiliary agent I is selected from one or more group VIII metals.

[0007] In a preferred embodiment, the molecular sieve is a basic molecular sieve.

[0008] In a further preferred embodiment, the molecular sieve is selected from at least one of X molecular sieve and Y molecular sieve.

[0009] In a preferred embodiment, the Group IA metal is selected from one, two, or three of potassium, rubidium, and cesium.

[0010] In a further preferred embodiment, the Group IA metal is 10-25 wt% based on 100 wt% of the molecular sieve, preferably 12-20 wt%, for example 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, or 25 wt%.

[0011] In a preferred embodiment, the auxiliary agent I is selected from one or both of iridium and ruthenium.

[0012] In a further preferred embodiment, based on 100 wt% of the molecular sieve, the additive I is 0.1 to 2 wt%, preferably 0.2 to 0.8 wt%, wherein the weight of additive I is based on the weight of the metal element.

[0013] For example, based on 100 wt% of the molecular sieve, the additive I is 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, or 2 wt%, wherein the weight of additive I is based on the weight of the metal element.

[0014] In a preferred embodiment, the carrier is optionally further loaded with an additive II, which is selected from one or more group IIIB metals, preferably from one or two of yttrium and scandium.

[0015] In a further preferred embodiment, based on 100 wt% of the molecular sieve, the additive II is 0.5 to 6 wt%, preferably 1.5 to 4 wt%, wherein the weight of additive II is based on the weight of the metal element.

[0016] For example, based on 100 wt% of the molecular sieve, the additive II is 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, or 6 wt%, wherein the weight of additive II is based on the weight of the metal element.

[0017] The second objective of this invention is to provide a method for preparing a side-chain alkylation catalyst, preferably for preparing the side-chain alkylation catalyst described in the first objective of this invention. The preparation method includes: (1) ion-exchanging a molecular sieve with at least one of group IA metal ions to obtain the support, and (2) loading an auxiliary agent I and optional auxiliary agent II onto the support to obtain the side-chain alkylation catalyst.

[0018] Preferably, when using additive II, additive II is loaded first, and then additive I is loaded (after drying).

[0019] In a preferred embodiment, the molecular sieve is a basic molecular sieve.

[0020] In a further preferred embodiment, the molecular sieve is selected from at least one of X molecular sieve and Y molecular sieve.

[0021] In a preferred embodiment, the group IA metal ion is selected from one, two, or three of potassium ions, rubidium ions, and cesium ions.

[0022] In a further preferred embodiment, based on 100 wt% of the molecular sieve described in step (1), the group IA metal is 10-25 wt%, preferably 12-20 wt%.

[0023] In a preferred embodiment, step (1) includes: mixing the molecular sieve with an aqueous solution of a group IA metal salt for ion exchange, filtering, and drying.

[0024] In a further preferred embodiment, step (1) is performed 1 to 5 times, that is, 1 to 5 ion exchanges are performed, and the group IA metal salts exchanged each time are the same or different.

[0025] In a further preferred embodiment, the ion exchange is carried out at 40–60°C, for example, 40°C, 45°C, 50°C, 55°C, or 60°C.

[0026] In a preferred embodiment, step (2) includes: loading the precursor of auxiliary agent I and the precursor of optional auxiliary agent II separately or together with the support, and drying and calcining the loaded catalyst.

[0027] In a further preferred embodiment, the precursor of the adjuvant I is selected from at least one of soluble Group VIII metal salts, such as nitrates and / or chlorides of soluble Group VIII metals.

[0028] In a further preferred embodiment, the precursor of the adjuvant II is selected from at least one of soluble Group IIIB metal salts, such as nitrates and / or chlorides of soluble Group IIIB metals.

[0029] In a preferred embodiment, when loading additive II, additive II is loaded first, and then additive II is loaded.

[0030] In a further preferred embodiment, when the auxiliary agent II is supported, step (2) includes: (2.1) immersing the support in an aqueous solution of a soluble group IIIB metal salt and drying it to obtain a catalyst precursor; (2.2) immersing the catalyst precursor in an aqueous solution of a soluble group VIII metal salt and drying it; (2.3) calcining it to obtain the side-chain alkylation catalyst.

[0031] The impregnation method described in this invention is preferably equal-volume impregnation. Preferably, based on 100 wt% of the molecular sieve described in step (1), the metal element content in the precursor of the auxiliary agent I is 0.1-2 wt%, preferably 0.2-0.8 wt%; and the metal element content in the precursor of the auxiliary agent II is 0.5-6 wt%, preferably 1.5-4 wt%.

[0032] In a further preferred embodiment, the calcination conditions include: a temperature of 300–800°C and a time of 0.2–6 hours.

[0033] For example, the roasting conditions include: a temperature of 300°C, 400°C, 500°C, 600°C, 700°C or 800°C, and a time of 0.2h, 0.5h, 1h, 2h, 3h, 4h, 5h or 6h.

[0034] In a further preferred embodiment, the calcination conditions include a temperature of 350–650°C and a time of 0.5–4 hours.

[0035] In a preferred embodiment, reduction is performed after calcination or before the catalyst is used.

[0036] In a further preferred embodiment, the reduction conditions include: a temperature of 200–300°C and a time of 1–3 hours.

[0037] For example, the reduction conditions include: a temperature of 200°C, 220°C, 240°C, 260°C, 280°C or 300°C, and a time of 1h, 1.5h, 2h, 2.5h or 3h.

[0038] In a preferred embodiment, the side-chain alkylation catalyst is optionally tableted.

[0039] A third objective of this invention is to provide the application of the side-chain alkylation catalyst described in the first objective of this invention or the side-chain alkylation catalyst obtained by the preparation method described in the second objective of this invention in the side-chain alkylation of aromatic hydrocarbons, such as the side-chain alkylation of toluene-methanol or the side-chain alkylation of toluene-propylene.

[0040] The fourth objective of this invention is to provide a method for preparing alkyl aromatics by side-chain alkylation, comprising: reacting raw materials, including aromatics and olefins, under a protective gas in a fixed-bed reactor packed with a side-chain alkylation catalyst to obtain alkyl aromatics; wherein the side-chain alkylation catalyst is the side-chain alkylation catalyst described in the first objective of this invention or the side-chain alkylation catalyst obtained by the preparation method described in the second objective of this invention.

[0041] For example, isobutylene is prepared by reacting toluene with propylene to induce side chain alkylation.

[0042] In a preferred embodiment, the aromatic hydrocarbon is toluene and the olefin is propylene.

[0043] In a preferred embodiment, the method is carried out in a continuous fixed-bed reactor.

[0044] The method employs a continuous fixed-bed reaction process.

[0045] In a preferred embodiment, the molar ratio of aromatic hydrocarbon to olefin is (0.1–5):1, preferably (0.3–3):1.

[0046] For example, the molar ratio of aromatics to olefins is 0.1:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1.

[0047] In a preferred embodiment, the mass hourly space velocity (MSV) of the aromatic hydrocarbon is 0.1–5 h⁻¹. -1 Preferably 0.3 to 3 hours -1 .

[0048] For example, the mass hourly space velocity of the aromatic hydrocarbon is 0.1 h⁻¹. -1 0.5h -1 0.8h -1 1h -1 1.5h -1 2h -1 2.5h -1 3h -1 3.5h -14h -1 4.5h -1 or 5h -1 .

[0049] In a preferred embodiment, the reaction conditions include a temperature of 400–600°C and a pressure of 0.2–0.5 MPa.

[0050] For example, the reaction conditions include: a temperature of 400°C, 500°C, or 600°C, and a pressure of 0.2 MPa, 0.3 MPa, 0.4 MPa, or 0.5 MPa.

[0051] This invention provides a fixed-bed reaction process for the synthesis of alkyl aromatics (e.g., the synthesis of isobutylene from the side chain alkylation of toluene and propylene) by the side chain alkylation of aromatic olefins. Compared with traditional batch reaction processes, it has the advantages of simple operation and mild process conditions, and can also realize continuous production of isobutylene.

[0052] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; 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. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] The side-chain alkylation catalyst can be used for the side-chain alkylation of aromatics, and has the advantages of high conversion rate and high selectivity. Specifically, when applied to the side-chain alkylation of toluene and propylene to prepare isobutylene, it has the advantages of high toluene conversion rate and high isobutylene selectivity. Detailed Implementation

[0055] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0056] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0057] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0058] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0059] In the examples and comparative examples, the content of Group IA elements, based on 100 wt% of the molecular sieve, was obtained by plasma coupling (i.e., ICP, also known as inductively coupled plasma) detection method, and measured by Thermo's IRIS Intrepid XSP inductively coupled plasma atomic emission spectrometer.

[0060] The activity and selectivity of the catalyst are calculated according to the following formula:

[0061]

[0062]

[0063]

Example 1

[0064] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, ion exchange with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours, filter, and dry overnight at 110 degrees Celsius to obtain the support.

[0065] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0066] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated in the above catalyst precursor with an equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0067]

Example 2

[0068] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange 4 times. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0069] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0070] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the above catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0071]

Example 3

[0072] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0073] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0074] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0075]

Example 4

[0076] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange 3 times. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0077] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0078] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0079]

Example 5

[0080] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0081] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0082] 0.12 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0083]

Example 6

[0084] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0085] Dissolve 1.55g of yttrium nitrate hexahydrate in an appropriate amount of water, impregnate an equal volume onto the above-mentioned support, air dry at room temperature, and then dry overnight at 110°C to obtain the catalyst precursor.

[0086] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0087]

Example 7

[0088] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L KNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0089] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0090] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0091]

Example 8

[0092] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L RbNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0093] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0094] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0095]

Example 9

[0096] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0097] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0098] 0.05 g of ruthenium chloride trihydrate was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0099]

Example 10

[0100] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours. Repeat the exchange twice. After filtration, dry it overnight at 110 degrees Celsius to obtain the support.

[0101] Dissolve 0.92g of scandium nitrate in an appropriate amount of water, impregnate the carrier with an equal volume, and dry at room temperature and then dry overnight at 110°C to obtain the catalyst precursor.

[0102] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0103]

Example 11

[0104] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, ion exchange with 1mol / L KNO3 solution at 40 degrees Celsius for 2 hours, then ion exchange with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours, filter, and dry overnight at 110 degrees Celsius to obtain the support.

[0105] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0106] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0107]

Example 12

[0108] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, and ion exchange it with 1mol / L KNO3 solution at 40°C for 2 hours, then with 1mol / L RbNO3 solution at 40°C for 2 hours, then with 1mol / L CsNO3 solution at 40°C for 2 hours. After filtration, dry it overnight at 110°C to obtain the support.

[0109] Dissolve 0.77g of yttrium nitrate hexahydrate in an appropriate amount of water, and impregnate the carrier with an equal volume. After drying at room temperature, dry overnight at 110°C to obtain the catalyst precursor.

[0110] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the catalyst precursor in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain the side-chain alkylation catalyst. The component content of the catalyst is shown in Table 1.

[0111] Comparative Example 1

[0112] 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19 was ion-exchanged with 1mol / L CsNO3 solution at 40°C for 2 hours. After filtration, it was dried overnight at 110°C, calcined at 500°C for 2 hours, and reduced at 250°C for 2 hours to obtain Comparative Example 1. The component content of the catalyst is shown in Table 1.

[0113] Comparative Example 2

[0114] 0.77 g of yttrium nitrate hexahydrate was dissolved in an appropriate amount of water and impregnated in an equal volume onto 10 g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19. After being air-dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain Comparative Example 2. The component content of the catalyst is shown in Table 1.

[0115] Comparative Example 3

[0116] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated in an equal volume onto 10 g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19. After being air-dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain Comparative Example 3. The component content of the catalyst is shown in Table 1.

[0117] Comparative Example 4

[0118] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, ion exchange with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours, filter, and dry overnight at 110 degrees Celsius to obtain the support.

[0119] 0.77 g of yttrium nitrate hexahydrate was dissolved in an appropriate amount of water and impregnated onto the above-mentioned carrier in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain Comparative Example 4. The component content of the catalyst is shown in Table 1.

[0120] Comparative Example 5

[0121] Take 10g of NaX molecular sieve with a silicon-to-aluminum ratio of SiO2 / Al2O3 = 2.19, ion exchange with 1mol / L CsNO3 solution at 40 degrees Celsius for 2 hours, filter, and dry overnight at 110 degrees Celsius to obtain the support.

[0122] 0.04 g of iridium trichloride hydrate (CAS No. 14996-61-3) was dissolved in an appropriate amount of water and impregnated onto the above-mentioned carrier in equal volume. After being dried at room temperature, it was dried overnight at 110 degrees Celsius, calcined at 500 degrees Celsius for 2 hours, and reduced at 250 degrees Celsius for 2 hours to obtain Comparative Example 5. The component content of the catalyst is shown in Table 1.

[0123] Catalyst Evaluation

[0124] The catalysts obtained in Examples 1-12 and Comparative Examples 1-5 were compressed into 40-60 mesh particles, loaded into a reactor, and reacted at a temperature of 400°C, a pressure of 0.2 MPa, and a toluene mass hourly space velocity of 0.3 h⁻¹. -1The molar ratio of toluene to propylene was 0.3:1, the carrier gas was N2, and the carrier gas flow rate was 10 ml / min. Toluene was introduced first, and after reacting for 0.1 h, propylene was introduced. The evaluation results are shown in Table 1.

[0125] Table 1

[0126]

[0127] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. A side chain alkylation catalyst comprising a support and an auxiliary I supported on the support, the support comprising a molecular sieve ion-exchanged with at least one of Group IA metal ions, the auxiliary I selected from one or more of Group VIII metals.

2. The side chain alkylation catalyst of claim 1, wherein, The molecular sieve is selected from at least one of X molecular sieve, Y molecular sieve, preferably from basic molecular sieve.

3. The side chain alkylated catalyst of claim 1, wherein, The Group IA metal is selected from one, two or three of potassium, rubidium, cesium; preferably, the Group IA metal is 10-25 wt%, preferably 12-20 wt% based on 100 wt% of the molecular sieve.

4. The side chain alkylation catalyst according to claim 1, wherein the auxiliary I is selected from one or both of iridium, ruthenium; and / or, the auxiliary I is 0.1-2 wt%, preferably 0.2-0.8 wt% based on 100 wt% of the molecular sieve, wherein the weight of auxiliary I is based on the weight of the metal element. The support is further optionally loaded with an auxiliary II selected from one or more of Group IIIB metals, preferably one or both of yttrium, scandium; More preferably, the auxiliary II is 0.5-6 wt%, preferably 1.5-4 wt% based on 100 wt% of the molecular sieve, wherein the weight of auxiliary II is based on the weight of the metal element.

5. The catalyst according to any one of claims 1 to 4, wherein (1) ion-exchanging the molecular sieve with at least one of Group IA metal ions to obtain the support, (2) loading the auxiliary I and optionally the auxiliary II on the support to obtain the side chain alkylation catalyst. Step (1) comprises mixing the molecular sieve with an aqueous solution of Group IA metal salt for ion-exchange, filtering, drying; 6. A process for the preparation of a side chain alkylation catalyst, preferably for the preparation of a side chain alkylation catalyst according to any one of claims 1 to 5, said process comprising: Preferably, step (1) is performed 1-5 times, each time with the same or different Group IA metal salt for ion-exchange; 7. The production method according to claim 6, wherein Preferably, the ion-exchange is performed at 40-60 °C. Step (2) comprises mixing the precursor of auxiliary I and optionally the precursor of auxiliary II separately or together with the support for loading, drying and calcining after loading to obtain the catalyst; Preferably, the precursor of auxiliary I is selected from at least one of soluble Group VIII metal salts; and / or, the precursor of auxiliary II is selected from at least one of soluble Group IIIB metal salts.

8. The preparation method according to claim 6, characterized in that, When loading auxiliary II, the auxiliary II is loaded first, then the auxiliary II is loaded; preferably, step (2) comprises (2.1) impregnating the support in an aqueous solution of soluble Group IIIB metal salt, drying to obtain a catalyst precursor; (2.2) impregnating the catalyst precursor in an aqueous solution of soluble Group VIII metal salt, drying; (2.3) calcining to obtain the side chain alkylation catalyst. The calcining conditions comprise a temperature of 300-800 °C and a time of 0.2-6 h; preferably, the calcining conditions comprise a temperature of 350-650 °C and a time of 0.5-4 h.

9. The production method according to claim 8, characterized by, ​ 10. The preparation method according to claim 8, characterized in that, ​ 11. Use of the side chain alkylation catalyst according to any one of claims 1 to 5 or the side chain alkylation catalyst obtained by the preparation method according to any one of claims 6 to 10 in the side chain alkylation of aromatic hydrocarbons, preferably in the side chain alkylation of toluene with methanol or in the side chain alkylation of toluene with propylene.

12. A process for the preparation of an alkylaromatic hydrocarbon by a side chain alkylation comprising: In a fixed bed reactor loaded with a side chain alkylation catalyst, a feedstock comprising an aromatic hydrocarbon and an olefin is reacted under a protective gas to obtain an alkylaromatic hydrocarbon; wherein the side chain alkylation catalyst is the side chain alkylation catalyst according to any one of claims 1 to 5 or the side chain alkylation catalyst obtained by the preparation method according to any one of claims 6 to 10.

13. The method according to claim 12, characterized in that, the aromatic hydrocarbon is toluene and the olefin is propylene; and / or, the molar ratio of the aromatic hydrocarbon to the olefin is (0.1 to 5): 1, preferably (0.3 to 3): 1; and / or, The mass space velocity of the aromatic hydrocarbon is 0.1 to 5 h -1 , preferably 0.3 to 3 h -1 ; and / or, the reaction conditions include a temperature of 400 to 600 °C and a pressure of 0.2 to 0.5 MPa.

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