CN115888800A - Shape-selective catalyst for p-diethylbenzene and preparation method and application thereof - Google Patents
Shape-selective catalyst for p-diethylbenzene and preparation method and application thereof Download PDFInfo
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- CN115888800A CN115888800A CN202211157794.3A CN202211157794A CN115888800A CN 115888800 A CN115888800 A CN 115888800A CN 202211157794 A CN202211157794 A CN 202211157794A CN 115888800 A CN115888800 A CN 115888800A
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- hzsm
- diethylbenzene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005470 impregnation Methods 0.000 claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000005804 alkylation reaction Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- JRZPDZRGTGCVNL-UHFFFAOYSA-N ethanol;ethylbenzene Chemical compound CCO.CCC1=CC=CC=C1 JRZPDZRGTGCVNL-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- IQHHLQVUUXLKFL-UHFFFAOYSA-N 2-(2-ethylphenyl)ethanol Chemical compound CCC1=CC=CC=C1CCO IQHHLQVUUXLKFL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- -1 rare earth nitrate Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding 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
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
Abstract
The invention belongs to the field of chemical material preparation, and particularly relates to a shape-selective catalyst for p-diethylbenzene, and a preparation method and application thereof. The invention provides a shape-selective catalyst for p-diethylbenzene, which has the diethylbenzene selectivity of over 91 percent and high selectivity during the ethylbenzene ethanol alkylation reaction, is favorable for reducing energy consumption and resource waste. The invention also provides a preparation method of the shape-selective catalyst for P-diethylbenzene, which comprises the steps of loading alumina and rare earth elements on the HZSM-5 molecular sieve, and then sequentially adopting silicon, magnesium and phosphorus for impregnation and activation to prepare the shape-selective catalyst for P-diethylbenzene (Si-Mg-P-HZSM-5 catalyst), wherein the shape-selective catalyst for P-diethylbenzene has strong stability and long one-way reaction period, and still has good activity after continuous reaction.
Description
Technical Field
The invention belongs to the field of chemical material preparation, and particularly relates to a shape-selective catalyst for p-diethylbenzene, and a preparation method and application thereof.
Background
P-diethylbenzene is used as an important basic organic chemical raw material, is mainly used as a desorbent in the process of producing p-xylene by an adsorption separation method, can also be used for producing divinylbenzene by dehydrogenation, and is used as a cross-linking agent for producing ion exchange resins, coatings and synthetic materials.
ZSM-5 is a molecular sieve catalyst with excellent performance, and the acid strength and the acid distribution of the ZSM-5 can be regulated and controlled in a large range, so that the ZSM-5 is a molecular sieve material widely used in research. However, the acidic centers on the outer surface of the ZSM-5 molecular sieve are usually unfavorable for shape-selective reaction, and in addition, the pore diameter is slightly larger, if the catalyst is directly used for producing p-diethylbenzene, a large amount of isomers can be generated, and the outer surface of the molecular sieve can be modified to improve the selectivity of the shape-selective catalytic reaction of the molecular sieve.
The industrial production of p-diethylbenzene generally adopts a catalyst which takes HZSM-5 as a main body, and under the condition of gas and solid phases, ethylbenzene and ethylene are subjected to alkylation reaction or ethylbenzene and ethanol are subjected to alkylation reaction to synthesize the p-diethylbenzene. At present, the selectivity of diethylbenzene in a reaction product of a diethylbenzene synthesis method is about 60%, the selectivity is low, the material circulation amount is large, the energy consumption is high, deep alkylation and disproportionation reactions are severe, byproducts such as benzene and heavy aromatics are more in the product, and resources with higher value such as ethylbenzene are consumed greatly, so that the improvement of the selectivity of diethylbenzene in the reaction product is urgently needed.
Disclosure of Invention
The invention aims to provide a shape-selective catalyst for p-diethylbenzene and a preparation method and application thereof. The shape-selective catalyst for p-diethylbenzene is used for ethylbenzene-ethanol alkylation, and the selectivity of diethylbenzene is high and reaches more than 91%.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a shape-selective catalyst for p-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and oxides loaded on the nano HZSM-5 molecular sieve, wherein the oxides comprise aluminum oxide, rare earth oxide, mgO and SiO 2 And P 2 O 5 The rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
the shape-selective catalyst for p-diethylbenzene comprises the following components in parts by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO and SiO 2 2 to 12% and P 2 O 5 2～12％。
Preferably, siO in the nano HZSM-5 molecular sieve 2 With Al 2 O 3 In a molar ratio of 20 to 600.
Preferably, the MgO and SiO are 2 And P 2 O 5 The mass ratio of (A) to (B) is 2 to 12.
The invention also provides a preparation method of the shape-selective catalyst for p-diethylbenzene, which comprises the following steps:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, a rare earth soluble salt and a binder, and then sequentially carrying out forming, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of ethyl orthosilicate, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
carrying out second impregnation on the Si-HZSM-5 catalyst and the aqueous solution of magnesium acetate, and then sequentially carrying out third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and the aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst for p-diethylbenzene.
Preferably, the binder is a nitric acid solution, and the mass fraction of nitric acid in the nitric acid solution is 3-10%.
Preferably, the organic solvent in the organic solution of ethyl orthosilicate is ethanol or cyclohexane.
Preferably, the time for the first impregnation, the second impregnation and the third impregnation is independently 2 to 20 hours.
Preferably, the temperature of the first drying, the second drying, the third drying and the fourth drying is independently 50 to 200 ℃ and the time is independently 5 to 12 hours.
Preferably, the first roasting, the second roasting, the third roasting and the fourth roasting independently have a temperature of 500 to 600 ℃ and a time of 5 to 12 hours.
The invention also provides the application of the shape-selective catalyst for p-diethylbenzene in the technical scheme in the preparation of p-diethylbenzene.
The invention provides a shape-selective catalyst for p-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and oxides loaded on the nano HZSM-5 molecular sieve, wherein the oxides comprise aluminum oxide, rare earth oxide, mgO and SiO 2 And P 2 O 5 The rare earth elements in the rare earth oxide comprise one or more of lanthanum, cerium and neodymium;
the shape-selective catalyst for p-diethylbenzene comprises the following components in parts by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO and SiO 2 2 to 12% and P 2 O 5 2～12％。
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a shape-selective catalyst for p-diethylbenzene, which is characterized in that MgO and SiO are loaded on a nano HZSM-5 molecular sieve 2 And P 2 O 5 The selectivity of diethylbenzene is over 91 percent when the ethylbenzene-ethanol alkylation reaction is carried out by using various active components of the modifier, and the selectivity is high, thereby being beneficial to reducing energy consumption and reducing resource waste.
Furthermore, the shape-selective catalyst for p-diethylbenzene has strong stability and long one-way reaction period, and still has good activity after continuous reaction.
The invention also provides a preparation method of the shape-selective catalyst for P-diethylbenzene, which comprises the step of loading the HZSM-5 molecular sieve with alumina and rare earth elements, and then sequentially adopting silicon, magnesium and phosphorus for impregnation and activation to prepare the shape-selective catalyst for P-diethylbenzene (Si-Mg-P-HZSM-5 catalyst).
The data of the embodiment of the invention show that when the shape selective catalyst is used for ethylbenzene-ethanol alkylation reaction, the selectivity of diethylbenzene is over 91 percent, the disproportionation and deep alkylation reactions are well controlled, the selectivity of diethylbenzene is over 97 percent, the single-pass conversion rate of ethylbenzene is over 30 percent, and the single-pass conversion rate of ethylbenzene can still be maintained over 25 percent after 1000 hours of continuous reaction.
Detailed Description
The inventionProvides a shape-selective catalyst for p-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and oxides loaded on the nano HZSM-5 molecular sieve, wherein the oxides comprise aluminum oxide, rare earth oxide, mgO and SiO 2 And P 2 O 5 The rare earth elements in the rare earth oxide comprise one or more of lanthanum, cerium and neodymium;
the shape-selective catalyst for p-diethylbenzene comprises the following components in parts by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO and SiO 2 2 to 12% and P 2 O 5 2～12％。
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the invention, siO in the nano HZSM-5 molecular sieve 2 With Al 2 O 3 The molar ratio of (a) is preferably 20 to 600, more preferably 30 to 200, most preferably 30 to 60.
In the invention, the particle size of the nano HZSM-5 molecular sieve is preferably 90-160 nm.
In the invention, the alumina and the rare earth oxide are formed carriers, and the sum of the mass fractions of the alumina and the rare earth oxide in the shape-selective catalyst for p-diethylbenzene is preferably 10-30%.
In the present invention, the alumina is preferably a product of pseudo-boehmite calcination, and the calcination temperature is preferably 500 to 600 ℃.
In the invention, the rare earth oxide is preferably a product of roasting a rare earth soluble salt, the roasting temperature is preferably 500-600 ℃, and the rare earth oxide can increase the stability of the shape-selective catalyst.
In the present invention, the rare earth oxide preferably includes one or more of cerium oxide, lanthanum oxide, and neodymium oxide, and the rare earth element in the rare earth oxide is preferably cerium; when the rare earth element in the rare earth oxide preferably includes a plurality of kinds of lanthanum, cerium and neodymium, the present invention has no particular requirement for the kind and proportion of the rare earth element.
In the present invention, the mass fraction of MgO in the shape-selective catalyst for p-diethylbenzene is preferably 3 to 5%.
In the invention, siO in the shape-selective catalyst of p-diethylbenzene 2 The mass fraction of (b) is preferably 2 to 5%.
In the invention, P in the shape-selective catalyst of P-diethylbenzene 2 O 5 The mass fraction of (b) is preferably 3 to 5%.
In the present invention, the MgO and SiO 2 And P 2 O 5 Is an active component of a modifier and influences the shape selective effect of the nano HZSM-5 molecular sieve on the p-diethylbenzene, wherein MgO and SiO in the shape selective catalyst of the p-diethylbenzene 2 And P 2 O 5 The sum of the mass fractions of (b) is preferably 8 to 20%.
In the present invention, the MgO and SiO 2 And P 2 O 5 Preferably, the mass ratio is 2 to 12.
The invention also provides a preparation method of the shape-selective catalyst for p-diethylbenzene, which comprises the following steps:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, a rare earth soluble salt and a binder, and then sequentially carrying out forming, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of ethyl orthosilicate, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
carrying out second impregnation on the Si-HZSM-5 catalyst and the aqueous solution of magnesium acetate, and then sequentially carrying out third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and the aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst for p-diethylbenzene.
The Al-rare earth-HZSM-5 catalyst is prepared by mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, a rare earth soluble salt and a binder, and then sequentially carrying out forming, first drying and first roasting.
The source of the nano HZSM-5 molecular sieve is not particularly limited, and the nano HZSM-5 molecular sieve can be prepared by adopting a method commonly used in the field.
In a specific embodiment of the present invention, the nano HZSM-5 molecular sieve is preferably prepared by a method comprising the steps of: adopting n-butylamine as a template agent, adjusting the pH value by using a water glass aqueous solution, aluminum sulfate and concentrated sulfuric acid, filtering and washing a product obtained after crystallization synthesis under a hydrothermal condition, and then carrying out fifth drying and fifth roasting to obtain a NaZSM-5 molecular sieve; and carrying out sixth roasting on the NaZSM-5 molecular sieve after ammonium ion exchange to obtain the nano HZSM-5 molecular sieve.
In the present invention, the temperature of the fifth drying is preferably 50 to 200 ℃ and the time is preferably 5 to 12 hours.
In the present invention, the temperature of the fifth baking is preferably 500 to 600 ℃, and the time is preferably 5 to 12 hours.
In the present invention, the pseudoboehmite is preferably a dry-based pseudoboehmite.
In the invention, the rare earth soluble salt is preferably a rare earth nitrate, and the rare earth nitrate is preferably cerium nitrate, lanthanum nitrate or neodymium nitrate, and more preferably cerium nitrate.
In the invention, the mass ratio of the nano HZSM-5 molecular sieve to the dry-based pseudoboehmite to the rare earth nitrate is preferably 150.
In the present invention, the molding is preferably extrusion molding, more preferably extrusion molding.
In the invention, the binder is preferably a nitric acid solution, the mass fraction of nitric acid in the nitric acid solution is preferably 3-10%, the invention has no special requirement on the dosage of the nitric acid solution, and the mixed powder can be formed after being bonded, and is a mixture of a nano HZSM-5 molecular sieve, pseudo-boehmite and a rare earth soluble salt.
In the present invention, the temperature of the first drying is preferably 50 to 200 ℃, more preferably 150 ℃, and the time is preferably 5 to 12 hours, more preferably 6 hours.
In the present invention, the temperature of the first calcination is preferably 500 to 600 ℃, more preferably 550 ℃, and the time is preferably 5 to 12 hours, more preferably 5 hours.
After the Al-rare earth-HZSM-5 catalyst is obtained, the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane are subjected to first impregnation, and then second drying and second roasting are sequentially performed to obtain the Si-HZSM-5 catalyst.
In the present invention, the organic solvent in the organic solution of ethyl orthosilicate is preferably ethanol or cyclohexane.
In the invention, the first impregnation is preferably equal-volume impregnation, the equal-volume impregnation refers to equal volume of the adsorption capacity of impregnation liquid and the molecular sieve, and the mass of the tetraethoxysilane can be calculated according to the content of the active component of the modifier in the shape-selective catalyst of the p-diethylbenzene.
In the present invention, the time for the first impregnation is preferably 2 to 20 hours, and more preferably 15 hours.
In the present invention, the temperature of the second drying is preferably 50 to 200 ℃, more preferably 150 ℃, and the time is preferably 5 to 12 hours, more preferably 6 hours.
In the present invention, the temperature of the second calcination is preferably 500 to 600 ℃, more preferably 550 ℃, and the time is preferably 5 to 12 hours, more preferably 5 hours.
After the Si-HZSM-5 catalyst is obtained, the Si-HZSM-5 catalyst and the aqueous solution of magnesium acetate are subjected to second impregnation, and then third drying and third roasting are sequentially performed to obtain the Si-Mg-HZSM-5 catalyst.
After the Si-Mg-HZSM-5 catalyst is obtained, the Si-Mg-HZSM-5 catalyst and the aqueous solution of ammonium dihydrogen phosphate are subjected to third impregnation, and then fourth drying and fourth roasting are sequentially performed to obtain the shape-selective catalyst for p-diethylbenzene.
In the present invention, the second impregnation and the third impregnation are independently preferably equivalent-volume impregnation.
In the present invention, the time of the second impregnation and the third impregnation is preferably the same as that of the first impregnation, and will not be described herein.
In the present invention, the temperature and time of the third drying and the fourth drying are preferably the same as those of the second drying, and are not described herein again.
In the present invention, the temperature and time of the third baking and the fourth baking are preferably the same as those of the second baking, and are not described in detail herein.
The invention also provides the application of the shape-selective catalyst for p-diethylbenzene in the technical scheme in the preparation of p-diethylbenzene.
In the present invention, the application preferably includes: mixing ethanol, ethylbenzene and the shape-selective catalyst of p-diethylbenzene to carry out alkylation reaction.
In the present invention, the reaction conditions of the alkylation reaction preferably include:
the molar ratio of the ethanol to the ethylbenzene is 1-5 to 2, the reaction pressure is 0-1.0 MPa, the reaction temperature is 320-420 ℃, the molar ratio of the carrier gas to the ethylbenzene is 1-1, and the mass space velocity of the ethylbenzene is 0.4-5 h -1 。
In the present invention, the carrier gas is preferably nitrogen or water vapor.
In the present invention, the mass space velocity of ethylbenzene is more preferably 0.7h -1 。
In order to further illustrate the present invention, the shape-selective catalyst for p-diethylbenzene and the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The synthesis method of the nano HZSM-5 molecular sieve comprises the following steps:
n-butylamine is used as template agent, water glass aqueous solution, aluminum sulfate and concentrated sulfuric acid are used for adjusting the pH value and SiO 2 /Al 2 O 3 Is 30; filtering, washing and drying a product synthesized by crystallization under a hydrothermal condition at 150 ℃ for 6 hours, and then transferring the product into a roasting furnace for roasting at 550 ℃ for 5 hours to prepare the Na-ZSM-5 molecular sieve; and then adopting a conventional ammonium ion exchange method and then using a roasting method to obtain the nano HZSM-5 molecular sieve.
Example 2
This example differs from example 1 above only in that SiO 2 /Al 2 O 3 Is 60.
Example 3
This example differs from example 1 above only in that SiO 2 /Al 2 O 3 Is 200.
Example 4
1) The nano HZSM-5 molecular Sieve (SiO) obtained in example 1 was subjected to 2 /Al 2 O 3 The molar ratio of 30) 150g, 51g of dry-based pseudo-boehmite and 12g of rare earth cerium nitrate, uniformly mixing the 3 kinds of powder, binding and extruding the mixture into strips by using dilute nitric acid with the mass concentration of 3%, drying the strips at 150 ℃ for 6 hours, and roasting the strips at 550 ℃ for 5 hours to obtain the formed HZSM-5 catalyst strips.
2) Impregnating the shaped HZSM-5 catalyst strip obtained in step 1) with an ethanol solution of ethyl orthosilicate in equal volume for 15 hours (to make the final catalyst A1 contain 4wt% of SiO 2 ) Drying at 150 deg.c for 6 hr, and roasting at 550 deg.c for 5 hr to obtain the formed Si-HZSM-5 catalyst strip.
3) Soaking the formed Si-HZSM-5 catalyst strip prepared in the step 2) in an aqueous solution of magnesium acetate for 15 hours in equal volume (the final product, namely the catalyst A1, contains 3wt% of MgO), drying at 150 ℃ for 6 hours, and then roasting at 550 ℃ for 5 hours to prepare the formed Si-Mg-HZSM-5 catalyst strip.
4) Impregnating the shaped Si-Mg-HZSM-5 catalyst strip obtained in step 3) with an aqueous solution of ammonium dihydrogen phosphate in equal volume for 15 hours (to give a final product catalyst A1 containing 4wt% of P 2 O 5 ) Drying the catalyst at 150 ℃ for 6 hours, and then roasting the catalyst at 550 ℃ for 5 hours to obtain a molded Si-Mg-P-HZSM-5 catalyst strip marked as catalyst A1.
Example 5
This example differs from example 4 only in that the final product contains 2wt% SiO 2 ，5wt％MgO，3wt％P 2 O 5 And is denoted as catalyst A2.
Example 6
This example differs from example 4 only in that the final product contains 3% by weight SiO 2 ，4wt％MgO，5wt％P 2 O 5 And is denoted as catalyst A3.
Example 7
This example differs from example 4 only in having 5wt% SiO in the final product 2 ，5wt％MgO，3wt％P 2 O 5 And is denoted as catalyst A4.
Example 8
This example is different from example 4 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 2 is used 2 /Al 2 O 3 The molar ratio of (B) to (c) was 60), the resulting shaped Si-Mg-P-HZSM-5 catalyst strip was designated as catalyst B1.
Example 9
This example is different from example 5 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 2 is used 2 /Al 2 O 3 The molar ratio of (B) to (c) was 60), the resulting shaped Si-Mg-P-HZSM-5 catalyst strip was designated as catalyst B2.
Example 10
This example is different from example 6 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 2 is used 2 /Al 2 O 3 The molar ratio of (a) to (B) is 60), the formed Si-Mg-P-HZSM-5 catalyst strip obtained is denoted as catalyst B3.
Example 11
This example is different from example 7 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 2 is used 2 /Al 2 O 3 The molar ratio of (a) to (B) is 60), the formed Si-Mg-P-HZSM-5 catalyst strip obtained is denoted as catalyst B4.
Example 12
This example is different from example 4 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 3 is used 2 /Al 2 O 3 The molar ratio of (a) to (b) is 200), and the prepared shaped Si-Mg-P-HZSM-5 catalyst strip is denoted as catalyst C1.
Example 13
This example is different from example 5 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 3 is used 2 /Al 2 O 3 The molar ratio of (a) to (b) is 200), and the prepared shaped Si-Mg-P-HZSM-5 catalyst strip is denoted as catalyst C2.
Example 14
This example is different from example 6 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 3 is used 2 /Al 2 O 3 The molar ratio of (a) to (b) is 200), and the prepared shaped Si-Mg-P-HZSM-5 catalyst strip is denoted as catalyst C3.
Example 15
This example is different from example 7 only in that the nano HZSM-5 molecular Sieve (SiO) obtained in example 3 is used 2 /Al 2 O 3 The molar ratio of (a) to (b) is 200), and the prepared shaped Si-Mg-P-HZSM-5 catalyst strip is denoted as catalyst C4.
Application example 1
The shape-selective catalysts obtained in examples 4 to 15 were applied to ethylbenzene and ethanol alkylation reactions to synthesize p-diethylbenzene, and the fixed bed reactor was used for catalytic reaction performance examination.
The invention adopts a 316 stainless steel reactor, adopts electric heating and automatically controls the temperature in multiple sections. The catalyst is arranged on a fixed bed evaluation device to carry out the alkylation reaction of ethylbenzene and ethanol, the loading amount of the catalyst is 100 g, the molar ratio of the ethylbenzene to the ethanol is 3 -1 The reaction temperature is 350 ℃, the reaction pressure is 0.2MPa, and the molar ratio of the carrier gas to the ethylbenzene is 2. The liquid and gas phase product analyses were performed on two GC9800 gas chromatographs, respectively.
The experimental data obtained by the reaction were calculated using the following formula, and the reaction results are shown in table 1:
ethylbenzene conversion = [ (ethylbenzene content in feed-ethylbenzene content in product)/ethylbenzene content in feed ] × 100%
Diethylbenzene selectivity = [ mixed diethylbenzene content in product/(total aromatic hydrocarbon content in product-ethylbenzene content in product) ] × 100%
P-diethylbenzene selectivity = (p-diethylbenzene content in product/mixed diethylbenzene content in product) × 100%
TABLE 1 results of the reaction
As can be seen from the data in Table 1, the shape-selective catalysts for p-diethylbenzene of examples 4-15 have diethylbenzene selectivity of 91% or more, better control of disproportionation and deep alkylation reactions, p-diethylbenzene selectivity of 97% or more, ethylbenzene single-pass conversion of 30% or more, and ethylbenzene single-pass conversion of 25% or more after 1000 hours of continuous reaction.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments of the present invention, and the embodiments are within the scope of the present invention.
Claims (10)
1. The shape-selective catalyst for p-diethylbenzene is characterized by comprising a nano HZSM-5 molecular sieve and oxides loaded on the nano HZSM-5 molecular sieve, wherein the oxides comprise aluminum oxide, rare earth oxide, mgO and SiO 2 And P 2 O 5 The rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
the shape-selective catalyst for p-diethylbenzene comprises the following components in parts by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO and SiO 2 2 to 12% and P 2 O 5 2～12％。
2. The shape selective catalyst of claim 1, wherein the nano HZSM-5 molecular sieve has SiO in it 2 With Al 2 O 3 The molar ratio of (a) to (b) is 20 to 600.
3. The shape selective catalyst of claim 1, wherein the MgO, siO is 2 And P 2 O 5 The mass ratio of (A) to (B) is 2 to 12.
4. A process for preparing a shape selective catalyst according to any one of claims 1 to 3, comprising the steps of:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, a rare earth soluble salt and a binder, and then sequentially carrying out forming, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
carrying out second impregnation on the Si-HZSM-5 catalyst and the aqueous solution of magnesium acetate, and then sequentially carrying out third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and the aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst for the p-diethylbenzene.
5. The preparation method according to claim 4, characterized in that the binder is a nitric acid solution, and the mass fraction of nitric acid in the nitric acid solution is 3-10%.
6. The method according to claim 4, wherein the organic solvent in the organic solution of ethyl orthosilicate is ethanol or cyclohexane.
7. The method of claim 4, wherein the first, second and third impregnations are independently carried out for a period of time of 2 to 20 hours.
8. The method according to claim 4, wherein the first drying, the second drying, the third drying, and the fourth drying are independently at a temperature of 50 to 200 ℃ for 5 to 12 hours.
9. The method of claim 4, wherein the first firing, the second firing, the third firing, and the fourth firing are independently at a temperature of 500 to 600 ℃ for 5 to 12 hours.
10. Use of a shape selective catalyst according to any one of claims 1 to 3 or obtained by the preparation method according to any one of claims 4 to 9 for the preparation of p-diethylbenzene.
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