CN116354360A - High-dispersity Ce-supported Beta molecular sieve and preparation method and application thereof - Google Patents
High-dispersity Ce-supported Beta molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 13
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 16
- 229940069096 dodecene Drugs 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical group CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000005804 alkylation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- -1 alkylbenzene sulfonate Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 2
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- 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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses a high-dispersity Ce-supported Beta molecular sieve and a preparation method and application thereof, and belongs to the technical field of fine chemical engineering. The high-dispersivity Ce-supported Beta molecular sieve is characterized in that the silicon-aluminum ratio of the molecular sieve is 41-45, the loading amount of Ce in the molecular sieve is 0.28-2.47 wt%, the average particle size of Ce oxide clusters is 2.37-3.00 nm, and the dispersivity index of the Ce oxide clusters is 1.059-1.071. The high-dispersity Ce-supported Beta molecular sieve provided by the invention has the high dispersibility of Ce metal elements, can effectively improve the selectivity of 2-LAB, and prolongs the service life of the catalyst.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a high-dispersity Ce-supported Beta molecular sieve and a preparation method and application thereof.
Background
Long-chain alkylbenzene is an important fine chemical raw material and intermediate, and the sulfonated product long-chain alkylbenzene sulfonic acid or long-chain alkylbenzene sulfonate plays a very important role in anionic surfactants.
Long-chain alkylbenzenes are classified into two major classes, linear alkylbenzenes and branched alkylbenzenes, according to structure. Branched alkylbenzenes are formed by condensing propylene tetramer with benzene, and the sulfonated products are difficult to degrade in the environment. Linear alkylbenzenes are produced from benzene and linear olefins by Friedel-Crafts alkylation, the sulphonated products of which are degradable in the environment. When linear long-chain olefin and benzene are subjected to alkylation reaction, the long-chain Linear Alkylbenzene (LAB) has a plurality of isomers under the influence of carbonium ion migration, wherein the long-chain alkylbenzene sulfonate produced by the 2-position linear alkylbenzene (2-LAB) has the best dissolving capacity, detergency and biodegradability. The main technology of the industrial production of long-chain linear alkylbenzene at present comprises an HF process and a Detal process, wherein the selectivity of 2-LAB prepared by the HF process is only 15-18%, and the selectivity of 2-LAB prepared by the Detal process is also only 30-35%. In addition, the catalyst of the Detal process using solid acid as the catalyst has short service life and high running cost.
The prior art discloses a solid acid catalyst for preparing linear alkylbenzene by alkylating linear olefine and benzene, and the adopted solid acid catalyst is in the common solid catalyst WO 3 /ZrO 2 On the basis of a complex trace of an alkali metal or alkaline earth metal oxide, wherein the conversion of 1-dodecene>The selectivity of 2-LAB is 44-46%. However, the selectivity of the catalyst to 2-LAB is still low. Moreover, it merely describes that the performance of the catalyst does not significantly decrease after 90 minutes of use, and the service life of the catalyst is not given.
Therefore, a new solid acid catalyst is needed to be studied, which not only can improve the selectivity of 2-LAB, but also can improve the catalytic efficiency and stability of the catalyst and prolong the service life of the catalyst in the process of preparing LAB by catalyzing alkylation of benzene and long-chain linear olefin.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of low selectivity and short service life of the catalyst of the existing solid acid catalyst for preparing linear alkylbenzene by alkylating linear olefin and benzene, and provides a high-dispersity Ce (cerium) supported Beta molecular sieve which has high dispersity of Ce metal elements, can effectively improve the selectivity of 2-LAB and prolong the service life of the catalyst.
The invention further aims at providing a preparation method of the Ce-supported Beta molecular sieve with high dispersity.
The invention further aims to provide an application of the high-dispersity Ce-supported Beta molecular sieve serving as a catalyst in preparing linear alkylbenzene by catalyzing linear long-chain olefin and benzene.
The above object of the present invention is achieved by the following technical scheme:
a high-dispersity Ce-supported Beta molecular sieve, wherein the silicon-aluminum ratio of the molecular sieve is 41-45, the loading amount of Ce in the molecular sieve is 0.28-2.47 wt%, the average particle size of Ce oxide clusters is 2.37-3.00 nm, and the dispersity index of the Ce oxide clusters is 1.059-1.071.
In the invention, the Ce loading is tested by an inductively coupled plasma emission spectrometer (ICP-OES).
In the present invention, the Ce oxide cluster dispersibility index is the degree of uniformity of dispersion of particle diameters.
The closer the Dispersibility Index (DI) is to 1, the better the dispersibility is.
In the Ce-supported Beta molecular sieve, the rare earth metal Ce adsorbs long-chain olefin through pi complexation, so that the electron cloud density of the long-chain olefin is reduced, carbon cations of the long-chain olefin are promoted to attack benzene rings with relatively large electron cloud density, alkylation reaction is carried out, thereby inhibiting the occurrence of olefin oligomerization side reaction and prolonging the service life of the catalyst. In the Ce-supported Beta molecular sieve of the present invention, the Ce oxide cluster has a Dispersibility Index (DI) of 1.059 to 1.071, which is very close to 1, indicating very high dispersibility.
The Ce-supported Beta molecular sieve has a unique three-dimensional twelve-membered ring pore channel structure, has shape selective catalytic performance on 2-LAB, and can effectively improve the selectivity of the 2-LAB.
In the present invention, the Ce loading directly affects the catalytic activity of the catalyst. In a certain range, the increase of Ce loading is beneficial to the improvement of the conversion rate of 1-dodecene.
Preferably, the loading amount of Ce in the molecular sieve is 0.933-2.47 wt%.
In the invention, the dispersity of Ce directly affects the reactivity, and the better the dispersity of Ce is under the same load, the more favorable the conversion rate of 1-dodecene is improved.
Preferably, the Ce oxide cluster has a dispersibility index of 1.059, 1.069 or 1.071.
Preferably, the average particle diameter of the Ce oxide cluster is 2.67-3.00 nm.
The average particle diameter of the Ce oxide cluster is 2.37nm, 2.67nm or 3.00nm.
The invention also provides a preparation method of the high-dispersity Ce-supported Beta molecular sieve, which comprises the following steps:
s1, mixing a Ce source, citric acid and water to obtain a solution A;
s2, sequentially adding a template agent, an aluminum source and a silicon source into the solution A obtained in the step S1, and aging to obtain gel B;
s3, crystallizing, washing, drying and calcining the gel B obtained in the step S2 to obtain the Ce-supported Beta molecular sieve with high dispersivity;
in S1, the mol ratio of the citric acid to the Ce source is (2-8) (0.5-5);
s2, the aging temperature is 15-35 ℃, and the aging time is 5-10 h;
in S3, the crystallization temperature is 130-160 ℃, and the crystallization time is 5-10 days.
Alternatively, the molar ratio of citric acid to templating agent is (0.03-0.16): 1.
Alternatively, the Ce source in S1 is cerium (iii) chloride heptahydrate, cerium (iii) nitrate hexahydrate, or cerium acetate.
Preferably, the Ce source in S1 is cerium (iii) chloride heptahydrate and/or cerium (iii) nitrate hexahydrate.
Optionally, the water is one or more of deionized water, ultrapure water and RO water.
Optionally, the template is tetraethylammonium hydroxide.
Optionally, the silicon source is fumed silica.
Optionally, the aluminum source is aluminum isopropoxide.
Optionally, the molar ratio of the silicon source to the aluminum source to the template agent is 100 (1-3) (30-70).
Optionally, the crystallization is finished and further comprises the steps of washing, drying and calcining, wherein the washing refers to repeatedly washing with the water in the step S1 to be neutral. The drying refers to drying for 8-15 h at 100-120 ℃. The calcination is performed in an air atmosphere at 550-600 ℃ for 5-8 hours.
According to the preparation method, citric acid is added into a precursor for synthesizing the Beta molecular sieve, and the Ce component of a cerium source and the citric acid can be utilized to form stable organic ligand salt, so that the Ce-supported Beta molecular sieve catalyst is synthesized by a one-step hydrothermal method. The method can overcome the problems that metal species are easy to precipitate and Ce active components are difficult to disperse effectively in the process of preparing the metal supported molecular sieve by a hydrothermal method, so that the dispersity of the Ce active components is improved, and the reactivity of the Beta molecular sieve in the process of preparing LAB by catalyzing alkylation of benzene and long-chain linear olefins is improved.
When the Ce source is an organic Ce source such as cerium acetate and citric acid is not added, a precipitate is generated in the Ce species, and the high-dispersity Ce-loaded Beta molecular sieve cannot be obtained.
In the invention S2, the template agent is added into the solution A first, which is beneficial to realizing the dissolution of the aluminum source.
In the present invention S2, after the silicon source is added, the whole solution becomes gel-like, so that the silicon source needs to be added last.
Preferably, the molar ratio of the citric acid to the Ce source is 5 (1-3).
More preferably, the molar ratio of the citric acid to the Ce source is 5 (2-3).
Still more preferably, the molar ratio of the citric acid to the Ce source is 5:3.
Preferably, in S2, the aging time is 6 to 7 hours.
Too short an aging time can result in too long a crystallization time of the molecular sieve and even a failure in synthesis.
The invention also protects application of the high-dispersity Ce-supported Beta molecular sieve serving as a catalyst in preparing linear alkylbenzene by catalyzing linear long-chain olefin and benzene.
Preferably, in said application, the linear long chain olefin has a carbon chain length of from 10 to 14.
The invention particularly protects the application of the high-dispersity Ce-supported Beta molecular sieve serving as a catalyst in preparing 2-dodecylbenzene by catalyzing 1-dodecene and benzene.
The high-dispersity Ce-supported Beta molecular sieve provided by the invention is used as a catalyst, can improve the reactivity of benzene and long-chain linear olefin in the liquid phase alkylation process, and can be used as a catalyst for catalyzing the alkylation of benzene and long-chain linear olefin to prepare 2-dodecylbenzene (2-LAB).
In said applications, the molar ratio of benzene to 1-dodecene may be from 5 to 25, preferably from 8 to 20.
In such applications, the catalytic temperature may be in the range of 60 to 100 ℃.
The catalytic temperature is lower and the reaction speed is reduced.
The catalytic temperature is higher and more energy is needed.
Preferably, in the application, the catalytic temperature is 70-90 ℃ and the mass airspeed is 30-50 h -1 The service life of the high-dispersity Ce-supported Beta molecular sieve is 9-13 h.
The pressure is normal pressure.
The high-dispersity Ce-supported Beta molecular sieve has the remarkable advantages of high catalytic activity and long service life. At the bed temperature of 70-90 ℃ and the mass airspeed of 30-50 h -1 Has a 1-dodecene conversion of more than 10% and a service life of 9 to 13 hours under severe reaction conditions.
The reaction is alkylation reaction, the alkylation reaction can be performed in a fixed bed reactor, the catalytic temperature is the bed temperature, and the reaction pressure can be normal pressure.
More preferably, the mass space velocity is 40h -1 。
Preferably, in said application, said 1-dodecene conversion is comprised between 10 and 37% and said 2-dodecylbenzene selectivity is comprised between 80 and 90%.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a high-dispersity Ce-supported Beta molecular sieve, wherein the silicon-aluminum ratio of the molecular sieve is 41-45, the loading amount of Ce in the molecular sieve is 0.28-2.47 wt%, the average particle size of Ce oxide clusters is 2.37-3.00 nm, and the dispersity index of the Ce oxide clusters is 1.059-1.071. The molecular sieve catalyst provided by the invention can be used for catalyzing the alkylation of benzene and long-chain linear olefin to prepare 2-LAB, has high dispersibility of Ce metal element, can effectively improve the selectivity of 2-LAB, and prolongs the service life of the catalyst.
The high-dispersity Ce-supported Beta molecular sieve provided by the invention is synthesized in one step by adopting a hydrothermal method, and has the characteristics of uniform dispersion of Ce active components and high activity.
The high-dispersity Ce-supported Beta molecular sieve provided by the invention has the advantages that the bed temperature is 80 ℃ and the mass airspeed is 40h -1 Under the severe reaction conditions, the selectivity of the 2-dodecylbenzene can reach 80-90 percent, and the service life can reach 9-13 hours.
Drawings
FIGS. 1 (a-f) are transmission electron microscope images (TEM images) and particle size distribution histograms of highly dispersible Ce-supported Beta molecular sieve catalysts prepared in examples 1-3 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the high-dispersity Ce-supported Beta molecular sieve catalyst prepared in examples 1-3 and comparative example 1 of the present invention.
FIG. 3 is a pyridine infrared spectrum of the high-dispersity Ce-supported Beta molecular sieve catalyst prepared in examples 1-3 and comparative example 1 of the present invention.
FIG. 4 is an infrared spectrum of 2, 6-di-tert-butylpyridine of the high-dispersity Ce-supported Beta molecular sieve catalyst prepared in examples 1-3 and comparative example 1 of the present invention.
FIG. 5 is a graph showing the 1-dodecene conversion and 2-dodecylbenzene selectivity of the high-dispersity Ce-supported Beta molecular sieve catalysts prepared in examples 1-3 and comparative example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
A high-dispersity Ce-supported Beta molecular sieve has a silicon-aluminum ratio of 43, a Ce loading amount in the molecular sieve of 0.283wt%, and a Ce oxide cluster dispersity index of 1.071.
The average particle size of the Ce oxide cluster was 2.37nm.
The preparation method of the high-dispersity Ce-supported Beta molecular sieve comprises the following steps:
weighing the raw materials:
the Ce source was cerium (III) chloride heptahydrate, 0.3726g.
Citric acid, 1.0560g.
The water was deionized water, 5.0755g.
The template was tetraethylammonium hydroxide, 21.0429g,35wt% aqueous solution.
The silicon source was fumed silica, 6.0084g.
The aluminum source was aluminum isopropoxide, 0.4093g.
S1, mixing and stirring a Ce source, citric acid and water until the solution is clear to obtain a solution A;
s2, sequentially adding a template agent, an aluminum source and a silicon source into the solution A obtained in the step S1, and aging to obtain gel B;
s3, transferring the gel B obtained in the step S2 into a reaction kettle for crystallization, washing, drying and calcining to obtain the high-dispersivity Ce-supported Beta molecular sieve;
in S1, the molar ratio of the citric acid to the Ce source is 5:1;
in S2, the molar ratio of the silicon source to the aluminum source to the template agent is 100:2:50.
The aging temperature is 25 ℃ at room temperature, and the aging time is 6 hours;
in S3, the crystallization temperature is 150 ℃ and the crystallization time is 6 days.
And after crystallization, washing, drying and calcining are further included, and after the product is filtered, the product is repeatedly washed to be neutral by deionized water. Calcination was carried out for 12h in a drying oven at 120 ℃. Calcining for 5h in an air atmosphere at 550 ℃.
Example 2
A high-dispersity Ce-supported Beta molecular sieve has a silicon-aluminum ratio of 41, a Ce loading amount of 0.933wt% in the molecular sieve and a Ce oxide cluster dispersity index of 1.059.
The average particle size of the Ce oxide cluster was 2.67nm.
The preparation method of the high-dispersity Ce-supported Beta molecular sieve is basically the same as that of the example 1, and the difference from the example 1 is that:
the Ce source was cerium (III) chloride heptahydrate, 0.7452g.
The water was deionized water, 4.9494g.
In S1, the molar ratio of citric acid to Ce source is 5:2.
Example 3
A high-dispersity Ce-supported Beta molecular sieve has a silicon-aluminum ratio of 43, a Ce loading amount in the molecular sieve of 2.469wt% and a Ce oxide cluster dispersity index of 1.069.
The average particle size of the Ce oxide cluster was 3.00nm.
The preparation method of the high-dispersity Ce-supported Beta molecular sieve is basically the same as that of the example 1, and the difference from the example 1 is that:
the Ce source was cerium (III) chloride heptahydrate, 1.1177g.
The water was deionized water, 4.8233g.
In S1, the molar ratio of citric acid to Ce source is 5:3.
Comparative example 1
A Beta molecular sieve, the silicon-aluminum ratio of the molecular sieve is 45, and the loading amount of Ce in the molecular sieve is 0.
The preparation method of the Ce-supported Beta molecular sieve is basically the same as that of the example 1, and the difference from the example 1 is that: beta molecular sieve has no Ce load.
Result detection
(1) High-dispersity Ce-loaded Beta fraction prepared in examples 1-3 by adopting FEI Talos 200S transmission electron microscopeAnd (5) characterizing the sub-sieve catalyst to obtain a transmission electron microscope image and a particle size distribution histogram. The test results are shown in FIGS. 1 (a) to (f) and Table 1. FIGS. 1 (a) to (c) are transmission electron micrographs of examples 1 to 3, respectively, and FIGS. 1 (d) to (f) are histograms of particle size distribution of Ce active species of examples 1 to 3, respectively. As can be seen from fig. 1 (a-c), the spheres are molecular sieve particles, wherein the bright spots are Ce active species. Wherein, the average particle diameter calculation formula of the Ce oxide cluster is d mean ＝∑d i The calculation formula of the Ce oxide cluster Dispersibility Index (DI) is:
wherein N is the counted N-th Ce oxide cluster crystal grain, d is the diameter of the Ce oxide cluster crystal grain, and N is the counted number of all crystal grains.
(2) The high-dispersity Ce-supported Beta molecular sieves prepared in examples 1 to 3 and the Beta molecular sieve catalyst prepared in comparative example 1 were characterized by using a D8 advanced type X-ray diffractometer from Bruker, germany, and the test results are shown in FIG. 2.
As can be seen from FIG. 2, the XRD patterns of examples 1-3 show that the characteristic peaks 2 theta of the XRD spectrum of the Beta molecular sieve are 7.6 degrees and 22.5 degrees, and the characteristic peaks of Ce oxide are not found at the 2 theta of 28.6 degrees, thus indicating that the high-dispersity Ce-loaded Beta molecular sieve is prepared.
(3) Pyridine and 2, 6-di-tert-butylpyridine are used as probe molecules, data acquisition is carried out on the high-dispersivity Ce-supported Beta molecular sieve prepared in examples 1-3 and the Beta molecular sieve catalyst prepared in comparative example 1 on a Germany Bruker Vertex 70 type Fourier transform infrared spectrometer, and calculation is carried out through the beer law
Acid and Lewis acid concentrations. The results are shown in FIG. 3, FIG. 4 and Table 1.
As can be seen from FIG. 3, in the Fourier transform infrared spectrum of the Ce-supported Beta molecular sieve of the present invention, 1545cm -1 The C-C stretching vibration peak of pyridine ion is
Characteristic peaks of acid sites; 1455cm -1 And 1445cm -1 The peak of the pyridine complex C-C stretching vibration is a characteristic peak of a Lewis acid site. As can be seen from FIG. 4, in the Fourier transform infrared spectrum of the Ce-supported Beta molecular sieve of the present invention, 1616cm -1 For the outer surface->
Characteristic peaks of acid sites.
TABLE 1 Ce dispersing Properties and acid concentration of the molecular sieves of examples 1-3 and comparative example 1
(3) The catalysts prepared in examples 1 to 3 and comparative example 1 were granulated, sieved with a 20 to 40 mesh sieve, and 0.25g of the sample was put into a fixed bed, activated in an air atmosphere at 400℃for 3 hours, and then cooled to 80 ℃. Preparing a reaction solution from benzene and 1-dodecene according to a molar ratio of 8.75:1, adding a certain amount of ethylcyclohexane as an internal standard, and regulating the flow rate of the reaction solution to a mass airspeed of 40h -1 The normal pressure reaction is considered to be deactivated when the catalyst conversion is less than 10%. The results of the tests for the conversion of 1-dodecene and the selectivity of 2-dodecylbenzene in examples 1 to 3 and comparative example 1 are shown in FIG. 5 and tables 2 and 3.
Table 2 catalytic activity of molecular sieves of examples 1 to 3 and comparative example 1
TABLE 3 catalytic Selectivity of molecular sieves of examples 1-3 and comparative example 1
As can be seen from the above tables 2 and 3, the high-dispersity Ce-supported Beta molecular sieve of the present invention is used in catalysisThe temperature is 80 ℃ and the mass airspeed is 40h -1 Under the condition of (1) the conversion rate of the Ce-supported Beta molecular sieve with high dispersity to 1-dodecene is 10-37%, the selectivity of 2-dodecylbenzene can reach 80-90%, and the service life can reach 9-13 h.
In contrast, the molecular sieve of comparative example 1, to which no Ce was added, had a 1-dodecene conversion of 24.71%, a 12.14% lower than that of example 3, and a catalytic life of 7 hours, which was 6 hours shorter than that of example 3.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The high-dispersivity Ce supported Beta molecular sieve is characterized in that the silicon-aluminum ratio of the molecular sieve is 41-45, the loading amount of Ce in the molecular sieve is 0.28-2.47 wt%, the average particle size of Ce oxide clusters is 2.37-3.00 nm, and the dispersivity index of the Ce oxide clusters is 1.059-1.071.
2. The high-dispersibility Ce-supported Beta molecular sieve according to claim 1, wherein the Ce loading in the molecular sieve is 0.933-2.47 wt%.
3. The high-dispersibility Ce-supported Beta molecular sieve according to claim 1, wherein the Ce oxide clusters have an average particle size of 2.67-3.00 nm.
4. A method for preparing the high-dispersity Ce-supported Beta molecular sieve according to any one of claims 1 to 3, comprising the following steps:
s1, mixing a Ce source, citric acid and water to obtain a solution A;
s2, sequentially adding a template agent, an aluminum source and a silicon source into the solution A obtained in the step S1, and aging to obtain gel B;
s3, crystallizing, washing, drying and calcining the gel B obtained in the step S2 to obtain the Ce-supported Beta molecular sieve with high dispersivity;
in S1, the mol ratio of the citric acid to the Ce source is (2-8) (0.5-5);
s2, the aging temperature is 15-35 ℃, and the aging time is 5-10 h;
in S3, the crystallization temperature is 130-160 ℃, and the crystallization time is 5-10 days.
5. The process for preparing a highly dispersible Ce-supported zeolite according to claim 4, wherein the molar ratio of citric acid to Ce source is 5 (2-3).
6. Use of a high-dispersity Ce-supported Beta molecular sieve according to any one of claims 1-3 as a catalyst for catalyzing linear long-chain olefins and benzene to prepare linear alkylbenzenes.
7. The use according to claim 6, wherein in said use the linear long chain olefins have a carbon chain length of from 10 to 14.
8. The use according to claim 7, wherein in the use the linear long-chain olefin is 1-dodecene and the linear alkylbenzene is 2-dodecylbenzene.
9. The process according to claim 8, wherein the catalyst temperature is 70-90℃and the mass space velocity is 30-50 h -1 The service life of the high-dispersity Ce-supported Beta molecular sieve is 9-13 h.
10. The use according to claim 8, wherein the 1-dodecene conversion is 10 to 37% and the selectivity for 2-dodecylbenzene is 80 to 90%.
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