WO2023124789A1 - Method for preparing alkylbenzene - Google Patents

Method for preparing alkylbenzene Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
alkylbenzene
molecular sieve
low
source
silicon
Prior art date
Application number
PCT/CN2022/136459
Other languages
French (fr)
Chinese (zh)
Inventor
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
Original Assignee
中国石油天然气股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国石油天然气股份有限公司 filed Critical 中国石油天然气股份有限公司
Publication of WO2023124789A1 publication Critical patent/WO2023124789A1/en

Links

Images

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention provides a method for preparing alkylbenzene, comprising: carrying out an alkylation reaction on benzene and an olefin raw material under the action of a solid acid catalyst to obtain alkylbenzene. The olefin raw material comprises a long-chain olefin which has a carbon number of no less than 6. The solid acid catalyst comprises a binder and a low-stack molecular sieve which has an MWW topological structure, wherein the axial direction of the crystal zone axis of the low-stack molecular sieve which has the MWW topological structure is a c-axis direction, the thickness of the low-stack molecular sieve which has the MWW topological structure in the c-axis direction is 1.5-25 nm, and the maximum length of the low-stack molecular sieve which has the MWW topological structure on a plane perpendicular to the c-axis direction is 200-3000 nm. The present invention has advantages such as a catalyst having a long single-pass service life, raw materials having a high conversion rate, 2-alkylbenzene and 3-alkylbenzene having high selectivity, as well as low costs and the like, and is beneficial to industrial application.

Description

烷基苯制备方法Alkylbenzene preparation method 技术领域technical field
本发明涉及一种烷基苯制备方法，属于烷基苯生产领域。The invention relates to a method for preparing alkylbenzene, which belongs to the field of alkylbenzene production.
背景技术Background technique
烷基化是石油化工中十分重要的一类反应，常用的催化剂可分为L酸催化剂及B酸催化剂，L酸催化剂以无水AlCl 3为主要代表，具有价格低廉、催化活性较好、技术成熟等优势，但是在生产过程中伴随着大量含铝废液的产生，且副反应过多，目前该催化剂已基本被市场淘汰，B酸催化剂以HF、H 2SO 4和H 3PO 4为代表，目前，线性烷基苯(LAB)工业生产主要采用HF催化剂，具有催化活性高、技术成熟等特点，然而，由于HF酸的强腐蚀性，对设备要求非常高，特别是HF酸接触部位均采用价格昂贵的蒙乃尔合金材质，建设投资费用及维护费用巨大，另外，生产过程中也会伴随排放各类废物，环保成本高昂。 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 . Mature and other advantages, but in the production process accompanied by a large amount of aluminum-containing waste liquid, and too many side reactions, the catalyst has been basically eliminated by the market, 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. However, due to the strong corrosiveness of HF acid, the requirements for equipment are very high, especially for the parts where HF acid contacts All of them are made of expensive Monel alloy, and the construction investment and maintenance costs are huge. In addition, various wastes will be discharged during the production process, and the environmental protection cost is high.
20世纪80年代，UOP开发了Detal固体酸烷基化技术，以固体酸催化剂代替了传统的HF催化剂，从根本上解决了HF催化剂所带来的设备腐蚀和环境污染等问题，对设备材质要求的降低也使得投资费用降低，另外，2-烷基苯等目标产物的选择性也相对于HF催化工艺在一定程度上有了提升。鉴于固体酸催化烷基化工艺的上述优点，其逐渐成为催化合成烷基苯的研究热点，例如，韩明汉等(Applied Catalysis A,General.2003,99-107.)开发了以β分子筛为主要活性组分的催化剂，可以催化合成2-烷基苯等烷基苯产物，然而该催化剂的单程寿命少于20h；专利文献CN101058523A公开了一种直链烷基苯的制备方法，以2～20个碳原子的直链烯烃与苯为原料，采用固体酸催化剂，在290～450℃、5～15MPa的超临界条件下进行烷基化反应，制得直链烷基苯，所用固体酸催化剂为下列之一或对下列之一负载改性得到的复合型固体酸催化剂：SBA-15型分子筛、HY型分子筛、USY型分子筛、Hβ型分子筛、H-Moderite型分子筛、HZSM-20型分子筛，该制备过程存在反应条件苛刻、能耗高、对设备要求高、成本高等缺陷； 专利文献CN103079698A公开了一种控制线性烷基苯的2-苯基异构体含量的方法和方法中使用的催化剂，该方法包括：使基本线性烯烃与芳基化合物在烷基化反应条件下在催化剂的存在下反应，线性烯烃包含具有8-28个碳原子的分子，催化剂包含选组含稀土元素八面沸石及其混合物的第一催化剂组分沸石和选自UZM-8、沸石MWW、沸石BEA、沸石OFF、沸石MOR、沸石LTL、沸石MTW、BPH/UZM-4及其混合物的第二催化剂组分沸石，该过程所用催化剂需引入稀土元素，催化剂组成复杂；专利文献CN108569945A公开了一种线性烷基苯的生产方法，包括使长链烯烃和苯在烷基化反应条件下与催化剂接触的步骤，催化剂以重量份计包括40～90份的有机硅沸石和10～60份的粘结剂，对该有机硅沸石的要求是：有机硅沸石包括以下摩尔关系的组成：(1/n)Al2O3：SiO2：(m/n)R，式中n＝5～250m＝0.01～50，R为烷基、烷烯基或苯基中的至少一种；所述沸石的Si 29NMR固体核磁图谱在-80～+50ppm之间至少包含有一个Si 29核磁共振谱峰；所述沸石的X-射线衍射图谱在12.4±0.2，10.5±0.3，9.3±0.3，6.8±0.2，6.1±0.2，5.5±0.2，4.4±0.2，4.0±0.2，3.5±0.l，3.4±0.1和3.3±0.1埃处有d-间距最大值，该过程采用特定结构的有机硅沸石作为催化剂活性主体，并需要引入氟元素进行氟改性以保证其稳定性等性能；专利文献CN112705252A公开了一种液相烷基化催化剂及其制备方法和应用以及苯与乙烯进行液相烷基化反应的方法，该液相烷基化催化剂包括具有MWW拓扑结构的分子筛和粘结剂，其中，以液相烷基化催化剂的总重量计，具有MWW拓扑结构的分子筛的含量为50～90重量％，粘结剂的含量为10～50重量％，液相烷基化催化剂的外表面积孔体积为0.45～0.65cm 3/g，此外，在具有MWW拓扑结构的分子筛的制备过程中需引入硼源，其实际是一种含硼MWW分子筛与粘结剂复合形成的液相烷基化催化剂，用于苯与短链烯烃(乙烯)的烷基化反应。 In the 1980s, UOP developed the Detal solid acid alkylation technology, which replaced the traditional HF catalyst with solid acid catalyst, which fundamentally solved the problems of equipment corrosion and environmental pollution caused by HF catalyst. The reduction of the cost of investment also reduces the investment cost. In addition, the selectivity of target products such as 2-alkylbenzene has also been improved to a certain extent compared with the HF catalytic process. In view of the above-mentioned advantages of the solid acid-catalyzed alkylation process, it has gradually become a research hotspot in the catalytic synthesis of alkylbenzenes. For example, Han Minghan et al. (Applied Catalysis A, General. 2003, 99-107.) 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, Hβ molecular sieve, H-Moderite molecular sieve, HZSM-20 molecular sieve, the preparation 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 binding agent. The requirements for the organosilicon zeolite are: organosilicon zeolite includes the composition of the following molar relationship: (1/n) Al2O3: SiO2: ( m/n) R, where n=5～250m=0.01～50, R is at least one of alkyl, alkenyl or phenyl; the Si 29 NMR solid nuclear magnetic spectrum of the zeolite is between -80～+ Contain at least one Si 29 NMR spectrum peak between 50ppm; The X-ray diffraction pattern of described zeolite is at 12.4±0.2, 10.5±0.3, 9.3±0.3, 6.8±0.2, 6.1±0.2, 5.5±0.2, 4.4± There are d-spacing maxima at 0.2, 4.0±0.2, 3.5±0.l, 3.4±0.1 and 3.3±0.1 Angstroms. This process uses organosilicon zeolite with a specific structure as the catalyst active host, and needs to introduce fluorine element for fluorine modification. To ensure its stability and other properties; patent document CN112705252A discloses a liquid-phase alkylation catalyst and its preparation method and application, and a method for liquid-phase alkylation reaction of benzene and ethylene. 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. In addition, 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).
虽然已有采用固体酸催化合成烷基苯的报道，但烷基苯的制备效率仍然有待进一步提升，尤其是采用长链烯烃为原料时，由于长链烯烃分子较大，更容易堵塞催化剂孔道，导致催化剂失活等问题，在提高催化剂单程使用寿命、原料转化率、烷基化产物中2-烷基苯和3-烷基苯的选择性、以及降低成本等方面，仍然是本领域技术人员所面临的重要课题。Although there have been reports on the synthesis of alkylbenzenes by solid acid catalysis, the production efficiency of alkylbenzenes still needs to be further improved, especially when long-chain olefins are used as raw materials. Due to the large molecules of long-chain olefins, it is easier to block the pores of the catalyst. Leading to problems such as catalyst deactivation, it is still a person skilled in the art in terms of improving the single-pass service life of the catalyst, the conversion rate of raw materials, the selectivity of 2-alkylbenzene and 3-alkylbenzene in the alkylation product, and reducing costs. important issues faced.
发明内容Contents of the invention
本发明提供一种烷基苯制备方法，具有催化剂单程寿命长、原料转化率高、2-烷基苯和3-烷基苯选择性高、以及成本低等优点，能够有效克服现有技术存在的缺陷。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.
本发明的一方面，提供一种烷基苯制备方法，包括：使苯与烯烃原料在固体酸催化剂作用下进行烷基化反应，得到烷基苯；其中，所述烯烃原料包括碳个数不少于6的长链烯烃，所述固体酸催化剂包含粘结剂和具有MWW拓扑结构的低叠层分子筛，所述具有MWW拓扑结构的低叠层分子筛的晶带轴的轴向为c轴方向，所述具有MWW拓扑结构的低叠层分子筛沿所述c轴方向的厚度为1.5nm～25nm，所述具有MWW拓扑结构的低叠层分子筛在在垂直于所述c轴方向的平面上的最大长度为200nm～3000nm。In one aspect of the present invention, there is provided 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.
根据本发明的一实施方式，所述具有MWW拓扑结构的低叠层分子筛按照包括如下步骤的过程制得：(I)将碱源、铝源、模板剂、硅源与水混合，制得晶化凝胶；(II)使所述晶化凝胶在温度为T 1的条件下进行一次晶化，得到一次晶化产物；其中，T 1为120℃～180℃，所述一次晶化的时间为12h～36h；(III)使所述一次晶化产物在温度为T 2的条件下进行二次晶化，得到二次晶化产物；其中，T 2＝T 1-T 3，0＜T 3≤50℃，所述二次晶化的时间为t，0＜t≤60h；(IV)将所述二次晶化产物降至常温，向其中加入季铵盐和硅剂，在50℃～85℃封闭搅拌3h～36h，然后将得到的产物依次进行干燥、一次焙烧、铵交换、二次焙烧，制得所述具有MWW拓扑结构的低叠层分子筛。 According to one embodiment of the present invention, the low stack molecular sieve with MWW topological structure is prepared according to a process comprising the following steps: (1) mixing an alkali source, an aluminum source, a templating agent, a silicon source and water to obtain a crystal (II) make the crystallization gel carry out primary crystallization under the condition of temperature T1 to obtain primary crystallization product; wherein, T1 is 120°C～180°C, the primary crystallization The time is 12h to 36h; (III) The secondary crystallization product is subjected to secondary crystallization at a temperature of T 2 to obtain a secondary crystallization product; wherein, T 2 =T 1 -T 3 , 0< T 3 ≤ 50°C, the time of the secondary crystallization is t, 0<t≤60h; (IV) The secondary crystallization product is lowered to normal temperature, and quaternary ammonium salt and silicon agent are added thereto, at 50 ℃ ~ 85 ℃ closed stirring for 3h ~ 36h, and then sequentially drying the obtained product, primary calcination, ammonium exchange, and secondary calcination to prepare the low stacked molecular sieve with MWW topology.
根据本发明的一实施方式，所述硅源以SiO 2计，所述铝源以Al 2O 3计，所述碱源以金属氧化物计，所述硅源与所述铝源的摩尔比为(22.5～97.5)：1，所述模板剂与所述硅源的摩尔比为(0.08～0.45)：1，所述碱源与所述硅源的摩尔比为(0.03～0.20)：1，所述水与硅源的摩尔比为(10～60)：1。 According to one embodiment of the present invention, the silicon source is counted as SiO2 , the aluminum source is counted as Al2O3 , the alkali source is counted as metal oxide, and the molar ratio of the silicon source to the aluminum source is is (22.5-97.5): 1, the molar ratio of the template agent to the silicon source is (0.08-0.45): 1, and 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.
根据本发明的一实施方式，所述硅源以SiO 2计，所述季铵盐以季铵阳离子计，所述硅剂以SiO 2计，所述季铵盐与所述硅源的摩尔比为(0.1～1.0)：1，所述硅剂与所述硅源的摩尔比为(0.05～2.5)：1。 According to one embodiment of the present invention, 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, and the molar ratio of the silicon agent to the silicon source is (0.05-2.5):1.
根据本发明的一实施方式，所述硅源包括硅溶胶和/或固体硅胶；和/或，所述铝源包括偏铝酸钠和/或硫酸铝；和/或，所述模板剂包括六亚甲基亚胺 或六亚甲基亚胺与环己胺的混合物；和/或，所述碱源包括氢氧化钠和/或氢氧化钾；和/或，所述季铵盐包括四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵中的至少一种；和/或，所述硅剂包括硅溶胶和/或正硅酸乙酯。According to an embodiment of the present invention, 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, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride; and/or, the silicon agent includes silica sol and/or normal Ethyl silicate.
根据本发明的一实施方式，制得晶化凝胶的过程包括：将碱源、铝源溶解在水中，再搅拌0～3h后，向其中加入模板剂，继续搅拌0～24h后，再向其中加入硅源，继续搅拌0～3h，制得所述晶化凝胶。According to one embodiment of the present invention, 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.
根据本发明的一实施方式，所述一次焙烧的过程包括：将产物在惰性氛围下于350℃～400℃焙烧3h～7h后，再在含氧气体氛围下于500℃～600℃焙烧3h～7h。According to one embodiment of the present invention, 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.
根据本发明的一实施方式，采用铵盐溶液进行所述铵交换，所述铵盐包括硝酸铵，所述铵交换的温度为70℃～90℃。According to an embodiment of the present invention, 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.
根据本发明的一实施方式，所述二次焙烧的温度为500℃～600℃，所述二次焙烧的时间为2h～6h。According to an embodiment of the present invention, the temperature of the secondary calcination is 500°C-600°C, and the time of the secondary calcination is 2h-6h.
根据本发明的一实施方式，所述具有MWW拓扑结构的低叠层分子筛中，以SiO 2和Al 2O 3计，硅铝摩尔比为(19～75):1。 According to an embodiment of the present invention, in the low laminated molecular sieve with MWW topological structure, based on SiO 2 and Al 2 O 3 , the molar ratio of silicon to aluminum is (19˜75):1.
根据本发明的一实施方式，所述固体酸催化剂按照包括如下步骤的过程制得：将所述具有MWW拓扑结构的低叠层分子筛与粘结剂混合，向其中加入无机酸和水，依次进行成型和干燥后，再在500℃～600℃焙烧4h～8h，制得所述固体酸催化剂。According to an embodiment of the present invention, 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.
根据本发明的一实施方式，所述固体酸催化剂中，所述具有MWW拓扑结构的低叠层分子筛的质量百分含量为10％～95％，余量为粘结剂。According to an embodiment of the present invention, in the solid acid catalyst, the mass percentage of the low laminated molecular sieve with MWW topology is 10%-95%, and the balance is binder.
根据本发明的一实施方式，所述粘结剂包括三氧化二铝、拟薄水铝石、薄水铝石、氢氧化铝中的至少一种。According to an embodiment of the present invention, the binder includes at least one of alumina, pseudoboehmite, boehmite, and aluminum hydroxide.
根据本发明的一实施方式，所述长链烯烃包括碳个数为6～22的线性烯烃。According to one embodiment of the present invention, the long-chain olefins include linear olefins with 6-22 carbons.
根据本发明的一实施方式，所述苯与所述长链烯烃的摩尔比为(5～50):1。According to one embodiment of the present invention, the molar ratio of the benzene to the long-chain olefin is (5-50):1.
根据本发明的一实施方式，所述烷基化反应的条件为：温度为100℃～200℃，压力为1MPa～7MPa，所述苯与所述长链烯烃的混合物的 质量空速为0.5h -1～12h -1。 According to one embodiment of the present invention, 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 .
本发明中，以特定结构的具有MWW拓扑结构的低叠层分子筛为固体酸催化剂，能够高效催化苯与长链烯烃的烷基化，提高长链烯烃的转化率、以及烷基化产物中2-烷基苯和3-烷基苯的选择性，同时催化剂单程寿命长，研究显示，催化剂单程寿命可达220h以上、甚至500h以上，长链烯烃转化率高达99％以上，2-烷基苯选择性达42％以上，2-烷基苯与3-烷基苯的选择性达63％以上。此外，本发明所用催化剂组成简单，无需引入卤素、氟、硼等元素，成本低，且还具有烷基化反应条件温和、效率高等优势，利于工业化应用。In the present invention, 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%. In addition, 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.
附图说明Description of drawings
图1为实施例1制得的H型分子筛的x射线衍射(XRD)谱图(横坐标为2θ角，纵坐标为峰强度(Intensity))；Fig. 1 is the x-ray diffraction (XRD) spectrogram (abscissa is 2θ angle, and ordinate is peak intensity (Intensity)) of the H-type molecular sieve that embodiment 1 makes;
图2为实施例1制得的H型分子筛的扫描电镜(SEM)图；Fig. 2 is the scanning electron microscope (SEM) picture of the H type molecular sieve that embodiment 1 makes;
图3为实施例2制得的H型分子筛的XRD谱图；Fig. 3 is the XRD spectrogram of the H type molecular sieve that embodiment 2 makes;
图4为实施例2制得的H型分子筛的SEM图；Fig. 4 is the SEM figure of the H type molecular sieve that embodiment 2 makes;
图5为对比例1所用的H型β沸石分子筛的XRD谱图；Fig. 5 is the XRD spectrogram of the H type beta zeolite molecular sieve used in comparative example 1;
图6为对比例1所用的H型β沸石分子筛的SEM图；Fig. 6 is the SEM figure of the H type beta zeolite molecular sieve used in comparative example 1;
图7为对比例2所用的H型MWW结构沸石分子筛的XRD谱图；Fig. 7 is the XRD spectrogram of the H type MWW structure zeolite molecular sieve used in comparative example 2;
图8为对比例2所用的H型MWW结构沸石分子筛的SEM图；Fig. 8 is the SEM picture of the H-type MWW structure zeolite molecular sieve used in comparative example 2;
图9为对比例3制得的H型分子筛的SEM图。FIG. 9 is an SEM image of the H-type molecular sieve prepared in Comparative Example 3.
具体实施方式Detailed ways
为使本领域技术人员更好地理解本发明的方案，下面对本发明作进一步地详细说明。以下所列举具体实施方式只是对本发明的原理和特征进行描述，所举实例仅用于解释本发明，并非限定本发明的范围。基于本发明实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本发明保护的范围。In order to enable those skilled in the art to better understand the solution of the present invention, the present invention will be further described in detail below. The specific embodiments listed below are only to describe the principles and features of the present invention, and the examples are only used to explain the present invention, not to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementations obtained by persons of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.
本发明提供的烷基苯制备方法，包括：使苯与烯烃原料在固体酸催化剂作用下进行烷基化反应，得到烷基苯；其中，烯烃原料包括碳个数不少于6 的长链烯烃，固体酸催化剂包含粘结剂和具有MWW拓扑结构的低叠层分子筛，具有MWW拓扑结构的低叠层分子筛的晶带轴的轴向为c轴方向，具有MWW拓扑结构的低叠层分子筛沿c轴方向的厚度为1.5nm～25nm，具有MWW拓扑结构的低叠层分子筛在在垂直于c轴方向的平面上的最大长度为200nm～3000nm。The preparation method of alkylbenzene provided by the present invention 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.
本发明中，具有MWW拓扑结构的低叠层分子筛沿c轴方向的厚度及其在垂直于c轴方向的平面上的最大长度(或称尺寸)具体可以通过电镜(SEM)扫描法测得。具体来说，a轴、b轴、c轴相互垂直形成空间直角坐标系，低叠层分子筛的晶带轴的轴向为c轴方向，其在c轴方向(即其晶带轴的轴向)上的厚度为1.5nm～25nm，例如1.5nm、3nm、5nm、10nm、15nm、20nm、25nm或其中的任意两者组成的范围，a轴和b轴共同所在的平面即为垂直于c轴方向的平面，低叠层分子筛在该平面上的尺寸(即最大长度)为200nm～3000nm，例如200nm、500nm、800nm、1000nm、1200nm、1500nm、1800nm、2000nm、2200nm、2500nm、2800nm、3000nm或其中的任意两者组成的范围。In the present invention, 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). Specifically, 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.
本发明中，上述具有MWW拓扑结构的低叠层分子筛按照包括如下步骤的过程制得：(I)将碱源、铝源、模板剂、硅源与水混合，制得晶化凝胶；(II)使晶化凝胶在温度为T 1的条件下进行一次晶化，得到一次晶化产物；其中，T 1为120℃～180℃，一次晶化的时间为12h～36h；(III)使一次晶化产物在温度为T 2的条件下进行二次晶化，得到二次晶化产物；其中，T 2＝T 1-T 3，0＜T 3≤50℃，二次晶化的时间为t，0＜t≤60h；(IV)将二次晶化产物降至常温，向其中加入季铵盐(或称季铵碱)和硅剂，在50℃～85℃封闭搅拌3h～36h，然后将得到的产物依次进行过滤、干燥、一次焙烧、铵交换、二次焙烧，制得具有MWW拓扑结构的低叠层分子筛。 In the present invention, the above-mentioned low laminated molecular sieve with MWW topological structure is prepared according to the process comprising the following steps: (1) mixing alkali source, aluminum source, templating agent, silicon source and water to obtain crystallized gel; ( II) Perform primary crystallization of the crystallized gel at a temperature of T1 to obtain a primary crystallization product; wherein, T1 is 120°C to 180°C, and the time for primary crystallization is 12h to 36h; (III) The secondary crystallization product is subjected to secondary crystallization at a temperature of T 2 to obtain a secondary crystallization product; wherein, T 2 =T 1 -T 3 , 0<T 3 ≤50°C, the secondary crystallization The time is t, 0<t≤60h; (IV) The secondary crystallization product is lowered to normal temperature, and a quaternary ammonium salt (or called a quaternary ammonium base) and a silicon agent are added thereto, and the mixture is closed and stirred at 50°C to 85°C for 3h to 36h, and then filter, dry, primary calcination, ammonium exchange, and secondary calcination of the obtained product in sequence to obtain a low-layered molecular sieve with a MWW topology.
一般情况下，在采用固体酸催化剂催化苯与长链烯烃烷基化时，长链烯烃、以及反应产生的长链副产物、多环芳烃副产物等大分子容易堵塞催化剂孔道，从而造成催化剂失活等现象。大孔十二元环分子筛具有较强的孔道内部扩散性能，对于缓解因孔道堵塞而造成的催化剂快速失活问题有一定的缓解作用，然而，传统的十二元环大孔分子筛(如八面沸石、beta沸石等)仍然容易被大分子堵塞晶体内部孔道从而失活，虽然现有技术中 已有采用不同种类的十二元环大孔分子筛作为主要活性组分的固体酸催化剂，但通常需要引入卤素等元素对分子筛进行改性以保证其扩散性能，存在催化剂制备成本繁琐、含有强腐蚀性的卤素、分子筛稳定性降低等问题。Generally, when solid acid catalysts are used to catalyze the alkylation of benzene and long-chain olefins, macromolecules such as long-chain olefins, long-chain by-products, and polycyclic aromatic hydrocarbon by-products are likely to block the pores of the catalyst, resulting in catalyst failure. Live etc. Large-pore twelve-membered ring molecular sieves have strong internal diffusion properties in the pores, which can alleviate the problem of rapid catalyst deactivation caused by channel blockage. However, traditional twelve-membered ring large-pore molecular sieves (such as octahedral zeolite, beta zeolite, etc.) are still easily blocked by macromolecules to deactivate the inner pores of the crystal, although there are solid acid catalysts using different types of twelve-membered ring macroporous molecular sieves as the main active components in the prior art, but usually need Introducing elements such as halogens to modify molecular sieves to ensure its diffusion performance has problems such as cumbersome preparation costs of catalysts, strong corrosive halogens, and reduced stability of molecular sieves.
而本发明中，通过上述分子筛的制备过程，可以制得适宜结构和组成的具有MWW拓扑结构的分子筛，与粘结剂复配形成固体酸催化剂，可以高效催化苯与长链烯烃的烷基化反应，提高长链烯烃转化率、以及2-烷基苯和3-烷基苯等目标产物的选择性，同时该固体酸催化剂还具有单程寿命长等优点，发明人经研究分析认为，通过上述过程制得的木有MWW拓扑结构的低叠层分子筛具有特殊的片层分子筛形貌，其表面分布的半超笼结构对长链烯烃等大分子具有良好的扩散作用，且可提高单位质量固体酸催化剂中活性催化位点(酸性位点)的暴露程度，由此可使固体酸催化剂具有更长的单程寿命和优异的催化活性等性能，实现苯与长链烯烃的高效烷基化；此外，上述过程无需引入卤素(如氟)等元素对分子筛进行改性，还具有催化剂组成简单、制备过程简单、成本低、稳定性好、再生性能优异等优点，利于工业化实施。However, in the present invention, through the preparation process of the above-mentioned molecular sieve, 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 inventor thinks through research and analysis that through the above 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.
在一些实施例中，硅源以SiO 2计，铝源以Al 2O 3计，碱源以金属氧化物计(例如，当碱源是碱金属(M)的氢氧化物(MOH)时，以M 2O计)，硅源与铝源的摩尔比为(22.5～97.5)：1，例如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或其中的任意两者组成的范围，模板剂与硅源的摩尔比为(0.08～0.45)：1，例如0.08：1、0.1：1、0.15：1、0.2：1、0.25：1、0.3：1、0.35：1、0.4：1、0.45：1或其中的任意两者组成的范围，碱源与硅源的摩尔比为(0.03～0.20)：1，例如0.03：1、0.05：1、0.08：1、0.1：1、0.12：1、0.15：1、0.18：1、0.2：1或其中的任意两者组成的范围，水与硅源的摩尔比为(10～60)：1，例如10：1、20：1、30：1、40：1、50：1、60：1或其中的任意两者组成的范围。 In some embodiments, the source of silicon is calculated as SiO2 , the source of aluminum is calculated as Al203 , and the source of alkalinity is calculated as metal oxide (for example, when the source of alkalinity is an alkali metal (M) hydroxide (MOH), Calculated as M2O ), 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 Range, 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. 0.45:1 or any two of them, 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.
在一些实施例中，硅源以SiO 2计，季铵盐以季铵阳离子(NR +)计，硅剂以SiO 2计，季铵盐与硅源的摩尔比为(0.1～1.0)：1，例如0.1：1、0.3：1、0.5：1、0.7：1、1：1或其中的任意两者组成的范围，硅剂与硅源的摩尔比为(0.05～2.5)：1，例如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或其中的任意两者组成的范围。 In some embodiments, 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 , and 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.
本发明中，所用铝源可以包括偏铝酸钠和/或硫酸铝，具体可以是偏铝酸钠、或硫酸铝、或偏铝酸钠与硫酸铝的混合物。In the present invention, 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.
本发明中，所用碱源具体可以包括无机碱，尤其可以包括可溶性无机碱，例如包括碱金属的氢氧化物。在一些具体实施例中，碱源包括碱源包括氢氧化钠和/或氢氧化钾。In the present invention, the alkali source used may specifically include inorganic bases, especially soluble inorganic bases, such as alkali metal hydroxides. In some embodiments, the source of alkalinity includes sodium hydroxide and/or potassium hydroxide.
本发明中，所用的模板剂具体可以包括有机模板剂，例如包括有机胺类模板剂，尤其可以包括六亚甲基亚胺，在一些优选实施例中，上述模板剂包括六亚甲基亚胺或六亚甲基亚胺与环己胺的混合物。In the present invention, the template used may specifically include an organic template, such as an organic amine template, especially hexamethyleneimine. In some preferred embodiments, the above template includes hexamethyleneimine Or a mixture of hexamethyleneimine and cyclohexylamine.
本发明中，所用硅源具体可以包括无机硅源，相对于采用有机硅源，利于进一步节约成本，此外，根据本发明的研究，采用无机硅源，通过上述分子筛制备过程，可进一步提高固体酸催化剂对苯和长链烯烃烷基化的催化活性以及催化剂使用寿命等性能。在一些优选实施例中，上述硅源包括硅溶胶和/或固体硅胶。In the present invention, 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. In addition, according to the research of the present invention, the use of an inorganic silicon source through the above molecular sieve preparation process can further improve the solid acidity. The catalytic activity of the catalyst for the alkylation of benzene and long-chain olefins and the service life of the catalyst. In some preferred embodiments, the aforementioned silicon source includes silica sol and/or solid silica gel.
本发明中，季铵盐可以包括四烷基氢氧化铵和/或四烷基卤化铵，四烷基卤化铵包括四烷基溴化案和/或四烷基氯化铵，其中的烷基可以是C1-C4的烷基，例如甲基、乙基、丙基、丁基等，在一些优选实施例中，上述季铵盐包括四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵中的至少一种。In the present invention, 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. In some preferred embodiments, 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.
本发明中，所用的硅剂可以包括有机硅和/或无机硅，有机硅例如包括正硅酸乙酯，无机硅例如包括硅溶胶。在一些具体实施例中，上述硅剂包括硅溶胶和/或正硅酸乙酯。In the present invention, the silicon agent used may include organic silicon and/or inorganic silicon. Organic silicon includes, for example, tetraethyl orthosilicate, and inorganic silicon includes, for example, silica sol. In some specific embodiments, the aforementioned silicon agent includes silica sol and/or tetraethyl orthosilicate.
具体地，上述制备过程中，将各原料混合后，分别在温度为T 1和T 2的条件下进行两个阶段的晶化，并控制二次晶化的温度T 2比一次晶化的问题T 1低T 3，即一次晶化结束后，在步骤(III)的一次晶化温度T 1的基准上下降T 3，使一次晶化产物再继续晶化，配合后续的加入季铵盐和硅剂后的封闭搅拌等处理，可以制得适宜结构的低叠层分子筛，根据本发明的研究，将其与粘结剂复配形成固体酸催化剂后，可高效催化苯与长链烯烃的烷基化反应。 Specifically, in the above preparation process, after mixing the raw materials, two stages of crystallization are carried out at temperatures T1 and T2 respectively, and the temperature T2 of the secondary crystallization is controlled compared to the problem of the primary crystallization T 1 is lower than T 3 , that is, after the primary crystallization is completed, T 3 is lowered on the basis of the primary crystallization temperature T 1 in step (III), so that the primary crystallization product continues to crystallize, and the subsequent addition of quaternary ammonium salt and After the silicon agent is closed and stirred, a low-layered molecular sieve with a suitable structure can be prepared. According to the research of the present invention, after it is compounded with a binder to form a solid acid catalyst, it can efficiently catalyze the alkanes of benzene and long-chain olefins. Kylation reaction.
在一些实施例中，制得晶化凝胶的过程包括：将碱源、铝源溶解在水中，再搅拌0～3h，例如0.5h、1h、1.5h、2h、2.5h、3h或其中的任意两者组成的范围，然后向其中加入模板剂，继续搅拌0～24h，例如0.5h、1h、3h、5h、7h、10h、12h、15h、18h、20h或其中的任意两者组成的范围，再向其中加入硅源，继续搅拌0～3h，例如0.5h、1h、1.5h、2h、2.5h、3h或其中的任意两者组成的范围，制得晶化凝胶。In some embodiments, 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.
可选地，步骤(II)中，T 1为120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃或其中的任意两者组成的范围，一次晶化时间为12h、15h、18h、20h、22h、25h、28h、30h、33h、36h或其中的任意两者组成的范围；步骤(III)中，T 3为5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃或其中的任意两者组成的范围，二次晶化时间t为5h、10h、15h、20h、25h、30h、35h、40h、45h、50h、55h、60h或其中的任意两者组成的范围。 Optionally, in step (II), 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; in step (III) , 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, and the secondary crystallization time t is 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h or any two of them.
上述两个阶段的晶化结束后，将得到的二次晶化产物(晶化母液)降至室温，向其中加入季铵盐和硅剂后，转移至封闭搅拌机中进行封闭搅拌(或者将晶化母液转移至封闭式搅拌机后再向其中加入季铵盐和硅剂，然后进封闭搅拌)。示例性地，封闭搅拌的温度为50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃或其中的任意两者组成的范围，封闭搅拌的时间为3h、5h、10h、15h、20h、25h、30h、33h、36h或其中的任意两者组成的范围。After the crystallization of above-mentioned two stages finishes, 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). Exemplarily, 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, and the closed stirring time is 3h, 5h , 10h, 15h, 20h, 25h, 30h, 33h, 36h or any two of them.
上述制备过程中，封闭搅拌完成后，将得到的产物依次进行水洗、过滤后，再对得到的固体产物依次进行干燥、一次焙烧、铵交换、二次焙烧等处理，其中，干燥温度可以为100℃～150℃，例如100℃、110℃、120℃、130℃、140℃、150℃或其中的任意两者组成的范围，干燥时间可以为3h～5h。In the above preparation process, after the closed stirring is completed, 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.
其中，经一次焙烧后，模板剂脱除，在一些优选实施例中，一次焙烧的过程包括：将产物(即经上述干燥后得到的干燥产物)在惰性氛围下于350℃～400℃焙烧(记为低温焙烧)3h～7h后，再在含氧气体氛围下于500℃～600℃焙烧(记为高温焙烧)3h～7h，其中，惰性氛围例如包括氮气，含氧气体包括氧气，低温焙烧的温度例如为350℃、360℃、370℃、380℃、390℃、400℃或其中的任意两者组成的范围，低温焙烧的时间例如为3h、4h、5h、6h、7h或其中的任意两者组成的范围，高温焙烧的温度例如为 500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃或其中的任意两者组成的范围，高温焙烧的时间为3h、4h、5h、6h、7h或其中的任意两者组成的范围，通过该惰性氛围低温焙烧和含氧气体高温焙烧过程，能够优化所制得的固体酸催化剂的性能，进一步提高烷基苯制备效率，Wherein, after one roasting, the template agent is removed, and in some preferred embodiments, 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, and 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. Through the process of low-temperature calcination in inert atmosphere and high-temperature calcination with oxygen-containing gas, the obtained solid acid can be optimized. Catalyst performance, further improve the production efficiency of alkylbenzene,
经一次焙烧后的产物一般是具有MWW拓扑结构的钠型分子筛，经铵交换等处理后，可以将其转化为H型分子筛。具体实施时，可以采用铵盐溶液进行铵交换，即将上述高温焙烧后的产物置于铵盐溶液中进行铵交换，经铵交换后，再将铵交换产物进行二次焙烧，得到H型分子筛(即上述具有MWW拓扑结构的低叠层分子筛)；其中，铵盐可以包括硝酸铵，铵盐溶液具体可以是铵盐的水溶液，铵交换的温度可以为70℃～90℃，例如70℃、75℃、80℃、85℃、90℃或其中的任意两者组成的范围，铵交换的时间一般可以为1h～3h。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. During specific implementation, 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 can generally be 1 h to 3 h.
在一些实施例中，二次焙烧的温度可以为500℃～600℃，例如500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃或其中的任意两者组成的范围，二次焙烧的时间可以为2h～6h，例如2h、3h、4h、5h、6h或其中的任意两者组成的范围。In some embodiments, 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.
本发明中，所用的水具体可以是去离子水，但不局限于此。In the present invention, the water used may specifically be deionized water, but is not limited thereto.
本发明中，固体酸催化剂具体可以按照包括如下步骤的过程制得：将具有MWW拓扑结构的低叠层分子筛与粘结剂混合，向其中加入无机酸和水后，依次进行成型、干燥和焙烧，制得固体酸催化剂；其中，无机酸可以包括硝酸，所述的成型具体可以是挤条成型，所述的干燥具体可以是在20℃～30℃(常温)阴干，焙烧的温度可以为500℃～600℃，例如500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃或其中的任意两者组成的范围，焙烧的时间可以为4h～8h，例如4h、5h、6h、7h、8h或其中的任意两者组成的范围。In the present invention, 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. (normal temperature), and the roasting temperature may be 500 ℃～600℃, such as 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃ or any combination thereof, calcined The time may range from 4h to 8h, such as 4h, 5h, 6h, 7h, 8h or any combination thereof.
在一些优选实施例中，上述具有MWW拓扑结构的低叠层分子筛中，以SiO 2和Al 2O 3计，硅铝摩尔比为(19～75):1，即该低叠层分子筛的化学组成中的硅、铝摩尔比满足：SiO 2:Al 2O 3＝(19～75):1，例如19:1、25:1、30:1、35:1、40:1、45:1、50:1、55:1、60:1、65:1、70:1、75:1或其中的任意两者 组成的范围。具体实施时，可以根据上述硅源、铝源等原料的用量调控所制得的低叠层分子筛的硅铝比。 In some preferred embodiments, in the above-mentioned low-layer molecular sieve with MWW topological structure, based on SiO 2 and Al 2 O 3 , the silicon-aluminum molar ratio is (19-75):1, that is, the chemical composition of the low-layer molecular sieve The molar ratio of silicon and aluminum in the composition satisfies: SiO 2 :Al 2 O 3 =(19～75):1, such as 19:1, 25:1, 30:1, 35:1, 40:1, 45:1 , 50:1, 55:1, 60:1, 65:1, 70:1, 75:1 or any two of them. During specific implementation, 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.
根据本发明的研究，通过调控固体酸中低叠层分子筛的含量，能够进一步优化固体酸催化剂的性能，提高苯与长链烯烃的烷基化效率，在一些优选实施例中，固体酸催化剂中，具有MWW拓扑结构的低叠层分子筛的质量百分含量为10％～95％，例如10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％、90％、95％或其中的任意两者组成的范围，余量为粘结剂。优选地，固体酸催化剂中，低叠层分子筛的含量高于粘结剂的含量，更优选低叠层分子筛的含量为85％～95％。According to the research of the present invention, by regulating the content of low laminated molecular sieves in the solid acid, the performance of the solid acid catalyst can be further optimized, and the alkylation efficiency of benzene and long-chain olefins can be improved. In some preferred embodiments, in the solid acid catalyst, , 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. Preferably, in the solid acid catalyst, 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%.
本发明中，所用的粘结剂可以包括无机氧化物类粘结剂，例如包括三氧化二铝、拟薄水铝石、薄水铝石、氢氧化铝中的至少一种。In the present invention, the binder used may include an inorganic oxide binder, for example, at least one of alumina, pseudoboehmite, boehmite, and aluminum hydroxide.
本发明中，长链烯烃具体可以包括碳个数不低于6的线性烯烃，一般优选包括碳个数为6～22的线性烯烃，长链烯烃所包含的烯烃分子的碳个数例如为6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22或其中的任意两者组成的范围，即长链烯烃可以包括碳个数分别为6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22的烯烃中的至少一种，优选地，上述长链烯烃包括碳个数为8～18的线性烯烃。此外，上述长链烯烃可以是末端具有双键的长链α线性烯烃，其中的C＝C双键的个数一般可以为1个，例如包括1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯中的至少一种。In the present invention, 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. In addition, the above-mentioned long-chain olefins can be long-chain alpha linear olefins with double bonds at the end, and the number of C=C double bonds in it can generally be 1, for example including 1-octene, 1-decene, 1-deca At least one of diene, 1-tetradecene, 1-hexadecene, and 1-octadecene.
一般情况下，上述烷基苯制备过程中，苯与长链烯烃的摩尔比可以为(5～50):1，例如5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1、50:1或其中的任意两者组成的范围。Generally, in the above-mentioned preparation process of alkylbenzene, 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.
本发明中，烷基化反应具体在反应器中进行，该反应器例如包括固定床反应器，但不局限于此。烷基化反应的条件可以为：温度为100℃～200℃，例如100℃、120℃、140℃、160℃、180℃、200℃或其中的任意两者组成的范围，压力为1MPa～7MPa，例如1MPa、2MPa、3MPa、4MPa、5MPa、6MPa、7MPa或其中的任意两者组成的范围，苯与长链烯烃的混合物的质量空速为0.5h -1～12h -1，例如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或其中的任意两者组成的范 围。 In the present invention, 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 A range consisting of any two of them.
具体实施时，可以向反应器中通入苯与长链烯烃的混合物，在反应器中，苯、长链烯烃与固体酸催化剂接触，在固体酸催化剂的催化作用下发生烷基化反应，制得烷基苯。该烷基苯具体可以包括线性烷基苯，其中，2-烷基苯和3-烷基苯具有溶解性好、易生物降解、环境友好等优点，是重要的化工产品，通过上述制备过程制得的烷基苯一般包括2-烷基苯和3-烷基苯，且能够提高2-烷基苯和3-烷基苯等目标产物的收率。During specific implementation, the mixture of benzene and long-chain olefins can be passed into the reactor. In 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.
为使本发明的目的、技术方案和优点更加清楚，下面将结合具体实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. Example. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
以下实施例中，所用原料规格如下：In the following examples, the raw material specifications used are as follows:
(1)硅源：硅溶胶(其中的SiO 2质量含量为40％)、固体硅胶(其中的SiO 2质量含量为97％)； (1) silicon source: silica sol (wherein SiO 2 mass content is 40%), solid silica gel (wherein SiO 2 mass content is 97%);
(2)模板剂：六亚甲基亚胺(纯度98％)、环己胺(纯度99％)；(2) Templating agent: hexamethyleneimine (purity 98%), cyclohexylamine (purity 99%);
(3)铝源：偏铝酸钠(其中的Al 2O 3质量含量为41％)、硫酸铝(其中的Al 2O 3质量含量为15％)； (3) Aluminum source: sodium metaaluminate (the mass content of Al2O3 is 41% ) , aluminum sulfate (the mass content of Al2O3 is 15%);
(4)碱源：氢氧化钠(纯度99％)、氢氧化钾(纯度99％)；(4) Alkali source: sodium hydroxide (purity 99%), potassium hydroxide (purity 99%);
(5)其他：去离子水。(5) Others: deionized water.
以下实施例中，2-烷基苯的选择性、3-烷基苯的选择性按照如下过程测定：通过高效液相色谱(HPLC)测定烷基化产物的色谱峰面积A 总(即苯被烷基化生成的所有烷基苯的峰面积之和)，确定其中的2-烷基苯的峰面积A 2和3-烷基苯的峰面积A 3，则2-烷基苯的选择性＝A 2/A 总，2-烷基苯+3烷基苯的选择性＝(A 2+A 3)/A 总。 In the following examples, the selectivity of 2-alkylbenzene and the selectivity of 3-alkylbenzene are determined according to the following process: the chromatographic peak area A of the alkylated product is measured by high performance liquid chromatography (HPLC) (that is, benzene is covered by The sum of the peak areas of all alkylbenzenes generated by alkylation), determine the peak area A 2 of 2-alkylbenzene and the peak area A 3 of 3-alkylbenzene, then the selectivity of 2-alkylbenzene =A 2 / Atotal , selectivity of 2-alkylbenzene+3-alkylbenzene=(A 2 +A 3 )/ Atotal .
以下实施例中，长链烯烃转化率＝(m 0-m 1)/m 0，m 0为长链烯烃原料的总摩尔数，m 1为经烷基化反应后体系中剩余的长链烯烃摩尔数。 In the following examples, 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, and m 1 is the remaining long-chain olefins in the system after the alkylation reaction number of moles.
实施例1Example 1
(1)具有MWW拓扑结构的低叠层分子筛的制备(1) Preparation of low stack molecular sieves with MWW topology
将36.5g氢氧化钠加入4000g去离子水中，搅拌溶解，向其中加入75g偏铝酸钠，搅拌溶解，再持续强烈搅拌1h，然后向其中缓慢加入352g六亚甲基亚胺，再持续强烈搅拌0.5h，然后再向其中缓慢加入1500g硅溶胶，再持续强烈搅拌3h，制得晶化凝胶；Add 36.5g of sodium hydroxide to 4000g of deionized water, stir to dissolve, add 75g of sodium metaaluminate to it, stir to dissolve, and continue to stir vigorously for 1h, then slowly add 352g of hexamethyleneimine to it, and continue to stir vigorously 0.5h, and then slowly add 1500g of silica sol therein, and then continue to stir vigorously for 3h to obtain a crystallized gel;
将晶化凝胶在160℃下晶化(即一次晶化)36h，然后降温至154℃继续晶化(即二次晶化)24h；晶化结束，将得到的晶化母液降至常温，在持续搅拌条件下，向其中慢速加入2750g四丙基氢氧化铵溶液(质量浓度为25％)和1230g正硅酸乙酯，在80℃水浴下封闭搅拌18h，然后将得到的产物以80℃去离子水洗涤、过滤，再在120℃下烘干4h，然后在氮气氛围下于375℃焙烧5h，再在氧气氛围下于540℃焙烧5h，得到具有MWW拓扑结构的低叠层钠型分子筛产物；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 ℃ 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;
将上述钠型分子筛产物置于1mol/L硝酸铵溶液中，于80℃下铵交换2h，然后将得到的铵交换产物在550℃焙烧4h，得到H型分子筛；Place the above-mentioned sodium-type molecular sieve product in a 1mol/L ammonium nitrate solution, exchange ammonium at 80°C for 2 hours, and then roast the obtained ammonium-exchange product at 550°C for 4 hours to obtain H-type molecular sieve;
经测试，该H型分子筛的XRD谱图见图1，SEM图见图2，该H型分子筛为具有MWW拓扑结构的低叠层分子筛，其沿c轴方向的厚度为5nm～10nm，在垂直于c轴方向的平面上的最大长度500nm-2000nm。After testing, the XRD spectrum of the H-type molecular sieve is shown in Figure 1, and the SEM image is shown in Figure 2. 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.
(2)固体酸催化剂的制备(2) Preparation of solid acid catalyst
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为
Figure PCTCN2022136459-appb-000001
的圆柱型基体，再将其截断为长度为2.5mm的圆柱形中间体；将中间体于常温阴干24h，然后在550℃下焙烧6h，得到固体酸催化剂B1。 Mix 90g of the above-mentioned H-type molecular sieve with 15g of pseudo-boehmite evenly, gradually add 55g of nitric acid solution while kneading, and extrude into
Figure PCTCN2022136459-appb-000001
The cylindrical matrix was cut into a cylindrical intermediate body with a length of 2.5mm; the intermediate body was dried in the shade at room temperature for 24 hours, and then calcined at 550°C for 6 hours to obtain solid acid catalyst B1.
(3)烷基化反应(3) Alkylation reaction
取2g上述固体酸催化剂B1，将其装入固定床反应器中，向其中通入苯与1-十二烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十二烯的摩尔比为15：1，反应温度为145℃，反应压力为4.0MPa，苯与1-十二烯的混合物的质量空速为4.0h -1； Get 2g of the above-mentioned solid acid catalyst B1, put it into a fixed-bed reactor, pass into it a mixture of benzene and 1-dodecene for alkylation reaction, and obtain alkylbenzene; wherein, benzene and 1-dodecene The molar ratio of ene is 15:1, the reaction temperature is 145°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-dodecene is 4.0h -1 ;
经测试，反应500h后，1-十二烯的转化率为99.65％，2-烷基苯选择性为46.5％，2-烷基苯+3-烷基苯的选择性为67.3％。After testing, after 500 hours of reaction, the conversion rate of 1-dodecene is 99.65%, the selectivity of 2-alkylbenzene is 46.5%, and the selectivity of 2-alkylbenzene+3-alkylbenzene is 67.3%.
实施例2Example 2
(1)具有MWW拓扑结构的低叠层分子筛的制备(1) Preparation of low stack molecular sieves with MWW topology
将43.5g氢氧化钠加入3500g去离子水中，搅拌溶解，向其中加入48.3g偏铝酸钠，搅拌溶解，再持续强烈搅拌0.5h，然后向其中缓慢加入182g六亚甲基亚胺和202g环己胺，再持续强烈搅拌1.5h，然后再向其中缓慢加入1500g硅溶胶，持续强烈搅拌5h，制得晶化凝胶；Add 43.5g of sodium hydroxide to 3500g of deionized water, stir to dissolve, add 48.3g of sodium metaaluminate to it, stir to dissolve, and continue to stir vigorously for 0.5h, then slowly add 182g of hexamethyleneimine and 202g of ring Hexylamine, continued to stir vigorously for 1.5h, then slowly added 1500g of silica sol to it, and continued to stir vigorously for 5h to obtain a crystallized gel;
将晶化凝胶在158℃下晶化26h，然后降温至148℃继续晶化20h；晶化结束，将得到的晶化母液降温至常温，在持续搅拌条件下，向其中慢速加入725g四丙基溴化铵固体和973g正硅酸乙酯，在80℃水浴下封闭搅拌10h，然后将得到的产物以80℃去离子水洗涤、过滤，再在120℃下烘干4h，然后在氮气氛围下于375℃焙烧5h，再在氧气氛围下于540℃焙烧5h，得到具有MWW拓扑结构的低叠层钠型分子筛产物；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;
将上述钠型分子筛产物置于1mol/L硝酸铵溶液中，于80℃下铵交换2h，然后将得到的铵交换产物在550℃焙烧4h，得到H型分子筛；Place the above-mentioned sodium-type molecular sieve product in a 1mol/L ammonium nitrate solution, exchange ammonium at 80°C for 2 hours, and then roast the obtained ammonium-exchange product at 550°C for 4 hours to obtain H-type molecular sieve;
经测试，该H型分子筛的XRD谱图见图3，SEM图见图4，其为具有MWW拓扑结构的低叠层分子筛，其沿c轴方向的厚度为15nm～20nm，在垂直于c轴方向的平面上的最大长度500nm-2000nm。After testing, 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.
(2)固体酸催化剂的制备(2) Preparation of solid acid catalyst
将90g上述H型分子筛与9g三氧化二铝混合均匀，边混捏边逐渐加入65g硝酸溶液，挤条成型为
Figure PCTCN2022136459-appb-000002
圆柱型基体，再将其截断为长度为2.5mm的圆柱形中间体；将中间体于常温阴干24h，然后在550℃下焙烧6h，得到固体酸催化剂B2。 Mix 90g of the above-mentioned H-type molecular sieve with 9g of aluminum oxide evenly, gradually add 65g of nitric acid solution while kneading, and extrude to form
Figure PCTCN2022136459-appb-000002
Cylindrical substrate, and then truncated into a cylindrical intermediate body with a length of 2.5 mm; the intermediate body was dried in the shade at room temperature for 24 hours, and then calcined at 550° C. for 6 hours to obtain solid acid catalyst B2.
(3)烷基化反应(3) Alkylation reaction
取2g上述固体酸催化剂B2，将其装入固定床反应器中，向其中通入苯与1-十二烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十二烯的摩尔比为20：1，反应温度140℃，反应压力3.5MPa，苯与1-十二烯的混合物的质量空速3.0h -1； Get 2g of the above-mentioned solid acid catalyst B2, put it into a fixed-bed reactor, feed a mixture of benzene and 1-dodecene into it for alkylation reaction, and obtain alkylbenzene; wherein, benzene and 1-dodecene The molar ratio of ene is 20:1, the reaction temperature is 140°C, the reaction pressure is 3.5MPa, and the mass space velocity of the mixture of benzene and 1-dodecene is 3.0h -1 ;
经测试，反应220h后，1-十二烯转化率为99.58％，2-烷基苯的选择性为43.7％，2-烷基苯+3-烷基苯的选择性为64.7％。After 220 hours of reaction, the conversion rate of 1-dodecene was 99.58%, the selectivity of 2-alkylbenzene was 43.7%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 64.7%.
实施例3Example 3
取2g实施例1中制得的固体酸催化剂B1，将其装入固定床反应器中，向其中通入苯与1-癸烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-癸烯的摩尔比为12:1，反应温度138℃，反应压力5.0MPa，苯与1-癸烯的混合物的质量空速为4.0h -1； Get 2g of the solid acid catalyst B1 prepared in Example 1, put it into a fixed-bed reactor, and feed a mixture of benzene and 1-decene into it to carry out the alkylation reaction to obtain alkylbenzene; wherein, benzene The molar ratio to 1-decene is 12:1, the reaction temperature is 138°C, the reaction pressure is 5.0MPa, and the mass space velocity of the mixture of benzene and 1-decene is 4.0h -1 ;
经测试，反应320h后，1-癸烯转化率为99.23％，2-烷基苯的选择性为48.3％，2-烷基苯+3-烷基苯的选择性为66.5％。After testing, after 320 hours of reaction, the conversion rate of 1-decene was 99.23%, the selectivity of 2-alkylbenzene was 48.3%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 66.5%.
实施例4Example 4
取2g实施例1中制得的固体酸催化剂B1，将其装入固定床反应器中，向其中通入苯与1-辛烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-辛烯的摩尔比为9：1，反应温度139℃，反应压力5.0MPa，苯与1-辛烯的混合物的质量空速为5.0h -1； Get 2g of the solid acid catalyst B1 prepared in Example 1, put it into a fixed-bed reactor, pass into it a mixture of benzene and 1-octene to carry out the alkylation reaction, and obtain alkylbenzene; wherein, benzene The molar ratio to 1-octene is 9:1, the reaction temperature is 139°C, the reaction pressure is 5.0MPa, and the mass space velocity of the mixture of benzene and 1-octene is 5.0h -1 ;
经测试，反应350h后，1-癸烯转化率为99.62％，2-烷基苯的选择性为42.2％，2-烷基苯+3-烷基苯的选择性为63.8％。After testing for 350 hours, the conversion rate of 1-decene was 99.62%, the selectivity of 2-alkylbenzene was 42.2%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 63.8%.
实施例5Example 5
取2g实施例2中制得的固体酸催化剂B2，将其装入固定床反应器中，向其中通入苯与1-十六烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十六烯的摩尔比为25:1，反应温度148℃，反应压力3.5MPa，苯与1-十六烯的混合物的质量空速为3.0h -1； Get 2g of the solid acid catalyst B2 prepared in Example 2, put it into a fixed-bed reactor, and feed a mixture of benzene and 1-hexadecene into it to carry out the alkylation reaction to obtain alkylbenzene; wherein, The molar ratio of benzene to 1-hexadecene is 25:1, the reaction temperature is 148°C, the reaction pressure is 3.5MPa, and the mass space velocity of the mixture of benzene and 1-hexadecene is 3.0h -1 ;
经测试，反应175h后，1-十六烯转化率为99.24％，2-烷基苯的选择性为48.1％，2-烷基苯+3-烷基苯的选择性为70.0％。After testing for 175 hours, the conversion rate of 1-hexadecene was 99.24%, the selectivity of 2-alkylbenzene was 48.1%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 70.0%.
实施例6Example 6
取2g实施例2中制得的固体酸催化剂B2，将其装入固定床反应器中，向其中通入苯与1-十四烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十四烯的摩尔比为25：1，反应温度144℃，反应压力4.0MPa，苯与1-十四烯的混合物的质量空速3.0h -1； Get 2g of the solid acid catalyst B2 prepared in Example 2, put it into a fixed-bed reactor, and feed a mixture of benzene and 1-tetradecene into it to carry out the alkylation reaction to obtain alkylbenzene; wherein, The molar ratio of benzene to 1-tetradecene is 25:1, the reaction temperature is 144°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-tetradecene is 3.0h -1 ;
经测试，反应220h后，1-十四烯转化率为99.05％，2-烷基苯的选择 性为47.2％，2-烷基苯+3-烷基苯的选择性为69.8％。After testing, after 220 hours of reaction, the conversion rate of 1-tetradecene was 99.05%, the selectivity of 2-alkylbenzene was 47.2%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 69.8%.
实施例7Example 7
取2g实施例2中制得的固体酸催化剂B2，将其装入固定床反应器中，向其中通入苯与1-十八烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十八烯的摩尔比为40：1，反应温度154℃，反应压力4.0MPa，苯与1-十八烯的混合物的质量空速为2.0h -1； Get 2g of the solid acid catalyst B2 prepared in Example 2, put it into a fixed-bed reactor, and feed a mixture of benzene and 1-octadecene into it to carry out the alkylation reaction to obtain alkylbenzene; wherein, The molar ratio of benzene to 1-octadecene is 40:1, the reaction temperature is 154°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-octadecene is 2.0h -1 ;
经测试，反应160h后，1-十八烯转化率为99.35％，2-烷基苯的选择性为50.2％，2-烷基苯+3-烷基苯的选择性为73.6％。After testing, after 160 hours of reaction, the conversion rate of 1-octadecene is 99.35%, the selectivity of 2-alkylbenzene is 50.2%, and the selectivity of 2-alkylbenzene+3-alkylbenzene is 73.6%.
对比例1Comparative example 1
采用市售的H型β沸石分子筛替换实施例1中制得的H型分子筛，其余条件与实施例1中的步骤(2)相同，参照实施例1中的步骤(2)制得催化剂D1；其中，该市售的H型β沸石分子筛的XRD谱图见图5，SEM图见图6；Adopt commercially available H-type beta zeolite molecular sieves to replace the H-type molecular sieves obtained in Example 1, and all the other conditions are the same as step (2) in Example 1, and catalyst D1 is obtained with reference to step (2) in Example 1; Wherein, 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;
取2g上述催化剂D1，将其装入固定床反应器中，向其中通入苯与1-十二烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十二烯的摩尔比为15：1，反应温度145℃，反应压力4.0MPa，苯与1-十二烯的混合物的质量空速为4.0；Get 2g of the above-mentioned catalyst D1, put it into a fixed-bed reactor, pass into it a mixture of benzene and 1-dodecene for alkylation reaction, and obtain alkylbenzene; wherein, the mixture of benzene and 1-dodecene The molar ratio is 15:1, the reaction temperature is 145°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-dodecene is 4.0;
经测试，反应16h后，1-十二烯转化率为97.32％，2-烷基苯的选择性为47％，2-烷基苯+3-烷基苯的选择性为63％；After testing, after 16 hours of reaction, the conversion rate of 1-dodecene was 97.32%, the selectivity of 2-alkylbenzene was 47%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 63%;
从实施例1和对比例1可以看到，实施例1制得的固体酸催化剂B1具有更好的催化活性，尤其是其单程寿命明显高于对比例1的催化剂D1。It can be seen from Example 1 and 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.
对比例2Comparative example 2
采用市售的H型MWW结构沸石分子筛替换实施例1中制得的H型分子筛，其余条件与实施例1中的步骤(2)相同，参照实施例1中的步骤(2)制得催化剂D2；其中，该市售的H型MWW结构沸石分子筛的XRD谱图见图7，SEM图见图8，其沿c轴方向的厚度为30nm以上；Adopt commercially available H-type MWW structure zeolite molecular sieve to replace the H-type molecular sieve obtained in embodiment 1, all the other conditions are the same as step (2) in embodiment 1, make catalyst D2 with reference to step (2) in embodiment 1 ; Wherein, 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;
取2g上述催化剂D2，将其装入固定床反应器中，向其中通入苯与 1-十二烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十二烯的摩尔比为15：1，反应温度145℃，反应压力4.0MPa，苯与1-十二烯的混合物的质量空速为4.0h -1； Get 2g of the above-mentioned catalyst D2, put it into a fixed-bed reactor, pass into it a mixture of benzene and 1-dodecene for alkylation reaction, and obtain alkylbenzene; wherein, the mixture of benzene and 1-dodecene The molar ratio is 15:1, the reaction temperature is 145°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-dodecene is 4.0h -1 ;
经测试，反应105h后，1-十二烯转化率为98.47％，2-烷基苯的选择性为41.9％，2-烷基苯+3-烷基苯的选择性为60.2％；After testing for 105 hours, the conversion rate of 1-dodecene was 98.47%, the selectivity of 2-alkylbenzene was 41.9%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 60.2%;
从实施例1和对比例1可以看到，实施例1制得的固体酸催化剂B1具有更好的催化活性，尤其是其单程寿命明显高于对比例2的催化剂D2，即采用常规MWW结构分子筛仍存在催化剂快速失活的问题，而通过实施例1的特定制备过程制得的具有MWW结构的低叠层分子筛能够有效解决该问题。As can be seen from Example 1 and Comparative 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.
对比例3Comparative example 3
(1)分子筛的制备(1) Preparation of molecular sieve
将36.5g氢氧化钠加入4000g去离子水中，搅拌溶解，再向其中加入75g偏铝酸钠，搅拌溶解，再持续强烈搅拌1h，然后向其中缓慢加入352g六亚甲基亚胺，持续强烈搅拌0.5h，再缓慢加入1500g硅溶胶，持续强烈搅拌3h，制得晶化凝胶；Add 36.5g of sodium hydroxide to 4000g of deionized water, stir to dissolve, then add 75g of sodium metaaluminate to it, stir to dissolve, continue to stir vigorously for 1 hour, then slowly add 352g of hexamethyleneimine to it, and continue to stir vigorously 0.5h, then slowly add 1500g of silica sol, and continue to stir vigorously for 3h to obtain a crystallized gel;
将晶化凝胶在155℃下晶化72h；晶化结束，将得到的晶化产物降温至常温，然后依次经洗涤、烘干，再在氧气氛围下于540℃焙烧5h脱除模板剂，然后置于1mol/L硝酸铵溶液中，于80℃下铵交换2h，然后将得到的铵交换产物在550℃焙烧4h，获得H型分子筛，测得该H型分子筛为MCM-22分子筛，其SEM图见图9，其沿c轴方向的厚度为30nm以上；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;
(2)固体酸催化剂的制备(2) Preparation of solid acid catalyst
将90g上述H型分子筛与15g拟薄水铝石混合均匀，边混捏边逐渐加入55g硝酸溶液，挤条成型为
Figure PCTCN2022136459-appb-000003
圆柱型基体，再将其截断为长度为2.5mm的圆柱形中间体；将中间体于常温阴干24h，然后在550℃下焙烧6h，得到催化剂D3； Mix 90g of the above-mentioned H-type molecular sieve with 15g of pseudo-boehmite evenly, gradually add 55g of nitric acid solution while kneading, and extrude into
Figure PCTCN2022136459-appb-000003
Cylindrical substrate, and then truncated into a cylindrical intermediate body with a length of 2.5 mm; the intermediate body was dried in the shade at room temperature for 24 hours, and then calcined at 550 ° C for 6 hours to obtain catalyst D3;
(3)烷基化反应(3) Alkylation reaction
取2g上述催化剂D3，将其装入固定床反应器中，向其中通入苯与 1-十二烯的混合物进行烷基化反应，得到烷基苯；其中，苯与1-十二烯的摩尔比为15：1，反应温度145℃，反应压力4.0MPa，苯与1-十二烯的混合物的质量空速为4.0h -1； Get 2g of the above-mentioned catalyst D3, put it into a fixed-bed reactor, pass into it a mixture of benzene and 1-dodecene for alkylation reaction, and obtain alkylbenzene; wherein, the mixture of benzene and 1-dodecene The molar ratio is 15:1, the reaction temperature is 145°C, the reaction pressure is 4.0MPa, and the mass space velocity of the mixture of benzene and 1-dodecene is 4.0h -1 ;
经测试，反应150h后，1-十二烯转化率为98.17％，2-烷基苯的选择性为41.2％，2-烷基苯+3-烷基苯的选择性为63.5％；After testing for 150 hours, the conversion rate of 1-dodecene was 98.17%, the selectivity of 2-alkylbenzene was 41.2%, and the selectivity of 2-alkylbenzene+3-alkylbenzene was 63.5%;
与实施例1相比，该对比例3中未加入季铵盐及硅剂，合成出的分子筛为MCM-22分子筛，该分子筛沿c轴方向的厚度为30nm以上，在采用由该分子筛与粘结剂复配形成的催化剂D3催化苯与1-十二烯的烷基化反应时，反应150h后出现催化剂失活，单程寿命远小于实施例1的固体酸催化剂B1。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. When 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.
以上对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种烷基苯制备方法，其特征在于，包括：使苯与烯烃原料在固体酸催化剂作用下进行烷基化反应，得到烷基苯；其中，所述烯烃原料包括碳个数不少于6的长链烯烃，所述固体酸催化剂包含粘结剂和具有MWW拓扑结构的低叠层分子筛，所述具有MWW拓扑结构的低叠层分子筛的晶带轴的轴向为c轴方向，所述具有MWW拓扑结构的低叠层分子筛沿所述c轴方向的厚度为1.5nm～25nm，所述具有MWW拓扑结构的低叠层分子筛在在垂直于所述c轴方向的平面上的最大长度为200nm～3000nm。A method for preparing alkylbenzene, characterized in that it comprises: 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 a carbon number not less than 6 The long-chain olefins, the solid acid catalyst comprises 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 The thickness of the low-layered molecular sieve with MWW topology along the c-axis direction is 1.5nm-25nm, and the maximum length of the low-layered molecular sieve with MWW topology on a plane perpendicular to the c-axis direction is 200nm ~ 3000nm.
  2. 根据权利要求1所述的烷基苯制备方法，其特征在于，所述具有MWW拓扑结构的低叠层分子筛按照包括如下步骤的过程制得：Alkylbenzene preparation method according to claim 1, is characterized in that, described low lamination molecular sieve with MWW topological structure is made according to the process comprising the following steps:
    (I)将碱源、铝源、模板剂、硅源与水混合，制得晶化凝胶；(1) mixing alkali source, aluminum source, templating agent, silicon source and water to obtain crystallized gel;
    (II)使所述晶化凝胶在温度为T 1的条件下进行一次晶化，得到一次晶化产物；其中，T 1为120℃～180℃，所述一次晶化的时间为12h～36h； (II) Perform primary crystallization of the crystallized gel at a temperature of T 1 to obtain a primary crystallization product; wherein, T 1 is 120° C. to 180° C., and the time for the primary crystallization is 12 hours to 1 hour 36h;
    (III)使所述一次晶化产物在温度为T 2的条件下进行二次晶化，得到二次晶化产物；其中，T 2＝T 1-T 3，0＜T 3≤50℃，所述二次晶化的时间为t，0＜t≤60h； (III) performing secondary crystallization on the primary crystallization product at a temperature of T 2 to obtain a secondary crystallization product; wherein, T 2 =T 1 -T 3 , 0<T 3 ≤50°C, The time for the secondary crystallization is t, 0<t≤60h;
    (IV)将所述二次晶化产物降至常温，向其中加入季铵盐和硅剂，在50℃～85℃封闭搅拌3h～36h，然后将得到的产物依次进行干燥、一次焙烧、铵交换、二次焙烧，制得所述具有MWW拓扑结构的低叠层分子筛。(IV) The secondary crystallization product is lowered to normal temperature, quaternary ammonium salt and silicon agent are added thereto, closed and stirred at 50°C to 85°C for 3h to 36h, and then the obtained product is sequentially dried, primary roasted, ammonium exchange and secondary calcination to prepare the low stacked molecular sieve with MWW topology.
  3. 根据权利要求2所述的烷基苯制备方法，其特征在于，Alkylbenzene preparation method according to claim 2, is characterized in that,
    所述硅源以SiO 2计，所述铝源以Al 2O 3计，所述碱源以金属氧化物计，所述硅源与所述铝源的摩尔比为(22.5～97.5)：1，所述模板剂与所述硅源的摩尔比为(0.08～0.45)：1，所述碱源与所述硅源的摩尔比为(0.03～0.20)：1，所述水与硅源的摩尔比为(10～60)：1；和/或， The silicon source is counted as SiO 2 , the aluminum source is counted as Al 2 O 3 , the alkali source is counted as metal oxide, and 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 water to the silicon source The molar ratio is (10～60):1; and/or,
    所述硅源以SiO 2计，所述季铵盐以季铵阳离子计，所述硅剂以SiO 2计，所述季铵盐与所述硅源的摩尔比为(0.1～1.0)：1，所述硅剂与所述硅源的摩尔比为(0.05～2.5)：1；和/或， The silicon source is counted as SiO2 , the quaternary ammonium salt is counted as a quaternary ammonium cation, the silicon agent is counted as SiO2 , and the molar ratio of the quaternary ammonium salt to the silicon source is (0.1-1.0):1 , the molar ratio of the silicon agent to the silicon source is (0.05-2.5): 1; and/or,
    所述硅源包括硅溶胶和/或固体硅胶；和/或，Described silicon source comprises silica sol and/or solid silica gel; And/or,
    所述铝源包括偏铝酸钠和/或硫酸铝；和/或，The aluminum source comprises sodium metaaluminate and/or aluminum sulfate; and/or,
    所述模板剂包括六亚甲基亚胺或六亚甲基亚胺与环己胺的混合物；和/或，The templating agent includes hexamethyleneimine or a mixture of hexamethyleneimine and cyclohexylamine; and/or,
    所述碱源包括氢氧化钠和/或氢氧化钾；和/或，The alkali source comprises sodium hydroxide and/or potassium hydroxide; and/or,
    所述季铵盐包括四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵中的至少一种；和/或，Described quaternary ammonium salt comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide At least one of ammonium chloride, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride; and/or,
    所述硅剂包括硅溶胶和/或正硅酸乙酯。The silicon agent includes silica sol and/or tetraethyl orthosilicate.
  4. 根据权利要求2所述的烷基苯制备方法，其特征在于，Alkylbenzene preparation method according to claim 2, is characterized in that,
    制得晶化凝胶的过程包括：将碱源、铝源溶解在水中，再搅拌0～3h后，向其中加入模板剂，继续搅拌0～24h后，再向其中加入硅源，继续搅拌0～3h，制得所述晶化凝胶；和/或，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, adding a silicon source to it, and continuing to stir for 0 ~3h, making the crystallized gel; and/or,
    所述一次焙烧的过程包括：将产物在惰性氛围下于350℃～400℃焙烧3h～7h后，再在含氧气体氛围下于500℃～600℃焙烧3h～7h；和/或，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 in an oxygen-containing gas atmosphere; and/or,
    采用铵盐溶液进行所述铵交换，所述铵盐包括硝酸铵，所述铵交换的温度为70℃～90℃；和/或，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 to 90°C; and/or,
    所述二次焙烧的温度为500℃～600℃，所述二次焙烧的时间为2h～6h。The temperature of the secondary calcination is 500°C-600°C, and the time of the secondary calcination is 2h-6h.
  5. 根据权利要求1-4任一项所述的烷基苯制备方法，其特征在于，所述具有MWW拓扑结构的低叠层分子筛中，以SiO 2和Al 2O 3计，硅铝摩尔比为(19～75):1。 According to the preparation method of alkylbenzene described in any one of claims 1-4, it is characterized in that, in the low laminated molecular sieve with MWW topological structure, in terms of SiO 2 and Al 2 O 3 , the silicon-aluminum molar ratio is (19～75):1.
  6. 根据权利要求1或2所述的烷基苯制备方法，其特征在于，所述固体酸催化剂按照包括如下步骤的过程制得：将所述具有MWW拓扑结构的低叠层分子筛与粘结剂混合，向其中加入无机酸和水，依次进行成型和干燥后，再在500℃～600℃焙烧4h～8h，制得所述固体酸催化剂。The preparation method of alkylbenzene according to claim 1 or 2, characterized in that, the solid acid catalyst is prepared according to a process comprising the following steps: mixing the low-layered molecular sieve with MWW topological structure with a binder , adding inorganic acid and water therein, followed by molding and drying, and then calcining at 500°C to 600°C for 4h to 8h to obtain the solid acid catalyst.
  7. 根据权利要求1所述的烷基苯制备方法，其特征在于，Alkylbenzene preparation method according to claim 1, is characterized in that,
    所述固体酸催化剂中，所述具有MWW拓扑结构的低叠层分子筛的质量百分含量为10％～95％，余量为粘结剂；和/或，In the solid acid catalyst, the mass percentage of the low laminated molecular sieve with MWW topology is 10% to 95%, and the balance is binder; and/or,
    所述粘结剂包括三氧化二铝、拟薄水铝石、薄水铝石、氢氧化铝中的至少一种。The binder includes at least one of alumina, pseudoboehmite, boehmite, and aluminum hydroxide.
  8. 根据权利要求1所述的烷基苯制备方法，其特征在于，所述长链烯烃包括碳个数为6～22的线性烯烃。The method for preparing alkylbenzene according to claim 1, wherein the long-chain olefins include linear olefins with 6-22 carbons.
  9. 根据权利要求1所述的烷基苯制备方法，其特征在于，所述苯与所述 长链烯烃的摩尔比为(5～50):1。Alkylbenzene preparation method according to claim 1, is characterized in that, the mol ratio of described benzene and described long-chain olefin is (5～50):1.
  10. 根据权利要求1所述的烷基苯制备方法，其特征在于，所述烷基化反应的条件为：温度为100℃～200℃，压力为1MPa～7MPa，所述苯与所述长链烯烃的混合物的质量空速为0.5h -1～12h -1。 The method for preparing alkylbenzene according to claim 1, wherein the conditions of the alkylation reaction are: the temperature is 100°C-200°C, the pressure is 1MPa-7MPa, the benzene and the long-chain olefin The mass space velocity of the mixture is 0.5h -1 ~ 12h -1 .
PCT/CN2022/136459 2021-12-28 2022-12-05 Method for preparing alkylbenzene WO2023124789A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111625579.7 2021-12-28
CN202111625579.7A CN116354782A (en) 2021-12-28 2021-12-28 Process for preparing alkylbenzene

Publications (1)

Publication Number Publication Date
WO2023124789A1 true WO2023124789A1 (en) 2023-07-06

Family

ID=86910587

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/136459 WO2023124789A1 (en) 2021-12-28 2022-12-05 Method for preparing alkylbenzene

Country Status (2)

Country Link
CN (1) CN116354782A (en)
WO (1) WO2023124789A1 (en)

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 (en) * 2020-06-22 2020-10-13 南京克米斯璀新能源科技有限公司 Method for producing long-chain alkylbenzene
CN113620766A (en) * 2020-05-07 2021-11-09 中国石油天然气股份有限公司 Production method of high-selectivity linear alkylbenzene

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 (en) * 2020-05-07 2021-11-09 中国石油天然气股份有限公司 Production method of high-selectivity linear alkylbenzene
CN111763130A (en) * 2020-06-22 2020-10-13 南京克米斯璀新能源科技有限公司 Method for producing long-chain alkylbenzene

Also Published As

Publication number Publication date
CN116354782A (en) 2023-06-30

Similar Documents

Publication Publication Date Title
JP5571950B2 (en) Molecular sieve composition (EMM-10), production method thereof, and hydrocarbon conversion method using the composition
KR101120395B1 (en) A mcm-22 family molecular sieve composition, its method of making, and use for hydrocarbon conversions
TWI380952B (en) A high throughput process for manufacturing molecular sieves
EP1756004B1 (en) High silica zeolites uzm-5hs
KR100958149B1 (en) Uzm-8 and uzm-8hs crystalline aluminosilicate zeolitic compositions and processes using the compositions
CN103071523B (en) Lanthanum-phosphorus double-heteroatom ZSM-5 molecular sieve catalyst and preparation method thereof
US8927798B2 (en) Aromatic transformation using UZM-39 aluminosilicate zeolite
JP2010515746A (en) Dual zone alkylation process for aromatic compounds
EA014135B1 (en) Catalyst and process for the preparation of alkylated aromatic hydrocarbons
JP6005878B2 (en) Aromatic transalkylation reaction using UZM-39 aluminosilicate zeolite
US8754279B1 (en) UZM-44 aluminosilicate zeolite
WO2010074889A2 (en) Uzm-26 family of crystalline aluminosilicate compositions, method of preparing the compositions and processes using the compositions
RU2617422C2 (en) High-selective process of alkylation in the presence of catalytic composition with low content of zeolite
US8609910B1 (en) Catalytic pyrolysis using UZM-39 aluminosilicate zeolite
JP2002509477A (en) Alkylation catalyst and its application
WO2023124789A1 (en) Method for preparing alkylbenzene
US8907151B2 (en) Conversion of methane to aromatic compounds using UZM-39 aluminosilicate zeolite
US6982074B2 (en) High silica zeolites: UZM-5HS
CN113620766B (en) Production method of high-selectivity linear alkylbenzene
US8889939B2 (en) Dehydrocyclodimerization using UZM-44 aluminosilicate zeolite
US20120004483A1 (en) Aromatic alkylation process using uzm-5, uzm-5p and uzm-6 zeolites
CN112387267B (en) Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier
JP5750300B2 (en) Method for synthesizing novel heterojunction porous crystal and novel heterojunction porous crystal
CN113912472A (en) Production method of linear alkylbenzene
CN118002192A (en) Solid acid alkylation catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22914044

Country of ref document: EP

Kind code of ref document: A1