WO2023124789A1 - Procédé de préparation d'alkylbenzène - Google Patents

Procédé de préparation d'alkylbenzène Download PDF

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WO2023124789A1
WO2023124789A1 PCT/CN2022/136459 CN2022136459W WO2023124789A1 WO 2023124789 A1 WO2023124789 A1 WO 2023124789A1 CN 2022136459 W CN2022136459 W CN 2022136459W WO 2023124789 A1 WO2023124789 A1 WO 2023124789A1
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alkylbenzene
molecular sieve
low
source
silicon
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PCT/CN2022/136459
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Chinese (zh)
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崔岩
韩明汉
邢世勇
沈宜泓
李梦晨
王晓化
郭成玉
于宏悦
张上
迟克彬
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中国石油天然气股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a method for preparing alkylbenzene, which belongs to the field of alkylbenzene production.
  • Alkylation is a very important reaction in petrochemical industry.
  • the commonly used catalysts can be divided into L-acid catalysts and B-acid catalysts.
  • the L-acid catalysts are mainly represented by anhydrous AlCl 3 .
  • the B acid catalyst is HF, H 2 SO 4 and H 3 PO 4 Representatives, at present, the industrial production of linear alkylbenzene (LAB) mainly uses HF catalyst, which has the characteristics of high catalytic activity and mature technology.
  • the catalyst of the component can catalyze the synthesis of alkylbenzene products such as 2-alkylbenzene, but the single-pass life of the catalyst is less than 20h;
  • the patent document CN101058523A discloses a preparation method of linear Linear olefins with carbon atoms and benzene are used as raw materials, and a solid acid catalyst is used to carry out an alkylation reaction under supercritical conditions of 290-450 ° C and 5-15 MPa to produce linear alkylbenzene.
  • the solid acid catalyst used is the following One or a composite solid acid catalyst obtained by loading and modifying one of the following: SBA-15 molecular sieve, HY molecular sieve, USY molecular sieve, H ⁇ molecular sieve, H-Moderite molecular sieve, HZSM-20 molecular sieve, the preparation
  • SBA-15 molecular sieve HY molecular sieve
  • USY molecular sieve H ⁇ molecular sieve
  • H-Moderite molecular sieve HZSM-20 molecular sieve
  • the process has defects such as harsh reaction conditions, high energy consumption, high equipment requirements, and high cost
  • patent document CN103079698A discloses a method for controlling the content of 2-phenyl isomers of linear alkylbenzenes and a catalyst used in the method.
  • the method comprises: reacting a substantially linear olefin comprising molecules having 8 to 28 carbon atoms with an aryl compound under alkylation reaction conditions in the presence of a catalyst comprising a selected group of rare earth-containing faujasites and The first catalyst component zeolite of the mixture and the second catalyst component zeolite selected from UZM-8, zeolite MWW, zeolite BEA, zeolite OFF, zeolite MOR, zeolite LTL, zeolite MTW, BPH/UZM-4 and mixtures thereof, the The catalyst used in the process needs to introduce rare earth elements, and the composition of the catalyst is complex;
  • patent document CN108569945A discloses a production method of linear alkylbenzene, including the step of contacting long-chain olefins and benzene with the catalyst under alkylation reaction conditions, and the catalyst is measured by weight Parts include 40 to 90 parts of organosilicon zeolite and 10 to 60 parts of
  • the liquid-phase alkylation catalyst includes A molecular sieve with a MWW topology and a binder, wherein, based on the total weight of the liquid-phase alkylation catalyst, the content of the molecular sieve with a MWW topology is 50-90% by weight, and the content of the binder is 10-50% by weight %, the external area and pore volume of the liquid-phase alkylation catalyst are 0.45-0.65 cm 3 /g.
  • a boron source needs to be introduced in the preparation process of molecular sieves with MWW topological structure, which is actually a boron-containing MWW molecular sieve and A liquid-phase alkylation catalyst formed by compounding binders, used for the alkylation reaction of benzene and short-chain olefins (ethylene).
  • the invention provides a method for preparing alkylbenzene, which has the advantages of long life of catalyst in one pass, high conversion rate of raw materials, high selectivity of 2-alkylbenzene and 3-alkylbenzene, and low cost, and can effectively overcome the existing problems in the prior art. Defects.
  • a method for preparing alkylbenzene comprising: performing an alkylation reaction between benzene and an olefin raw material under the action of a solid acid catalyst to obtain an alkylbenzene; wherein, the olefin raw material includes Long-chain olefins less than 6, the solid acid catalyst includes a binder and a low-layered molecular sieve with a MWW topology, and the axial direction of the crystal band axis of the low-layered molecular sieve with a MWW topology is the c-axis direction , the thickness of the low-layered molecular sieve with MWW topology along the direction of the c-axis is 1.5 nm to 25 nm, and the thickness of the low-layered molecular sieve with MWW topology on a plane perpendicular to the direction of the c-axis The maximum length is 200nm to 3000nm.
  • the silicon source is counted as SiO2
  • the aluminum source is counted as Al2O3
  • the alkali source is counted as metal oxide
  • the molar ratio of the silicon source to the aluminum source is (22.5-97.5): 1
  • the molar ratio of the template agent to the silicon source is (0.08-0.45): 1
  • the molar ratio of the alkali source to the silicon source is (0.03-0.20): 1
  • the molar ratio of the water to the silicon source is (10-60):1.
  • the silicon source is counted as SiO 2
  • the quaternary ammonium salt is counted as quaternary ammonium cation
  • the silicon agent is counted as SiO 2
  • the molar ratio of the quaternary ammonium salt to the silicon source is is (0.1-1.0):1
  • the molar ratio of the silicon agent to the silicon source is (0.05-2.5):1.
  • the silicon source includes silica sol and/or solid silica gel; and/or, the aluminum source includes sodium metaaluminate and/or aluminum sulfate; and/or, the templating agent includes six A mixture of methyleneimine or hexamethyleneimine and cyclohexylamine; and/or, the alkali source includes sodium hydroxide and/or potassium hydroxide; and/or, the quaternary ammonium salt includes tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide At least one of ammonium, tetramethylammonium chloride, tetra
  • the process of preparing the crystallized gel includes: dissolving the alkali source and the aluminum source in water, stirring for 0-3 hours, adding a template agent to it, continuing to stir for 0-24 hours, and then adding A silicon source is added therein, and the stirring is continued for 0-3 hours to obtain the crystallized gel.
  • the primary roasting process includes: roasting the product at 350°C-400°C for 3h-7h in an inert atmosphere, and then roasting the product at 500°C-600°C for 3h- 7h.
  • the ammonium exchange is carried out by using an ammonium salt solution, the ammonium salt includes ammonium nitrate, and the temperature of the ammonium exchange is 70°C-90°C.
  • the temperature of the secondary calcination is 500°C-600°C, and the time of the secondary calcination is 2h-6h.
  • the molar ratio of silicon to aluminum is (19 ⁇ 75):1.
  • the solid acid catalyst is prepared according to a process comprising the following steps: mixing the low-layered molecular sieve with MWW topology and a binder, adding inorganic acid and water to it, and performing sequentially After molding and drying, it is calcined at 500°C to 600°C for 4h to 8h to prepare the solid acid catalyst.
  • the mass percentage of the low laminated molecular sieve with MWW topology is 10%-95%, and the balance is binder.
  • the binder includes at least one of alumina, pseudoboehmite, boehmite, and aluminum hydroxide.
  • the long-chain olefins include linear olefins with 6-22 carbons.
  • the molar ratio of the benzene to the long-chain olefin is (5-50):1.
  • the conditions of the alkylation reaction are as follows: the temperature is 100°C-200°C, the pressure is 1MPa-7MPa, and the mass space velocity of the mixture of benzene and the long-chain olefin is 0.5h -1 ⁇ 12h -1 .
  • a low-layered molecular sieve with a specific structure and a MWW topology is used as a solid acid catalyst, which can efficiently catalyze the alkylation of benzene and long-chain olefins, improve the conversion rate of long-chain olefins, and increase the 2 -
  • the selectivity of alkylbenzene and 3-alkylbenzene, and the catalyst has a long one-way life. Studies have shown that the one-way life of the catalyst can reach more than 220h, or even more than 500h, and the conversion rate of long-chain olefins is as high as 99%.
  • 2-Alkylbenzene The selectivity reaches over 42%, and the selectivity between 2-alkylbenzene and 3-alkylbenzene reaches over 63%.
  • the catalyst used in the present invention is simple in composition, does not need to introduce elements such as halogen, fluorine, and boron, has low cost, and also has the advantages of mild alkylation reaction conditions and high efficiency, which is beneficial to industrial application.
  • Fig. 1 is the x-ray diffraction (XRD) spectrogram (abscissa is 2 ⁇ angle, and ordinate is peak intensity (Intensity)) of the H-type molecular sieve that embodiment 1 makes;
  • Fig. 2 is the scanning electron microscope (SEM) picture of the H type molecular sieve that embodiment 1 makes;
  • Fig. 3 is the XRD spectrogram of the H type molecular sieve that embodiment 2 makes;
  • Fig. 4 is the SEM figure of the H type molecular sieve that embodiment 2 makes;
  • Fig. 5 is the XRD spectrogram of the H type beta zeolite molecular sieve used in comparative example 1;
  • Fig. 6 is the SEM figure of the H type beta zeolite molecular sieve used in comparative example 1;
  • Fig. 7 is the XRD spectrogram of the H type MWW structure zeolite molecular sieve used in comparative example 2;
  • Fig. 8 is the SEM picture of the H-type MWW structure zeolite molecular sieve used in comparative example 2;
  • FIG. 9 is an SEM image of the H-type molecular sieve prepared in Comparative Example 3.
  • the preparation method of alkylbenzene comprises: carrying out the alkylation reaction of benzene and olefin raw material under the action of solid acid catalyst to obtain alkylbenzene; wherein, the olefin raw material includes long-chain olefin with carbon number not less than 6 , the solid acid catalyst contains a binder and a low-layered molecular sieve with a MWW topology.
  • the axial direction of the crystal band axis of the low-layered molecular sieve with a MWW topology is the c-axis direction, and the low-layered molecular sieve with a MWW topology is along the
  • the thickness in the c-axis direction is 1.5nm-25nm, and the maximum length of the low stack molecular sieve with MWW topological structure on a plane perpendicular to the c-axis direction is 200nm-3000nm.
  • the thickness of the low laminated molecular sieve with MWW topology along the c-axis direction and its maximum length (or size) on a plane perpendicular to the c-axis direction can be specifically measured by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the a-axis, b-axis, and c-axis are perpendicular to each other to form a spatial rectangular coordinate system.
  • the axial direction of the crystal zone axis of the low-layer molecular sieve is the c-axis direction, and it is in the c-axis direction (that is, the axial direction of its crystal zone axis) ) with a thickness of 1.5nm to 25nm, such as 1.5nm, 3nm, 5nm, 10nm, 15nm, 20nm, 25nm or any two of them, the plane where the a-axis and the b-axis are common is perpendicular to the c-axis
  • the plane of the direction, the size i.e.
  • the maximum length) of the low stacked molecular sieve on this plane is 200nm ⁇ 3000nm, such as 200nm, 500nm, 800nm, 1000nm, 1200nm, 1500nm, 1800nm, 2000nm, 2200nm, 2500nm, 2800nm, 3000nm or where The range of any combination of the two.
  • a molecular sieve with a MWW topological structure with a suitable structure and composition can be prepared, and compounded with a binder to form a solid acid catalyst, which can efficiently catalyze the alkylation of benzene and long-chain olefins reaction, improve the conversion rate of long-chain olefins and the selectivity of target products such as 2-alkylbenzene and 3-alkylbenzene, and the solid acid catalyst also has the advantages of long single-pass life.
  • the low laminated molecular sieve with MWW topological structure prepared by the process has a special lamella molecular sieve morphology, and the semi-supercage structure distributed on its surface has a good diffusion effect on macromolecules such as long-chain olefins, and can increase the solid mass per unit mass.
  • the degree of exposure of the active catalytic sites (acid sites) in the acid catalyst which can make the solid acid catalyst have longer single-pass life and excellent catalytic activity, and achieve efficient alkylation of benzene and long-chain olefins; in addition , the above process does not need to introduce elements such as halogen (such as fluorine) to modify the molecular sieve, and also has the advantages of simple catalyst composition, simple preparation process, low cost, good stability, and excellent regeneration performance, which is beneficial to industrial implementation.
  • halogen such as fluorine
  • the source of silicon is calculated as SiO2
  • the source of aluminum is calculated as Al203
  • the source of alkalinity is calculated as metal oxide
  • the molar ratio of silicon source to aluminum source is (22.5 ⁇ 97.5):1, such as 22.5:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50 :1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 97.5:1 or any two of them
  • the molar ratio of template agent to silicon source is (0.08 ⁇ 0.45):1, such as 0.08:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4: 1.
  • the molar ratio of alkali source to silicon source is (0.03 ⁇ 0.20):1, such as 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.12 : 1, 0.15: 1, 0.18: 1, 0.2: 1 or any two of them
  • the molar ratio of water to silicon source is (10-60): 1, such as 10: 1, 20: 1, 30 :1, 40:1, 50:1, 60:1, or any two of them.
  • the silicon source is counted as SiO 2
  • the quaternary ammonium salt is counted as quaternary ammonium cation (NR + )
  • the silicon agent is counted as SiO 2
  • the molar ratio of quaternary ammonium salt to silicon source is (0.1-1.0):1 , such as 0.1:1, 0.3:1, 0.5:1, 0.7:1, 1:1 or any two of them
  • the molar ratio of silicon agent to silicon source is (0.05 ⁇ 2.5):1, such as 0.05 :1, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, 0.22:1, 0.25:1 or any two of them.
  • the aluminum source used may include sodium metaaluminate and/or aluminum sulfate, specifically sodium metaaluminate, or aluminum sulfate, or a mixture of sodium metaaluminate and aluminum sulfate.
  • the alkali source used may specifically include inorganic bases, especially soluble inorganic bases, such as alkali metal hydroxides.
  • the source of alkalinity includes sodium hydroxide and/or potassium hydroxide.
  • the template used may specifically include an organic template, such as an organic amine template, especially hexamethyleneimine.
  • an organic amine template especially hexamethyleneimine.
  • the above template includes hexamethyleneimine Or a mixture of hexamethyleneimine and cyclohexylamine.
  • the silicon source used may specifically include an inorganic silicon source, which is beneficial to further cost savings compared to the use of an organic silicon source.
  • the use of an inorganic silicon source through the above molecular sieve preparation process can further improve the solid acidity.
  • the aforementioned silicon source includes silica sol and/or solid silica gel.
  • the quaternary ammonium salt may include tetraalkylammonium hydroxide and/or tetraalkylammonium halide, and tetraalkylammonium halide includes tetraalkylammonium bromide and/or tetraalkylammonium chloride, wherein the alkyl It can be C1-C4 alkyl, such as methyl, ethyl, propyl, butyl, etc.
  • the above-mentioned quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, Propyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride At least one of ammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride.
  • the silicon agent used may include organic silicon and/or inorganic silicon.
  • Organic silicon includes, for example, tetraethyl orthosilicate
  • inorganic silicon includes, for example, silica sol.
  • the aforementioned silicon agent includes silica sol and/or tetraethyl orthosilicate.
  • the process of preparing the crystallized gel includes: dissolving the alkali source and the aluminum source in water, and then stirring for 0-3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h or any of them Any combination of the two, then add template agent to it, and continue to stir for 0 ⁇ 24h, such as 0.5h, 1h, 3h, 5h, 7h, 10h, 12h, 15h, 18h, 20h or any combination of the two , and then add a silicon source therein, and continue to stir for 0-3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h or any combination thereof, to obtain a crystallized gel.
  • T1 is 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C °C or the range of any combination thereof
  • the primary crystallization time is 12h, 15h, 18h, 20h, 22h, 25h, 28h, 30h, 33h, 36h or the range of any combination thereof
  • T 3 is the range of 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C or any two of them
  • the secondary crystallization time t is 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h or any two of them.
  • the secondary crystallization product (crystallization mother liquor) that obtains is down to room temperature, after adding quaternary ammonium salt and silicon agent wherein, transfer to closed stirrer and carry out closed stirring (or crystallization After the mother liquor is transferred to a closed mixer, quaternary ammonium salt and silicon agent are added thereto, and then closed and stirred).
  • the closed stirring temperature is 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or any combination thereof
  • the closed stirring time is 3h, 5h , 10h, 15h, 20h, 25h, 30h, 33h, 36h or any two of them.
  • the obtained product is sequentially washed with water and filtered, and then the obtained solid product is sequentially dried, primary roasted, ammonium exchange, and secondary roasted, wherein the drying temperature can be 100 °C to 150°C, for example, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or any combination thereof, and the drying time may be 3h to 5h.
  • the process of one roasting includes: roasting the product (that is, the dried product obtained after the above-mentioned drying) at 350° C. to 400° C. under an inert atmosphere ( It is recorded as low-temperature roasting) for 3h to 7h, and then roasted at 500°C to 600°C in an oxygen-containing gas atmosphere (referred to as high-temperature roasting) for 3h-7h, wherein the inert atmosphere includes nitrogen, oxygen-containing gas includes oxygen, and low-temperature roasting
  • the temperature is, for example, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C or any combination thereof
  • the low-temperature calcination time is, for example, 3h, 4h, 5h, 6h, 7h or any of them.
  • the range of the composition of the two, the high-temperature calcination temperature is, for example, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C or any two of them
  • the range of composition, the time of high-temperature calcination is 3h, 4h, 5h, 6h, 7h or any two of them.
  • the product after one calcination is generally a sodium-type molecular sieve with MWW topology, which can be converted into an H-type molecular sieve after ammonium exchange and other treatments.
  • ammonium salt solution can be used to carry out ammonium exchange, that is, the product after the above-mentioned high-temperature roasting is placed in ammonium salt solution for ammonium exchange, and after ammonium exchange, the ammonium exchange product is subjected to secondary roasting to obtain H-type molecular sieve (That is, the above-mentioned low laminated molecular sieve with MWW topology); wherein, the ammonium salt may include ammonium nitrate, the ammonium salt solution may be an aqueous solution of ammonium salt, and the ammonium exchange temperature may be 70°C to 90°C, for example, 70°C, 75°C °C, 80 °C, 85 °C, 90 °C or any combination thereof, the ammonium exchange time
  • the temperature of secondary baking can be 500°C to 600°C, such as 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600° C. or the range of any combination thereof
  • the time for the second calcination may be 2h to 6h, such as 2h, 3h, 4h, 5h, 6h or the range of any combination thereof.
  • the water used may specifically be deionized water, but is not limited thereto.
  • the solid acid catalyst can be prepared according to a process including the following steps: mixing a low-layered molecular sieve with a MWW topology and a binder, adding inorganic acid and water to it, followed by molding, drying and calcining , to obtain a solid acid catalyst; wherein, the inorganic acid may include nitric acid, the molding may specifically be extrusion molding, and the drying may specifically be drying in the shade at 20° C. to 30° C.
  • the roasting temperature may be 500 °C ⁇ 600°C, such as 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C or any combination thereof, calcined
  • the time may range from 4h to 8h, such as 4h, 5h, 6h, 7h, 8h or any combination thereof.
  • the silicon-aluminum molar ratio is (19-75):1, that is, the chemical composition of the low-layer molecular sieve
  • the silicon-aluminum ratio of the prepared low laminated molecular sieve can be regulated according to the amount of raw materials such as the above-mentioned silicon source and aluminum source.
  • the performance of the solid acid catalyst can be further optimized, and the alkylation efficiency of benzene and long-chain olefins can be improved.
  • the mass percentage of the low laminated molecular sieve with MWW topology is 10% to 95%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or any two of them, and the balance is binder.
  • the content of the low-layer molecular sieve is higher than that of the binder, and more preferably the content of the low-layer molecular sieve is 85% to 95%.
  • the binder used may include an inorganic oxide binder, for example, at least one of alumina, pseudoboehmite, boehmite, and aluminum hydroxide.
  • the long-chain olefins may specifically include linear olefins with a carbon number of not less than 6, and generally preferably include linear olefins with a carbon number of 6 to 22.
  • the carbon number of the olefin molecules contained in the long-chain olefins is, for example, 6. . at least one of olefins whose numbers are 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, preferably, the above long chain
  • the olefins include linear olefins with 8-18 carbons.
  • the molar ratio of benzene to long-chain olefins can be (5-50):1, such as 5:1, 10:1, 15:1, 20:1, 25:1 , 30:1, 35:1, 40:1, 45:1, 50:1 or any two of them.
  • the alkylation reaction is specifically carried out in a reactor, which includes, for example, a fixed-bed reactor, but is not limited thereto.
  • the conditions of the alkylation reaction can be: the temperature is 100°C to 200°C, such as 100°C, 120°C, 140°C, 160°C, 180°C, 200°C or any combination thereof, and the pressure is 1MPa to 7MPa , such as 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa or any combination thereof, the mass space velocity of the mixture of benzene and long-chain olefins is 0.5h -1 ⁇ 12h -1 , for example 0.5h - 1 , 1h -1 , 2h -1 , 3h -1 , 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h -1 , 9h -1 , 10h -1 , 11h -1 , 12h -1 or
  • the mixture of benzene and long-chain olefins can be passed into the reactor.
  • benzene and long-chain olefins contact with the solid acid catalyst, and an alkylation reaction occurs under the catalysis of the solid acid catalyst to produce Alkylbenzenes are obtained.
  • the alkylbenzenes may specifically include linear alkylbenzenes. Among them, 2-alkylbenzenes and 3-alkylbenzenes have the advantages of good solubility, easy biodegradation, and environmental friendliness, and are important chemical products.
  • the obtained alkylbenzenes generally include 2-alkylbenzenes and 3-alkylbenzenes, and can increase the yield of target products such as 2-alkylbenzenes and 3-alkylbenzenes.
  • silicon source silica sol (wherein SiO 2 mass content is 40%), solid silica gel (wherein SiO 2 mass content is 97%);
  • Templating agent hexamethyleneimine (purity 98%), cyclohexylamine (purity 99%);
  • Aluminum source sodium metaaluminate (the mass content of Al2O3 is 41% ) , aluminum sulfate (the mass content of Al2O3 is 15%);
  • Alkali source sodium hydroxide (purity 99%), potassium hydroxide (purity 99%);
  • HPLC high performance liquid chromatography
  • the conversion rate of long-chain olefins (m 0 -m 1 )/m 0
  • m 0 is the total number of moles of long-chain olefin raw materials
  • m 1 is the remaining long-chain olefins in the system after the alkylation reaction number of moles.
  • the crystallized gel was crystallized (i.e. primary crystallization) at 160°C for 36h, and then cooled to 154°C to continue crystallization (i.e. secondary crystallization) for 24h; after the crystallization was completed, the obtained crystallization mother liquor was lowered to room temperature, Under the condition of continuous stirring, 2750g tetrapropylammonium hydroxide solution (mass concentration is 25%) and 1230g tetraethyl orthosilicate were slowly added thereinto, closed and stirred under 80 °C of water baths for 18h, then the product obtained was dissolved in 80 °C deionized water, filtered, dried at 120 °C for 4 h, then calcined at 375 °C for 5 h in a nitrogen atmosphere, and then calcined at 540 °C for 5 h in an oxygen atmosphere to obtain a low stacked sodium type with MWW topology Molecular sieve products;
  • the H-type molecular sieve is a low-layered molecular sieve with a MWW topology, and its thickness along the c-axis direction is 5nm-10nm. The maximum length on the plane in the c-axis direction is 500nm-2000nm.
  • the conversion rate of 1-dodecene is 99.65%
  • the selectivity of 2-alkylbenzene is 46.5%
  • the selectivity of 2-alkylbenzene+3-alkylbenzene is 67.3%.
  • the crystallized gel was crystallized at 158° C. for 26 hours, then cooled to 148° C. to continue crystallization for 20 hours; after the crystallization was completed, the obtained crystallized mother liquor was cooled to room temperature, and 725 g tetrahydrogel was slowly added to it under continuous stirring.
  • Propyl ammonium bromide solid and 973g tetraethyl orthosilicate were sealed and stirred in a water bath at 80°C for 10h, then the obtained product was washed with deionized water at 80°C, filtered, dried at 120°C for 4h, and then Calcined at 375°C for 5h in the atmosphere, and then calcined at 540°C for 5h in the oxygen atmosphere to obtain a low stacked sodium molecular sieve product with MWW topology;
  • the XRD spectrum of the H-type molecular sieve is shown in Figure 3, and the SEM image is shown in Figure 4. It is a low-layered molecular sieve with a MWW topology, and its thickness along the c-axis direction is 15nm-20nm. The maximum length on the plane of the direction is 500nm-2000nm.
  • the conversion rate of 1-octadecene is 99.35%
  • the selectivity of 2-alkylbenzene is 50.2%
  • the selectivity of 2-alkylbenzene+3-alkylbenzene is 73.6%.
  • the XRD spectrum of the commercially available H-type zeolite beta molecular sieve is shown in Figure 5, and the SEM picture is shown in Figure 6;
  • Example 1 Comparative Example 1 that the solid acid catalyst B1 prepared in Example 1 has better catalytic activity, especially the one-pass life of which is significantly higher than that of the catalyst D1 in Comparative Example 1.
  • the XRD spectrum of the commercially available H-type MWW structure zeolite molecular sieve is shown in Figure 7, and the SEM figure is shown in Figure 8, and its thickness along the c-axis direction is more than 30nm;
  • Example 1 the solid acid catalyst B1 prepared in Example 1 has better catalytic activity, especially its single-pass life is significantly higher than that of the catalyst D2 of Comparative Example 2, that is, the conventional MWW structure molecular sieve There is still the problem of rapid deactivation of the catalyst, but the low stacked molecular sieve with MWW structure prepared by the specific preparation process in Example 1 can effectively solve this problem.
  • the crystallized gel was crystallized at 155°C for 72 hours; after the crystallization was completed, the obtained crystallized product was cooled to room temperature, then washed and dried in sequence, and then baked at 540°C for 5 hours in an oxygen atmosphere to remove the template agent. Then place it in 1mol/L ammonium nitrate solution, exchange ammonium at 80°C for 2h, then roast the obtained ammonium exchanged product at 550°C for 4h to obtain H-type molecular sieve, which was found to be MCM-22 molecular sieve, which The SEM image is shown in Figure 9, and its thickness along the c-axis direction is more than 30nm;
  • Example 1 Compared with Example 1, no quaternary ammonium salt and silicon agent were added in this comparative example 3, and the molecular sieve synthesized was MCM-22 molecular sieve, and the thickness of the molecular sieve along the c-axis direction was more than 30nm.
  • the catalyst D3 formed by compounding the binder catalyzed the alkylation reaction of benzene and 1-dodecene the catalyst deactivated after 150 hours of reaction, and the single-pass life was much shorter than that of the solid acid catalyst B1 in Example 1.

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Abstract

La présente invention concerne un procédé de préparation d'alkylbenzène, comprenant : la mise en œuvre d'une réaction d'alkylation sur du benzène et une matière première oléfinique sous l'action d'un catalyseur acide solide pour obtenir un alkylbenzène. La matière première oléfinique comprend une oléfine à longue chaîne qui a un nombre d'atomes de carbone supérieur à 6. Le catalyseur acide solide comprend un liant et un tamis moléculaire à faible empilement qui a une structure topologique MWW, la direction axiale de l'axe de zone cristalline du tamis moléculaire à faible empilement qui a la structure topologique MWW étant une direction sur l'axe c, l'épaisseur du tamis moléculaire à faible empilement qui a la structure topologique MWW dans la direction de l'axe c étant de 1,5 à 25 nm, et la longueur maximale du tamis moléculaire à faible empilement qui a la structure topologique MWW sur un plan perpendiculaire à la direction de l'axe c étant de 200 à 3000 nm. La présente invention a les avantages d'un catalyseur ayant une longue durée de vie à passage unique, des matières premières ayant un taux de conversion élevé, du 2-alkylbenzène et du 3-alkylbenzène ayant une sélectivité élevée, ainsi que des faibles coûts et similaires, et est bénéfique pour une utilisation sur le plan industriel.
PCT/CN2022/136459 2021-12-28 2022-12-05 Procédé de préparation d'alkylbenzène WO2023124789A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110118521A1 (en) * 2008-07-22 2011-05-19 Duncan Carolyn B Preparation Of Molecular Sieve Catalysts And Their Use In The Production Of Alkylaromatic Hydrocarbons
CN111763130A (zh) * 2020-06-22 2020-10-13 南京克米斯璀新能源科技有限公司 一种用于生产长链烷基苯的方法
CN113620766A (zh) * 2020-05-07 2021-11-09 中国石油天然气股份有限公司 一种高选择性线性烷基苯的生产方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110118521A1 (en) * 2008-07-22 2011-05-19 Duncan Carolyn B Preparation Of Molecular Sieve Catalysts And Their Use In The Production Of Alkylaromatic Hydrocarbons
CN113620766A (zh) * 2020-05-07 2021-11-09 中国石油天然气股份有限公司 一种高选择性线性烷基苯的生产方法
CN111763130A (zh) * 2020-06-22 2020-10-13 南京克米斯璀新能源科技有限公司 一种用于生产长链烷基苯的方法

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