CN105381814A - Catalyst used in alkylation reaction of ethylbenzene and ethanol and preparation method thereof - Google Patents
Catalyst used in alkylation reaction of ethylbenzene and ethanol and preparation method thereof Download PDFInfo
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- CN105381814A CN105381814A CN201510648937.4A CN201510648937A CN105381814A CN 105381814 A CN105381814 A CN 105381814A CN 201510648937 A CN201510648937 A CN 201510648937A CN 105381814 A CN105381814 A CN 105381814A
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- zsm
- molecular sieve
- ethylbenzene
- catalyst
- ethanol
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 25
- 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 169
- 239000002808 molecular sieve Substances 0.000 claims abstract description 168
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 117
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 73
- 239000001257 hydrogen Substances 0.000 claims description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims description 73
- 150000002431 hydrogen Chemical class 0.000 claims description 72
- 238000005516 engineering process Methods 0.000 claims description 47
- 239000000428 dust Substances 0.000 claims description 39
- 230000008569 process Effects 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 18
- 238000010306 acid treatment Methods 0.000 claims description 16
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 230000029936 alkylation Effects 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 abstract description 54
- 230000005496 eutectics Effects 0.000 abstract description 51
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000010555 transalkylation reaction Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- JRZPDZRGTGCVNL-UHFFFAOYSA-N ethanol;ethylbenzene Chemical compound CCO.CCC1=CC=CC=C1 JRZPDZRGTGCVNL-UHFFFAOYSA-N 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 carbonium ion Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 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
- 150000007517 lewis acids Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a catalyst in an alkylation reaction of ethylbenzene and ethanol. The catalyst comprises the following raw materials in percentages by weight: 10%-30% of aluminum oxide, and 70%-90% of a modified hydrogen form eutectic crystallization ZSM-5/ZSM-11 molecular sieve; and the modified hydrogen form eutectic crystallization ZSM-5/ZSM-11 molecular sieve is a citric acid modified hydrogen form ZSM-5/ZSM-11 molecular sieve. Moreover, the present invention also discloses a preparation method of the catalyst. The method comprises the following steps: firstly, kneading the raw materials and baking the raw materials to obtain a mixture; and secondly, roasting the mixture in steam atmosphere to obtain the catalyst. The catalyst disclosed by the present invention is used in the alkylation reaction of ethylbenzene and ethanol to prepare p-diethylbenzene, a high ethylbenzene (ethanol) conversion rate can be obtained, side reactions such as transalkylation can be greatly suppressed, and the selectivity of reaction products diethylbenzene and p-diethylbenzene are improved.
Description
Technical field
The invention belongs to petrochemical catalyst technical field, be specifically related to a kind of ethylbenzene and ethanol alkylation reaction Catalysts and its preparation method and application.
Background technology
P-Diethylbenzene is a kind of important Organic Chemicals, main application is the special strippant of para-xylene production unit p-xylene separation process, also can be used to produce divinylbenzene, be further used for ion exchange resin, the modifier of synthetic rubber divinylbenzene and polystyrene and the polymerization single polymerization monomer of unsaturated polyester (UP) glass steel etc.
The production of p-Diethylbenzene mainly contains two kinds of techniques, and separating technology adopts rectificating method purification p-Diethylbenzene product from mixing diethylbenzene (PDX+ODX+MDX), and separating energy consumption is high, and purity is difficult to reach the requirement being greater than 95%.At present, the industrial production of p-Diethylbenzene generally adopts the catalyst based on HZSM-5, under gas solid phase conditions, carries out alkylated reaction to synthesize the technology path of p-Diethylbenzene with ethylbenzene and ethene or ethanol.Adopt this technology can utilize the production p-Diethylbenzene selecting shape effect high selectivity of catalyst.Researcher is constantly devoted to carry out to molecular sieve the research that modification obtains high-purity p-Diethylbenzene technology, such as US Patent No. 4100217, US4094921, US4128592, US4465886, US5406015 etc. adopt ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-38 equimolecular to sieve to carry out steam or Si modification process to improve the selective of p-Diethylbenzene respectively.Chinese patent CN200410020397.7, CN200310116628.X, CN101618335B, CN94110202.5 etc. all relate to employing ZSM-5 molecular sieve or adopt various method of modifying to produce p-Diethylbenzene to it.Nearest Chinese patent CN103664474A discloses and utilizes MWW type molecular sieve to produce the method for p-Diethylbenzene for high catalyst selectivity.The process of above-mentioned patent or the ethylbenzene involved by open source literature and ethanol synthesis generation paraxylene, the dominant catalyst adopted is generally ZSM-5 or modified ZSM-5, the selective problem on the low side of ubiquity p-Diethylbenzene, there is the disclosed selective height of p-Diethylbenzene adopting novel molecular sieve to produce as alkylation catalyst of patent, but shortcoming possibility catalyst preparing high expensive, the activity stability of this catalyst is not also mentioned in addition.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned deficiency of the prior art, provides a kind of ethylbenzene and ethanol alkylation reaction Catalysts and its preparation method.This catalyst is used for ethylbenzene and ethanol alkylation reaction is prepared in p-Diethylbenzene, can while obtaining higher conversion of ethylbenzene, the side reactions such as great suppression transalkylation, improve the selective of product p-Diethylbenzene or diethylbenzene, and catalyst has very long activity stability simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of ethylbenzene and the anti-applications catalyst of ethanol alkylation, is made up: aluminium oxide 10% ~ 30%, modified hydrogen ZSM-5/ZSM-11 molecular sieve 70% ~ 90% of the raw material of following percentage by weight; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 50 ~ 120, and crystallite dimension is 0.5 μm ~ 1 μm.
Further improvement is, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 60 ~ 90, and crystallite dimension is 0.8 μm ~ 1 μm.
Further improvement is, the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80.
Further improvement is, the preparation process of described modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is: adopt citric acid solution to carry out acid treatment 3h ~ 5h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 80 DEG C ~ 90 DEG C conditions, obtain modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve; The mass concentration of described citric acid solution is 0.8% ~ 1.2%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 molecular sieve is 5 ~ 8:1.
Present invention also offers a kind of method preparing above-mentioned catalyst, the detailed process of the method is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve and dust technology are carried out kneading, dry 80 DEG C ~ 130 DEG C conditions after extruded moulding, then in steam atmosphere, the product calcination process 1h ~ 6h will obtained after oven dry under temperature is 450 DEG C ~ 600 DEG C conditions, obtains alkylated reaction catalyst after cooling naturally.
Further improvement is, the mass concentration of described dust technology is 5% ~ 8%, and the consumption of dust technology is 55% ~ 65% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve quality sum.
Present invention also offers the application of a kind of above-mentioned catalyst in catalysis ethylbenzene and ethanol alkylation reaction, it is characterized in that, the method of described alkylated reaction is: loaded by catalyst in fixed bed reactors, it is 330 DEG C ~ 380 DEG C in reaction temperature, reaction pressure is 0.7MPa ~ 0.9MPa, ethylbenzene and ethanol mol ratio are 4.8 ~ 5.2, and mass space velocity is 0.4h
-1~ 0.6h
-1condition under, catalysis ethylbenzene and ethanol synthesis.
Further improvement is, described reaction temperature is 350 DEG C, and reaction pressure is 0.6MPa, and ethylbenzene and ethanol mol ratio are 5.0, and mass space velocity is 0.5h
-1.
The present invention compared with prior art has the following advantages:
1, catalyst of the present invention prepares p-Diethylbenzene for ethylbenzene and ethanol alkylation reaction, or benzene and ethanol alkylation reaction prepare in ethylbenzene, can while obtaining higher conversion of ethylbenzene, the side reactions such as great suppression transalkylation, improve the selective of product p-Diethylbenzene or diethylbenzene.
2, the active component used in catalyst of the present invention is through modified Hydrogen ZSM-5/ZSM-11 molecular sieve, Hydrogen ZSM-5/ZSM-11 molecular sieve is the one in ZSM-5/ZSM-11 molecular sieve, ZSM-5/ZSM-11 molecular sieve is a kind of mesopore height silicon eutectic molecular sieve of novelty, there is one dimension and three-dimensional micropore pore passage structure, this in two crystal formation eutectic define a lot of crystal defect, be a kind of molecular sieve having very much feature on pore passage structure, a lot of reaction all shows the reactivity worth more excellent than single crystal.Its skeleton is the ten-ring duct be made up of silica and aluminum-oxygen tetrahedron, in ellipse opening, orifice diameter is 0.56nm × 0.58nm, compared with being the catalyst of active component with conventional ZSM-5 molecular sieve, ZSM-5/ZSM-11 eutectic molecular sieve structure is similar to ZSM-5, but aperture is more bigger than ZSM-5 molecular sieve, diethylbenzene selective activization is better in theory.Due to special pore passage structure, ZSM-5/ZSM-11 eutectic molecular sieve can show excellent catalytic performance in the alkylated reaction of ethylbenzene and ethanol, has good industrial application value at petrochemical industry.
3, the SiO of Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve in the present invention
2/ Al
2o
3mol ratio is 50 ~ 90, mild acidity, be particularly suitable in the alkylated reaction of ethylbenzene and ethanol, because the alkylated reaction of ethanol and ethylbenzene it has been generally acknowledged that to be undertaken by Rideal mechanism, ethanol first catalyzed dose of Bronst acid site activation forms carbonium ion, then reacts with the ethylbenzene species of absorption and generates ethyl ethylbenzene.According to organic group location rule, ethanol based carbonium ion is easily positioned at ortho position and the para postion of ethylbenzene, want the diethylbenzene obtaining high contraposition, require that in the pore size of catalyst, grain size and hole, acid site intensity is coordinated, prevent the side reaction such as disproportionation and isomerization, in catalyst of the present invention, the special hole mouth structure of Hydrogen ZSM-5/ZSM-11 molecular sieve makes this catalyst have specific Studies On The Shape-selective Catalysis, and this catalyst application has excellent catalytic performance in the alkylated reaction of ethanol and ethylbenzene.
4, first the present invention carries out acid treatment modification to Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve, the Al on its surface (Lewis acid position) is removed through citric acid treatment, effectively can improve acidity distribution like this and expand specific surface area of catalyst, again by the calcination process in steam atmosphere, make the relocation bit of Bronst acid site further, effectively can improve B acid/L acid ratio, significantly improve the selective of catalyst and hydrothermal stability.
5, catalyst of the present invention is not high for solving conversion of ethylbenzene in prior art in ethylbenzene and ethanol alkylation reaction under specific process conditions, p-Diethylbenzene/diethylbenzene selective lower, the problem that the side reaction such as disproportionated reaction and isomerization reaction is serious, there is conversion ratio high, selectivity of product is high, the features such as side reaction is few, and catalyst stability is good.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Fig. 1 is the XRD spectra of the embodiment of the present invention 1 and comparative example 1-1 Kaolinite Preparation of Catalyst;
Wherein: a-ZSM-5; B-ZSM-5/ZSm-11;
The reactivity curve of Fig. 2 embodiment of the present invention 1 and comparative example 1-1 Kaolinite Preparation of Catalyst;
Wherein: the p-Diethylbenzene of A-embodiment 1 is selective; The p-Diethylbenzene of B-comparative example 1-1 is selective; The conversion of ethylbenzene of C-embodiment 1; The conversion of ethylbenzene of D-comparative example 1-1.
Detailed description of the invention
In catalyst of the present invention, the preparation method of Hydrogen ZSM-5/ZSM-11 molecular sieve is:
First reference literature (the synthesis of small-grain ZSM-5/ZSM-11 cocrystallization molecular sieve, petrochemical industry, 2008,37 (supplementary issues): 556 ~ 558 pages) method reported prepares ZSM-5/ZSM-11 eutectic molecular sieve, then prepares Hydrogen ZSM-5/ZSM-11 molecular sieve in accordance with the following steps:
Step one, ZSM-5/ZSM-11 molecular sieve is warming up to 200 DEG C ~ 600 DEG C calcination process in dry air, the organic template agent existed in removing ZSM-5/ZSM-11 microporous molecular sieve;
Step 2, the ZSM-5/ZSM-11 eutectic molecular sieve after calcination process in step one is placed in the ammonium nitrate solution that concentration is 0.5mol/L ~ 1.0mol/L, be (5 ~ 10) in liquid-solid ratio: 1, temperature is, under the condition of 80 DEG C ~ 90 DEG C, ZSM-5/ZSM-11 molecular sieve ammonium is exchanged process 2h ~ 4h;
Step 3, by step 2 through ammonium exchange process after ZSM-5/ZSM-11 eutectic molecular sieve under 500 DEG C of conditions roasting dry, obtain Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve.
Embodiment 1:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 10%, modified hydrogen ZSM-5/ZSM-11 molecular sieve 90%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.8 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 4h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 85 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 molecular sieve; The mass concentration of described citric acid solution is 1.0%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 molecular sieve is 6:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 molecular sieve and dust technology are carried out kneading, dry 110 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 3h will obtained after oven dry under temperature is 550 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 5%, and the consumption of dust technology is 60% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 molecular sieve quality sum.
In Fig. 1, curve a is X-ray (XRD) spectrogram of catalyst prepared by the present embodiment, and in Fig. 2, curve C is the reactivity curve map of catalyst prepared by the present embodiment.
Comparative example 1-1:
The catalyst of this comparative example is made primarily of the raw material of following percentage by weight: aluminium oxide 10%, modified hydrogen ZSM-5 molecular sieve 90%; Described modified hydrogen ZSM-5 molecular sieve is the Hydrogen ZSM-5 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 1.5 μm ~ 5 μm; The preparation process of modified hydrogen ZSM-5 molecular sieve is: adopt citric acid solution to carry out acid treatment 4h to Hydrogen ZSM-5 molecular sieve under 85 DEG C of conditions, obtain modified hydrogen ZSM-5 molecular sieve; The mass concentration of described citric acid solution is 1.0%, and the mass ratio of citric acid solution and Hydrogen ZSM-5 molecular sieve is 6:1; Described Hydrogen ZSM-5 molecular sieve is obtained through non-amine method production by Catalyst Factory, Nankai Univ.
The concrete preparation process of this comparative example catalyst is: aluminium oxide, modified hydrogen ZSM-5 molecular sieve and dust technology are carried out kneading, dry 110 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 3h will obtained after oven dry under temperature is 550 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 5%, and the consumption of dust technology is 60% of aluminium oxide and modified hydrogen ZSM-5 molecular sieve quality sum.
In Fig. 1, spectrogram b is that in X-ray (XRD) figure, Fig. 2 of catalyst prepared by this comparative example, curve D is the reactivity curve map of catalyst prepared by this comparative example.
Spectrogram a in comparison diagram 1 and spectrogram b, can find out, catalyst active component spectrogram a used prepared by embodiment 1 is a kind of shape selectivity preferably eutectic ZSM-5/ZSM-11 molecular sieve of ad hoc structure; What comparative example 1-1 catalyst adopted is then traditional ZSM-5 molecular sieve (spectrogram b).This catalyst all making the embodiment of the present invention 1 prepare has better active and selective.
Comparative example 1-2:
The catalyst of this comparative example is made primarily of the raw material of following percentage by weight: aluminium oxide 10%, Hydrogen ZSM-5/ZSM-11 molecular sieve 90%; The SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.8 μm ~ 1 μm.
The concrete preparation process of this comparative example catalyst is: aluminium oxide and Hydrogen ZSM-5/ZSM-11 molecular sieve and dust technology are carried out kneading, dry 110 DEG C of conditions after extruded moulding, under 550 DEG C of air atmosphere, obtain product after calcination process 3h, naturally obtain alkylated reaction catalyst after cooling; The mass concentration of described dust technology is 5%, and the consumption of dust technology is 60% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 molecular sieve quality sum.
Embodiment 2:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 20%, modified hydrogen ZSM-5/ZSM-11 molecular sieve 80%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve
2/ Al
2o
3mol ratio is 60, and crystallite dimension is 0.5 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 5h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 80 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve; The mass concentration of described citric acid solution is 0.8%, and the mass ratio of described citric acid solution and Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is 8:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve and dust technology are carried out kneading, dry 80 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 4.5h will obtained after oven dry under temperature is 500 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 8%, and the consumption of dust technology is 55% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve quality sum.
Comparative example 2:
The catalyst of this comparative example is made primarily of the raw material of following percentage by weight: aluminium oxide 20%, Hydrogen ZSM-5 molecular sieve 80%; Described Hydrogen ZSM-5 molecular sieve is the Hydrogen ZSM-5 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is 78, and crystallite dimension is 1.5 μm ~ 5 μm; The preparation process of modified hydrogen ZSM-5 molecular sieve is: adopt citric acid solution to carry out acid treatment 5h to Hydrogen ZSM-5 molecular sieve under 80 DEG C of conditions, obtain modified hydrogen ZSM-5 molecular sieve; The mass concentration of described citric acid solution is 0.8%, and the mass ratio of citric acid solution and Hydrogen ZSM-5 molecular sieve is 8:1; Described Hydrogen ZSM-5 molecular sieve is obtained through non-amine method production by Catalyst Factory, Nankai Univ.
The concrete preparation process of this comparative example catalyst is: aluminium oxide, modified hydrogen ZSM-5 molecular sieve and dust technology are carried out kneading, dry 80 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 4.5h will obtained after oven dry under temperature is 500 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 8%, and the consumption of dust technology is 55% of aluminium oxide and modified hydrogen ZSM-5 molecular sieve quality sum.
Embodiment 3:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 30%, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve 70%; Described modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve
2/ Al
2o
3mol ratio is 90, and crystallite dimension is 0.5 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 3h to Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve under 90 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve; The mass concentration of described citric acid solution is 1.2%, and the mass ratio of described citric acid solution and Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is 5:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve and dust technology are carried out kneading, dry 130 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 6h will obtained after oven dry under temperature is 450 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 7%, and the consumption of dust technology is 65% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve quality sum.
Comparative example 3:
The catalyst of this comparative example is made primarily of the raw material of following percentage by weight: aluminium oxide 30%, modified hydrogen ZSM-5 molecular sieve 70%; Described modified hydrogen ZSM-5 molecular sieve is the Hydrogen ZSM-5 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is 102, and crystallite dimension is 1.5 μm ~ 5 μm; The preparation process of modified hydrogen ZSM-5 molecular sieve is: adopt citric acid solution to carry out acid treatment 3h to Hydrogen ZSM-5 molecular sieve under 90 DEG C of conditions, obtain modified hydrogen ZSM-5 molecular sieve; The mass concentration of described citric acid solution is 1.2%, and the mass ratio of citric acid solution and Hydrogen ZSM-5 molecular sieve is 5:1; Described Hydrogen ZSM-5 molecular sieve is obtained through there being amine method to produce by Catalyst Factory, Nankai Univ.
The concrete preparation process of this comparative example catalyst is: aluminium oxide, modified hydrogen ZSM-5 molecular sieve and dust technology are carried out kneading, dry 130 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 6h will obtained after oven dry under temperature is 450 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 7%, and the consumption of dust technology is 65% of aluminium oxide and modified hydrogen ZSM-5 molecular sieve quality sum.
Embodiment 4:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 20%, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve 80%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.8 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is: adopt citric acid solution to carry out acid treatment 4h to Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve under 85 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve; The mass concentration of described citric acid solution is 1.0%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is 7:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve and dust technology are carried out kneading, dry 120 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 1h will obtained after oven dry under temperature is 600 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 6%, and the consumption of dust technology is 58% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve quality sum.
Embodiment 5:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 30%, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve 70%; Described modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is the Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.5 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is: adopt citric acid solution to carry out acid treatment 3h to Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve under 90 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve; The mass concentration of described citric acid solution is 0.9%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve is 6:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve and dust technology are carried out kneading, dry 100 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 2h will obtained after oven dry under temperature is 600 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 6%, and the consumption of dust technology is 62% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve quality sum.
Embodiment 6:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 10%, modified hydrogen ZSM-5/ZSM-11 eutectic molecular sieve 90%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.5 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 5h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 80 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 molecular sieve; The mass concentration of described citric acid solution is 1.1%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 molecular sieve is 5.5:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 molecular sieve and dust technology are carried out kneading, dry 110 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 3.5h will obtained after oven dry under temperature is 500 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 5%, and the consumption of dust technology is 63% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 molecular sieve quality sum.
Embodiment 7:
The catalyst of the present embodiment is made primarily of the raw material of following percentage by weight: aluminium oxide 20%, modified hydrogen ZSM-5/ZSM-11 molecular sieve 80%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80, and crystallite dimension is 0.5 μm ~ 1 μm; The preparation process of modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 4h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 85 DEG C of conditions, obtain modified hydrogen ZSM-5/ZSM-11 molecular sieve; The mass concentration of described citric acid solution is 1.0%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 molecular sieve is 6:1.
The concrete preparation process of the present embodiment catalyst is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 molecular sieve and dust technology are carried out kneading, dry 110 DEG C of conditions after extruded moulding, then in steam atmosphere, the product calcination process 2.5h will obtained after oven dry under temperature is 580 DEG C of conditions, obtains alkylated reaction catalyst after cooling naturally; The mass concentration of described dust technology is 7%, and the consumption of dust technology is 56% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 molecular sieve quality sum.
Embodiment 8:
Adopt the catalyst ethylbenzene of embodiment 1 ~ 7, comparative example 1-1, comparative example 1-2 and comparative example 2 ~ 3 and the alkylated reaction of ethanol, the method of described alkylated reaction is: loaded by catalyst in fixed bed reactors, it is 360 DEG C in reaction temperature, reaction pressure is 0.8MPa, ethylbenzene and ethanol mol ratio are 5.0, and mass space velocity is 0.5h
-1condition under, catalysis ethylbenzene and ethanol synthesis.
The performance of catalyst prepared by the present invention is evaluated as follows:
Catalyst ethylbenzene and the ethanol alkylation reaction result of embodiment 1 ~ 7, comparative example 1-1, comparative example 1-2 and comparative example 2 ~ 3 are as shown in table 1.
Table 1 different catalysts catalysis ethylbenzene and ethanol alkylation reaction 16h result
| Catalyst | Conversion of ethylbenzene/% | P-Diethylbenzene is selective/% |
| Embodiment 1 | 19.23 | 98.15 |
| Comparative example 1-1 | 22.65 | 30.38 |
| Comparative example 1-2 | 20.09 | 87.56 |
| Embodiment 2 | 20.29 | 97.36 |
| Comparative example 2 | 18.01 | 91.37 |
| Embodiment 3 | 18.76 | 96.46 |
| Comparative example 3 | 17.05 | 94.65 |
| Embodiment 4 | 19.26 | 97.58 |
| Embodiment 5 | 18.95 | 98.32 |
| Embodiment 6 | 19.37 | 97.48 |
| Embodiment 7 | 21.18 | 96.65 |
Embodiment 9:
Adopt the catalyst ethylbenzene of embodiment 5 and the alkylated reaction of ethanol, the method of described alkylated reaction is: loaded by catalyst in fixed bed reactors, is 330 DEG C in reaction temperature, and reaction pressure is 0.9MPa, ethylbenzene and ethanol mol ratio are 5.2, and mass space velocity is 0.4h
-1condition under, catalysis ethylbenzene and ethanol synthesis.
Embodiment 10:
Adopt the catalyst ethylbenzene of embodiment 5 and the alkylated reaction of ethanol, the method of described alkylated reaction is: loaded by catalyst in fixed bed reactors, is 380 DEG C in reaction temperature, and reaction pressure is 0.7MPa, ethylbenzene and ethanol mol ratio are 4.8, and mass space velocity is 0.6h
-1condition under, catalysis ethylbenzene and ethanol synthesis.
Adopt the catalytic reaction of aforesaid assessment method to embodiment 9 ~ 10 to evaluate, result is as shown in table 2.
The catalytic reaction result of catalyst under different technology conditions of table 2 embodiment 5
| Process conditions | Conversion of ethylbenzene/% | P-Diethylbenzene is selective/% |
| Embodiment 9 | 16.08 | 98.26 |
| Embodiment 10 | 19.88 | 97.06 |
As can be seen from Table 1 and Table 2, compared to adopting Hydrogen ZSM-5 molecular sieve as active component in prior art, the catalyst adopting Hydrogen ZSM-5/ZSM-11 molecular sieve to prepare as active component in the present invention under specific process conditions in the alkylated reaction of ethylbenzene and ethanol, there is higher conversion of ethylbenzene and p-Diethylbenzene selective.In conjunction with the embodiments 1 and the data result of comparative example 1-2 can find out, the technique of citric acid treatment Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve Bound moisture steam calcination process catalyst is adopted in the present invention, can make the catalyst prepared while the conversion of ethylbenzene that maintenance is higher, there is the selective of high p-Diethylbenzene.
As can be seen from table 1 and table 2 and Fig. 2, compared to adopting Hydrogen ZSM-5 molecular sieve as active component in prior art, the catalyst adopting Hydrogen ZSM-5/ZSM-11 molecular sieve to prepare as active component in the present invention under specific process conditions in the alkylated reaction of ethylbenzene and ethanol, there is higher conversion of ethylbenzene and p-Diethylbenzene selective.In conjunction with the embodiments 1 and the data result of comparative example 1-2 can find out equally, the technique of citric acid treatment Hydrogen ZSM-5/ZSM-11 eutectic molecular sieve Bound moisture steam calcination process catalyst is adopted in the present invention, can make the catalyst for preparing on the basis keeping higher conversion of ethylbenzene, there is the selective of high p-Diethylbenzene, and catalyst life is longer more stable.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (8)
1. ethylbenzene and the anti-applications catalyst of ethanol alkylation, is characterized in that, be made up of the raw material of following percentage by weight: aluminium oxide 10% ~ 30%, modified hydrogen ZSM-5/ZSM-11 molecular sieve 70% ~ 90%; Described modified hydrogen ZSM-5/ZSM-11 molecular sieve is the Hydrogen ZSM-5/ZSM-11 molecular sieve through citric acid-modified, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 50 ~ 120, and crystallite dimension is 0.5 μm ~ 2 μm.
2. ethylbenzene according to claim 1 and the anti-applications catalyst of ethanol alkylation, is characterized in that, before modified the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 60 ~ 90, and crystallite dimension is 0.8 μm ~ 1 μm.
3. ethylbenzene according to claim 2 and the anti-applications catalyst of ethanol alkylation, is characterized in that, the SiO of described Hydrogen ZSM-5/ZSM-11 molecular sieve
2/ Al
2o
3mol ratio is 80.
4. the ethylbenzene according to claim 1,2 or 3 and the anti-applications catalyst of ethanol alkylation, is characterized in that,
The preparation process of described modified hydrogen ZSM-5/ZSM-11 molecular sieve is: adopt citric acid solution to carry out acid treatment 3h ~ 5h to Hydrogen ZSM-5/ZSM-11 molecular sieve under 80 DEG C ~ 90 DEG C conditions, obtain modified hydrogen ZSM-5/ZSM-11 molecular sieve; The mass concentration of described citric acid solution is 0.8% ~ 1.2%, and the mass ratio of citric acid solution and Hydrogen ZSM-5/ZSM-11 molecular sieve is 5 ~ 8:1.
5. prepare the method for ethylbenzene as described in claim 1,2 or 3 and the anti-applications catalyst of ethanol alkylation for one kind, it is characterized in that, the detailed process of the method is: aluminium oxide, modified hydrogen ZSM-5/ZSM-11 molecular sieve and dust technology are carried out kneading, dry 80 DEG C ~ 130 DEG C conditions after extruded moulding, then in steam atmosphere, the product calcination process 1h ~ 6h will obtained after oven dry under temperature is 450 DEG C ~ 600 DEG C conditions, obtains alkylated reaction catalyst after cooling naturally.
6. the method preparing ethylbenzene and the anti-applications catalyst of ethanol alkylation according to claim 5, it is characterized in that, the mass concentration of described dust technology is 5% ~ 8%, and the consumption of dust technology is 55% ~ 65% of aluminium oxide and modified hydrogen ZSM-5/ZSM-11 molecular sieve quality sum.
7. an ethylbenzene as described in claim 1,2 or 3 and the application of the anti-applications catalyst of ethanol alkylation in catalysis ethylbenzene and ethanol alkylation reaction, it is characterized in that, the method of described alkylated reaction is: loaded by catalyst in fixed bed reactors, it is 330 DEG C ~ 380 DEG C in reaction temperature, reaction pressure is 0.7MPa ~ 0.9MPa, ethylbenzene and ethanol mol ratio are 4.8 ~ 5.2, and mass space velocity is 0.4h
-1~ 0.6h
-1condition under, catalysis ethylbenzene and ethanol synthesis.
8. ethylbenzene according to claim 7 and the application of the anti-applications catalyst of ethanol alkylation in catalysis ethylbenzene and ethanol alkylation reaction, it is characterized in that, described reaction temperature is 350 DEG C, and reaction pressure is 0.6MPa, ethylbenzene and ethanol mol ratio are 5.0, and mass space velocity is 0.5h
-1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669818A (en) * | 2016-12-27 | 2017-05-17 | 西安元创化工科技股份有限公司 | Preparation method of catalyst for preparing p-methyl ethylbenzene by alkylation and application of catalyst |
| CN112387303A (en) * | 2019-08-14 | 2021-02-23 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, catalyst and application thereof |
| CN113045375A (en) * | 2021-03-22 | 2021-06-29 | 浙江大学衢州研究院 | Method for preparing 2-pentylanthracene from diamyl anthracene through transalkylation |
| CN113185378A (en) * | 2021-04-30 | 2021-07-30 | 江苏常青树新材料科技股份有限公司 | Method for preparing divinylbenzene by taking ethanol and ethylbenzene as raw materials |
| CN114797961A (en) * | 2021-01-19 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
-
2015
- 2015-10-09 CN CN201510648937.4A patent/CN105381814B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李婷婷: "ZSM-5/11共晶分子筛与多级孔道ZSM-5分子筛的合成", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669818A (en) * | 2016-12-27 | 2017-05-17 | 西安元创化工科技股份有限公司 | Preparation method of catalyst for preparing p-methyl ethylbenzene by alkylation and application of catalyst |
| CN112387303A (en) * | 2019-08-14 | 2021-02-23 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, catalyst and application thereof |
| CN112387303B (en) * | 2019-08-14 | 2024-04-26 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, and catalyst and application thereof |
| CN114797961A (en) * | 2021-01-19 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction |
| CN114797961B (en) * | 2021-01-19 | 2023-09-26 | 中国科学院大连化学物理研究所 | Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene |
| CN113045375A (en) * | 2021-03-22 | 2021-06-29 | 浙江大学衢州研究院 | Method for preparing 2-pentylanthracene from diamyl anthracene through transalkylation |
| CN113185378A (en) * | 2021-04-30 | 2021-07-30 | 江苏常青树新材料科技股份有限公司 | Method for preparing divinylbenzene by taking ethanol and ethylbenzene as raw materials |
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