CN1079285C - Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene - Google Patents
Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene Download PDFInfo
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- CN1079285C CN1079285C CN97106449A CN97106449A CN1079285C CN 1079285 C CN1079285 C CN 1079285C CN 97106449 A CN97106449 A CN 97106449A CN 97106449 A CN97106449 A CN 97106449A CN 1079285 C CN1079285 C CN 1079285C
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- Prior art keywords
- ethylene
- zeolite
- weight
- benzene
- catalyst
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000005977 Ethylene Substances 0.000 title claims abstract description 28
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 20
- 230000029936 alkylation Effects 0.000 title claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 45
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical group C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 10
- 230000009849 deactivation Effects 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910002796 Si–Al Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- -1 rare-earth salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 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 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical compound C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-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 present invention relates to an alkylation catalyst for manufacturing ethylbenzene from benzene and ethylene, which comprises ZSM-5 zeolite whose molar ratio of SiO2 /Al2O3 is 30 to 500, and alkaline earth and rare earth oxide which are loaded on the ZSM-5 zeolite. The catalyst is used for the alkylation reaction of benzene and ethylene, and has the advantages of high reactivity and high stability. The alkylation catalyst can be used for industrial production.
Description
The present invention relates to the alkylation catalyst of a kind of benzene and ethylbenzene manufactured from ethylene, especially about the alkylation catalyst of ZSM-5 zeolite.
Ethylbenzene is important chemical material, is mainly used in production vinylbenzene.Ethylbenzene can be produced with various method, and one of successful method is in the presence of a kind of solid acid ZSM-5 zeolite catalyst, with ethene benzene is carried out vapor-phase alkylation.Discussed ethene in the early stage United States Patent (USP) 3751504 benzene has been carried out the situation of vapor phase alkylation, used unmodified ZSM-5 in this patent as catalyzer.Studies show that afterwards, unmodified ZSM-5 molecular sieve has a significant disadvantage as the catalyzer of synthesizing ethyl benzene: poor catalyst stability, deactivation rate is fast.Domestic and international for this reason many investigators have proposed multiple method to the ZSM-5 modification, and purpose is to improve the activity stability of ZSM-5 catalyzer in the synthesizing ethyl benzene reaction.Wherein representational method of modifying has: (a) phosphoric modification (US3962364), (b) rare-earth element modified (CN1074392A), (c) water vapour modification (US4663492, US4594146, US4522929 and US4429176) etc.Catalyzer described in these documents, though increase than early stage catalyst activity stability, industry needs the catalyzer of high stability, is beneficial to the long-term operation of production equipment.
The purpose of this invention is to provide a kind of new benzene and the alkylation catalyst of ethylbenzene manufactured from ethylene, under benzene and ethylene alkylation condition, this catalyzer has the good advantage of activity stability.
The objective of the invention is to realize by following technical scheme: the alkylation catalyst of a kind of benzene and ethylbenzene manufactured from ethylene comprises:
(a) SiO
2/ Al
2O
3Mol ratio is 30～500 ZSM-5 zeolite; Be stated from the zeolite
(b) rare-earth oxide of the alkaline earth metal oxide of 0.1～10% (weight) and 0.1～10% (weight).
The amount of the alkaline earth metal oxide that contains in the catalyzer in the technique scheme is 0.5～6% by weight percentage, and alkaline earth metal oxide can be beryllium oxide, magnesium oxide or calcium oxide, and its preferred version is a magnesium oxide.The amount that contains rare-earth oxide in the catalyzer is 0.3～4% by weight percentage, and rare-earth oxide can be lanthanum trioxide, Samarium trioxide, cerium oxide or its mixture, and its preferred version is a lanthanum trioxide.The SiO of ZSM-5 zeolite in the catalyzer
2/ Al
2O
3The mol ratio preferable range is 40～200.
Catalyzer of the present invention is to be the primary activity component with ZSM-5 type Si-Al zeolite.The type zeolite is synthesized by template with the organic amine.And in prepared crystal silicon-aluminate zeolite molecular sieve, add alumina binder again and mix and to pinch and extruded moulding.The process ammonium salt carries out ion-exchange and roasting changes Hydrogen into.Pass through the finished catalyst that further interpolation alkaline earth, rare-earth element modified processing make again.
Catalyst preparation process of the present invention is:
One, zeolite is synthetic
Water glass and organic amine, Tai-Ace S 150, sulfuric acid etc. are mixed with solution, under agitation, solution are mixed into glue.Colloid was 140～175 ℃ of crystallization 2～4 days.After crystallization is finished, filter, wash and drying, promptly get the ZSM-5 Si-Al zeolite.
Two, Preparation of catalysts
(1), with above-mentioned synthetic zeolite and binding agent Al
2O
3By roasting behind 65/35 the weight ratio kneading and compacting.
(2), above-mentioned zeolite is transformed into Hydrogen ZSM-5 zeolite by ion-exchange.
(3), above-mentioned Hydrogen ZSM-5 zeolite is added a certain amount of alkaline earth, rare-earth salts properties-correcting agent with impregnation method.Catalyzer behind the dipping was 500～600 ℃ of roastings of temperature 2～15 hours, and catalyzer gets product.
Because the present invention adopts alkaline earth and rare earth compound dipping method of modifying, the intensity and the concentration of having regulated ZSM-5 molecular sieve catalyst surface acid center have reached the purpose that improves catalyst activity stability, have obtained effect preferably.
In order to compare with former method of modifying, we have prepared the catalyst B of phosphorus modification, the catalyzer C of La modification and the catalyzer D of water vapour modification respectively according to patent USP3962364, CN1074392A and the described method of USP4663492.The index of evaluate catalysts stability is under the same reaction conditions, the deactivation rate of identical time inner catalyst.Reaction conditions divides normal pressure and pressurizes two kinds: 400 ℃ of (1) temperature of reaction, reaction pressure are normal pressure, benzene/ethylene ratio (mol ratio)=1: 1, the weight space velocity WHSV=4.0hr of ethene
-1(2) 400 ℃ of temperature of reaction, reaction pressure 1.6MPa, benzene/ethylene ratio (mol ratio)=8: 1, the weight space velocity WHSV=2.0hr of ethene
-1Give further detailed explanation below in conjunction with embodiment to technology of the present invention.
[embodiment 1]
Synthesizing of zeolite
Get the 889ml water glass solution, 150ml deionized water and 32g hexanediamine mix.Other gets content is 99% Al
2(SO
4)
318H
2O14g, 98%H
2SO
410ml and deionized water 170ml mix.Crystallization 24hr under 150 ℃ of conditions in autoclave.Product is chilled to room temperature rapidly, the mother liquor that inclines, with deionized water wash to the pH value of solution be till 8～9.110 ℃ of dryings 10 hours promptly get silica alumina ratio and are 150 ZSM-5 type zeolite.[embodiment 2]
Synthesizing of zeolite
Press the method for embodiment 1, preparation ZSM-5 type Si-Al zeolite, the silica alumina ratio of its ZSM-5 zeolite is 45.[embodiment 3]
Synthesizing of zeolite
Press the method for embodiment 1, preparation ZSM-5 type Si-Al zeolite, the silica alumina ratio of its ZSM-5 zeolite is 450.[embodiment 4]
The preparation of zeolite catalyst A
The exsiccant zeolite powder and the alumina trihydrate of embodiment 1 gained are mixed, mediate extrusion.The consumption of alumina trihydrate is so that butt Al
2O
3With the zeolite weight ratio be 35/65, the bar of the diameter 2mm that is extruded into, more than 110 ℃ of dry 12hr, then 550 ℃ of roastings 4～6 hours in air, the sample of gained is used 1NNH at 90 ℃
4NO
3Solution carries out ion-exchange 3～4 times, and then at 110 ℃ of baking 18hr, 550 ℃ of roasting 4hr obtain hydrogen zeolite catalyst.[embodiment 5]
The foregoing description 4 is mixed with the 2mm extrusion HZSM-5 zeolite 4g of 35% (weight) alumina binder, with (the NH of 6.6% (weight)
4)
2HPO
4Solution 15g dipping, drying is at 500 ℃ of roasting 10hr.The gained catalyst B contains the phosphorus oxide of 5.5% (weight).[embodiment 6]
The 2mm extrusion HZSM-5 zeolite 4g that is mixed with 35% (weight) alumina binder that embodiment 4 is made is with the La (NO of 5% (weight)
3)
3Solution 15g dipping, drying is at 500 ℃ of roasting 10hr.Gained catalyzer C contains the lanthanum trioxide of 7.6% (weight).[embodiment 7]
The 2mm extrusion HZSM-5 zeolite 4g that is mixed with 35% (weight) alumina binder with embodiment 4 makes handles 1hr with water vapour at 500 ℃.Obtain water vapour modified catalyst D.[embodiment 8]
The 2mm extrusion HZSM-5 zeolite 4g that is mixed with 35% (weight) alumina binder that embodiment 4 is made is with the Mg (NO of 3% (weight)
3)
2With 3% (weight) La (NO
3)
3Mixing solutions 15g dipping, drying is at 500 ℃ of roasting 10hr.Gained catalyzer E contains the lanthanum trioxide of the magnesium oxide and 4.7% (weight) of 2.8% (weight).[embodiment 9]
Benzene with 1: 1 mol ratio: the catalyzer of ethene by 1.75g embodiment 4～8, reaction conditions and the results are shown in table 1.
| Embodiment number | Temperature ℃ | Pressure MPa | Total air speed hr -1 | React initial conversion of ethylene % | The conversion of ethylene % of reaction 24hr | Average deactivation rate %/hr | Ethylbenzene+diethylbenzene selectivity % |
| 4 | 410 | 0.1 | 22.4 | 48.7 | 32.9 | 0.65 | 98.78 |
| 5 | 410 | 0.1 | 22.4 | 42.6 | 30.2 | 0.52 | 98.86 |
| 6 | 410 | 0.1 | 22.4 | 42.3 | 33.1 | 0.38 | 98.95 |
| 7 | 410 | 0.1 | 22.4 | 42.4 | 34.5 | 0.33 | 98.90 |
| 8 | 410 | 0.1 | 22.4 | 42.4 | 37.3 | 0.21 | 99.00 |
As seen from the above table, embodiment 8 catalyzer with magnesium and lanthanum modification have the slowest deactivation rate, activity stability the best under the synthesis under normal pressure condition.[embodiment 10]
Benzene with 8: 1 mol ratios: ethene passes through the catalyst reaction condition of 1.75g embodiment 4,6,8 and the results are shown in table 2.
| Embodiment number | Temperature ℃ | Pressure MPa | Total air speed hr -1 | React initial conversion of ethylene % | The conversion of ethylene % of reaction 400hr | Average deactivation rate %/hr | Ethylbenzene+diethylbenzene selectivity % |
| 4 | 410 | 1.6 | 46.5 | 100.0 | 89.2 | 27×10 -2 | 99.10 |
| 6 | 410 | 1.6 | 46.5 | 100.0 | 95.6 | 1.1×10 -2 | 99.25 |
| 8 | 410 | 1.6 | 46.5 | 100.0 | 99.8 | 0.5×10 -3 | 99.68 |
As seen from the above table, use the catalyzer of the embodiment 8 of magnesium and lanthanum modification, under the reaction conditions of pressurization, also have the slowest deactivation rate, active and selectivity the best.The reaction conditions basically identical of this reaction conditions and industrial gas phase hydrocarbonylation legal system ethylbenzene, therefore, this result has a potential using value industrial.[embodiment 11]
ZSM-5 zeolite with embodiment 2 acquisitions, the preparation method who earlier presses embodiment 4, the 2mm extrusion HZSM-5 zeolite 4g that is mixed with 35% (weight) alumina binder that makes, method with embodiment 8 makes catalyzer F, wherein contains the lanthanum trioxide of the beryllium oxide and 3.8% (weight) of 3.5% (weight).
Benzene with 1: 1 mol ratio: ethene is by the above-mentioned catalyzer that makes of 1.75g, and temperature of reaction is 410 ℃, and reaction pressure is 0.1MPa, and the total air speed of benzene and ethene is 22.4hr
-1, reacting initial conversion of ethylene is 42.7%, and the conversion of ethylene behind the reaction 24hr is 32.9%, and on average per hour deactivation rate is 0.41%, and the overall selectivity of ethylbenzene and diethylbenzene is 98.9%.[embodiment 12]
ZSM-5 zeolite with embodiment 3 acquisitions, the first 2mm extrusion HZSM-5 zeolite 4g that is mixed with 35% (weight) alumina binder that makes by the preparation method of embodiment 4, method with embodiment 8 makes catalyzer G, wherein contains the cerium oxide of the magnesium oxide and 3.5% (weight) of 6.0% (weight).
Benzene with 1: 1 mol ratio: ethene is by the above-mentioned catalyzer that makes of 1.75g, and temperature of reaction is 410 ℃, and reaction pressure is 0.1MPa, and the total air speed of benzene and ethene is 22.4hr
-1, reacting initial conversion of ethylene is 42.1%, and the conversion of ethylene behind the reaction 24hr is 36.5%, and on average per hour deactivation rate is 0.23%, and the overall selectivity of ethylbenzene and diethylbenzene is 98.95%.[embodiment 13]
With the ZSM-5 zeolite that embodiment 2 obtains, the preparation method who presses embodiment 4 makes the 2mm extrusion HZSM-5 catalyzer H that is mixed with 35% (weight) alumina binder.[embodiment 14]
The HZSM-5 zeolite catalyst 4g that embodiment 4 is made is with the Mg (NO of 3% (weight)
3)
2Solution 5g, dipping, drying is at 500 ℃ of roasting 10hr.The gained catalyst I contains the magnesium oxide of 0.8% (weight).[embodiment 15]
The HZSM-5 zeolite catalyst 4g that embodiment 4 is made is with the Mg (NO of 5% (weight)
3)
2Solution 20g, dipping, drying is at 500 ℃ of roasting 10hr.Gained catalyzer J contains the magnesium oxide of 6.2% (weight).[embodiment 16]
With the ZSM-5 zeolite that embodiment 3 obtains, the preparation method who presses embodiment 4 makes the 2mm extrusion HZSM-5 catalyzer K that is mixed with 35% (weight) alumina binder.[embodiment 17]
The HZSM-5 zeolite catalyst 4g that embodiment 4 is made is with the La (NO of 1% (weight)
3)
3Solution 6g, dipping, drying is at 500 ℃ of roasting 10hr.Gained catalyzer L contains the lanthanum trioxide of 0.65% (weight).[embodiment 18]
The HZSM-5 zeolite catalyst 4g that embodiment 4 is made is with the La (NO of 5% (weight)
3)
3Solution 15g, dipping, drying is at 500 ℃ of roasting 10hr.Gained catalyzer M contains the lanthanum trioxide of 7.2% (weight).[embodiment 19]
With the benzene of 1: 1 mol ratio, ethene catalyzer by 1.75g embodiment 13～18, reaction conditions and the results are shown in table 3.
| Embodiment number | Temperature ℃ | Pressure MPa | Total air speed hr -1 | React initial conversion of ethylene % | The conversion of ethylene % of reaction 24hr | Average deactivation rate %/hr | Ethylbenzene ten ethylbenzene selectivity % |
| 13 | 410 | 0.1 | 22.4 | 51.8 | 35.4 | 0.68 | 98.72 |
| 14 | 410 | 0.1 | 22.4 | 48.9 | 34.8 | 0.59 | 98.76 |
| 15 | 410 | 0.1 | 22.4 | 43.7 | 34.5 | 0.38 | 98.83 |
| 16 | 410 | 0.1 | 22.4 | 46.5 | 36.7 | 0.41 | 98.80 |
| 17 | 410 | 0.1 | 22.4 | 44.8 | 36.4 | 0.35 | 98.82 |
| 18 | 410 | 0.1 | 22.4 | 41.9 | 35.4 | 0.27 | 98.98 |
Claims (8)
1, the alkylation catalyst of a kind of benzene and ethylbenzene manufactured from ethylene comprises
(a) SiO
2/ Al
2O
3Mol ratio is 30～500 ZSM-5 zeolite; Be stated from the zeolite
(b) rare-earth oxide of the alkaline earth metal oxide of 0.1～10% (weight) and 0.1～10% (weight).
2,, it is characterized in that wherein containing the alkaline earth metal oxide of 0.5～6% (weight) according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
3,, it is characterized in that alkaline earth metal oxide is beryllium oxide, magnesium oxide or calcium oxide according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
4,, it is characterized in that alkaline earth metal oxide is a magnesium oxide according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
5,, it is characterized in that wherein containing the rare-earth oxide of 0.3～4% (weight) according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
6,, it is characterized in that rare-earth oxide is lanthanum trioxide, Samarium trioxide, cerium oxide or its mixture according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
7,, it is characterized in that rare-earth oxide is a lanthanum trioxide according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene.
8,, it is characterized in that the SiO of ZSM-5 zeolite according to the alkylation catalyst of described benzene of claim 1 and ethylbenzene manufactured from ethylene
2/ Al
2O
3Mol ratio is 40～200.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106449A CN1079285C (en) | 1997-06-06 | 1997-06-06 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106449A CN1079285C (en) | 1997-06-06 | 1997-06-06 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201717A CN1201717A (en) | 1998-12-16 |
| CN1079285C true CN1079285C (en) | 2002-02-20 |
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| CN97106449A Expired - Lifetime CN1079285C (en) | 1997-06-06 | 1997-06-06 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101584993B (en) * | 2009-06-19 | 2011-11-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing phenylethane from dilute ethylene and benzene alkylation and method for preparing same |
| RU2410368C1 (en) * | 2009-08-03 | 2011-01-27 | Открытое акционерное общество "Салаватнефтеоргсинтез" | Method for alkylation of benzene with ethylene and catalyst for realising said method |
| CN103041846B (en) * | 2011-10-17 | 2014-10-15 | 中国石油化工股份有限公司 | Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst |
| CN103041845B (en) * | 2011-10-17 | 2014-08-20 | 中国石油化工股份有限公司 | Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition |
| CN103964994B (en) * | 2013-01-31 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method of alkylated reaction |
| CN111054429A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62151490A (en) * | 1985-12-26 | 1987-07-06 | Res Assoc Util Of Light Oil | Production of gasoline having high octane value |
| CN1031072A (en) * | 1987-08-04 | 1989-02-15 | 抚顺石油化工公司石油二厂 | Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof |
| CN1072353A (en) * | 1991-11-20 | 1993-05-26 | 中国石油化工总公司金陵石油化工公司 | Alkene and benzene alkylation solid acid catalyst |
| CN1074392A (en) * | 1992-01-13 | 1993-07-21 | 中国科学院大连化学物理研究所 | The zeolite catalyst of preparing ethyl benzene from alkylated styrene |
| CN1103607A (en) * | 1993-12-11 | 1995-06-14 | 中国科学院大连化学物理研究所 | Zeolite catalyst for producing p-methyl-ethyl benzene with ethylene and toluene |
| CN1110628A (en) * | 1994-04-18 | 1995-10-25 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
-
1997
- 1997-06-06 CN CN97106449A patent/CN1079285C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62151490A (en) * | 1985-12-26 | 1987-07-06 | Res Assoc Util Of Light Oil | Production of gasoline having high octane value |
| CN1031072A (en) * | 1987-08-04 | 1989-02-15 | 抚顺石油化工公司石油二厂 | Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst thereof |
| CN1072353A (en) * | 1991-11-20 | 1993-05-26 | 中国石油化工总公司金陵石油化工公司 | Alkene and benzene alkylation solid acid catalyst |
| CN1074392A (en) * | 1992-01-13 | 1993-07-21 | 中国科学院大连化学物理研究所 | The zeolite catalyst of preparing ethyl benzene from alkylated styrene |
| CN1103607A (en) * | 1993-12-11 | 1995-06-14 | 中国科学院大连化学物理研究所 | Zeolite catalyst for producing p-methyl-ethyl benzene with ethylene and toluene |
| CN1110628A (en) * | 1994-04-18 | 1995-10-25 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
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| CN1201717A (en) | 1998-12-16 |
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