CN102872900A - Catalyst for dry gas and benzene alkylation to prepare ethylbenzene - Google Patents
Catalyst for dry gas and benzene alkylation to prepare ethylbenzene Download PDFInfo
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- CN102872900A CN102872900A CN2011101926526A CN201110192652A CN102872900A CN 102872900 A CN102872900 A CN 102872900A CN 2011101926526 A CN2011101926526 A CN 2011101926526A CN 201110192652 A CN201110192652 A CN 201110192652A CN 102872900 A CN102872900 A CN 102872900A
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- molecular sieve
- alkylation
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 25
- 230000029936 alkylation Effects 0.000 title claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 61
- 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 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- 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 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 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
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 20
- 239000005977 Ethylene Substances 0.000 abstract description 14
- 230000008929 regeneration Effects 0.000 abstract description 12
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000004615 ingredient Substances 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
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 238000000465 moulding Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- -1 rare earth salt Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 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 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005406 washing Methods 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 relates to a catalyst for dry gas and benzene alkylation to prepare ethylbenzene and mainly solves the problem that a catalyst has poor stability and short regeneration period during the reaction process of dilute ethylene (dry gas) and benzene for production of ethylbenzene in the prior art. The catalyst provided by the invention contains the following ingredients of: by weight, a) 40-90% of a ZSM-5 molecular sieve with the grain size being 5-500 nm and the silicon-aluminium mol ratio SiO2/Al2O3 being 30-400; b) 9-59% of a binder alumina or silicon dioxide; and c) 0.1-10% of alkaline earth oxide and 0.1-10% of rare-earth oxide. The catalyst undergoes high-temperature steam treatment, drying and roasting to obtain the required finished product, wherein the steam treatment is carried out at normal pressure at the temperature of 400-800 DEG C for 1-20 hours. By the adoption of the technical scheme, the above problem is solved well. The catalyst provided by the invention can be used in industrial production of dry gas and benzene alkylation to prepare ethylbenzene.
Description
Technical field
The present invention relates to a kind of catalyst for dry gas and producing phenylethane from alkylation of benzene, particularly a kind of catalyst of under the vapor-phase alkylation condition, producing ethylbenzene for dry gas and benzene.
Background technology
Ethylbenzene is important petrochemical materials, is mainly used in cinnamic production, and styrene is the primary raw material of producing polystyrene and other copolymer resins.
Ethylbenzene can be produced with various process, and traditional catalyst has crystallization and noncrystalline silica, boron fluoride, aluminium oxide, phosphoric acid, alchlor and solid phosphoric acid catalyst.All there are the shortcomings such as seriously corroded, equipment investment is large, the three wastes are many in these conventional catalyst techniques.In recent years, people have carried out extensive and deep research to molecular sieve, and some companies constantly are devoted to utilize molecular sieve to produce the new technology of ethylbenzene as catalyst.Wherein having obtained great commercial a kind of method is in the presence of a kind of solid acid ZSM-5 zeolite catalyst, carries out vapor phase alkylation with pure ethylene and benzene.US Patent No. 3751504, US3751506, US4016218 and US4547605 all are described in detail this, but all exist short shortcoming of catalyst regeneration cycle.
ZL96100371.5 and ZL98113847.0 have reported respectively the technique of two kinds of dry gas and benzene preparing ethylbenzene by reaction.A kind of technique is the dry gas from plant catalytic refinery or catalytic pyrolysis or thermal cracking, do not need directly to enter the vapor phase alkylation device that molecular sieve catalyst is housed and react through refining, the many ethylbenzene that produce enter a gas phase transalkylation reactor, be converted into again ethylbenzene, and another technique alkylation part is substantially similar, difference is that the many ethylbenzene that produce enter a liquid-phase transalkylation reactor, are translated into ethylbenzene.But the shortcomings such as these two kinds of techniques all exist poor catalyst stability, and regeneration period and service life are short.
ZL94113403.2, ZL96106561.3 and ZL200510011505.9 have reported respectively ZSM-5/ZSM-11 eutectic molecular sieve and the application of Y zeolite in the preparing ethylbenzene from dry gas reaction, wherein only have ZL96106561.3 to relate to the activity stability (regeneration period) of catalyst, namely to contain 19.5% (body) ethene, the catalytic cracked dry gas of 0.8% (body) propylene is that raw material is when carrying out benzene and ethylene alkylation, at reaction pressure 0.9MPa, weight ethylene air speed 0.8h-1, benzene/ethylene molecule is than under 10 the condition, can only continuous operation 95 days, can not satisfy the requirement of industrial production long-period stable operation.
CN200810032814.8 discloses a kind of benzene alkylation nano molecular sieve catalyst and its preparation method and application.Can be used for benzene alkylation reaction although the document discloses nano molecular sieve, how many nanometers the particle diameter of synthetic molecular sieve is not actually in the disclosed embodiment, and the service life of catalyst.The inventor has synthesized molecular sieve catalyst according to the disclosed preparation method of the document, uses it in the reaction of preparing ethylbenzene from dry gas, finds still to exist poor catalyst stability, the shortcoming that service life is short.
In sum, exist rare ethene (dry gas) and benzene reaction to produce in the process of ethylbenzene poor catalyst stability, the problem that the regeneration period is short in the prior art.
Summary of the invention
Technical problem to be solved by this invention is to exist rare ethene (dry gas) and benzene reaction to produce in the process of ethylbenzene in the prior art, poor catalyst stability, the problem that regeneration period is short provides a kind of new catalyst that is used for dry gas and producing phenylethane from alkylation of benzene.This catalyst has good stability, the characteristics that the regeneration period is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for dry gas and producing phenylethane from alkylation of benzene, contain following component by weight percentage:
A) 40～90% crystal grain diameter is 5～500 nanometers, silica alumina ratio SiO
2/ Al
2O
3It is 30～400 ZSM-5 molecular sieve;
B) 9～59% binding agent aluminium oxide or silica;
C) 0.1～10% alkaline earth oxide and 0.1～10% rare-earth oxide;
Described catalyst is processed through high-temperature vapor, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is for being under 400～800 ℃ of conditions in normal pressure, temperature, steam treatment 1～20 hour.
In the technique scheme, the crystal grain diameter preferable range of ZSM-5 molecular sieve is 10～450 nanometers, and more preferably scope is＞100～400 nanometers.ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Preferable range is 50～300.In the used catalyst, the consumption preferable range of ZSM-5 molecular sieve is 55～85% by weight percentage, the consumption preferable range of binding agent is 14～44%, and the consumption preferable range of alkaline earth oxide is 0.1～3.0%, and the consumption preferable range of rare-earth oxide is 0.1～3.0%.Described alkaline earth oxide preferred version is for being selected from magnesia, calcium oxide or beryllium oxide, and more preferably scheme is for being selected from magnesia.Described rare-earth oxide preferred version is for being selected from lanthana, cerium oxide or praseodymium oxide, and more preferably scheme is for being selected from lanthana.Steam treatment condition preferred version is that normal pressure, temperature are 480～650 ℃, steam treatment 3～10 hours.
Catalyst of the present invention prepares in accordance with the following methods:
1) with crystal grain diameter is 5～500 nanometers, silica alumina ratio SiO
2/ Al
2O
3Be that 30～400 ZSM-5 molecular sieve well known to a person skilled in the art that hydrochloric acid exchange, washing, oven dry and roasting obtain the HZSM-5 molecular sieve under the condition.
2) molecular sieve carried alkaline earth oxide and rare-earth oxide.The alkaline earth salt aqueous solution that is 0.002～2.0 mol/L with above-mentioned HZSM-5 molecular sieve concentration flooded 1～15 hour at 10～60 ℃, and the weight ratio of the alkaline earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting; The HZSM-5 molecular sieve concentration that will contain again alkaline earth is that the rare earth salt aqueous solution of 0.002～2.0 mol/L flooded 1～15 hour at 10～60 ℃, and the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting.The immersion condition preferred version is that alkaline earth salt and rare earth salt aqueous solution concentration are 0.05～1.0 mol/L, and the weight ratio of alkaline earth salt and rare earth salt aqueous solution and HZSM-5 molecular sieve is 1～5, and dipping temperature is 20～40 ℃, and dip time is 2～10 hours.
3) shaping of catalyst.With step 2) preparation the HZSM-5 molecular sieve that contains alkaline earth and rare earth and aluminium oxide or Ludox moulding, extrusion is in strip catalyst.Above-mentioned catalyst is again through 110 ℃ of oven dry in 10 hours and 550 ℃ of roastings in 4 hours.
4) steam treatment.Preformed catalyst was normal pressure, 400～800 ℃ of steam treatment 1～20 hour, and then drying, roasting obtain described catalyst.
When catalyst of the present invention was used for dry gas and producing phenylethane from alkylation of benzene, reaction condition was: 280～430 ℃ of reaction temperatures, reaction pressure 0.5～2.8MPa, weight ethylene air speed 0.2～5.0 hour
-1, total benzene/ethylene molar ratio 2～10; Preferable range is: 320～400 ℃ of reaction temperatures, reaction pressure are 0.7～1.6MPa, weight ethylene air speed 0.4～3.0 hour
-1, total benzene/ethylene molar ratio 5～8.The raw material dry gas does not contain free water, H
2S content＜8500 milligram/meter
3, CO
2Content＜4.0 volume %, C
3 =And C
4 =Content＜0.8 volume % does not need to make with extra care in advance directly and can react with benzene.
In the catalytic reaction process of benzene and ethene vapor phase alkylation ethylbenzene processed, because reaction carries out under hot conditions, so catalyst is easy to because of the coking inactivation, and activity stability is relatively poor, and the regeneration period is short.At first, the present invention adopts nano level ZSM-5 molecular sieve, because Kong Cheng is relatively short, reactant and product are at the time shorten of pore diffusion, the probability reduction that the side reactions such as oligomerisation, cyclisation generate polycyclic aromatic hydrocarbon occurs in the hole, thereby establishment the generation of catalyst coking, improved the activity stability of catalyst.Secondly, the present invention adopts alkaline earth and rare-earth element modified catalyst, but one side alkaline earth element regulating catalyst acid strength suppresses the easily strong acidic site of generation coking reaction, the activity stability of raising catalyst and selective; Rare earth element is with the hydrothermal stability that improves catalyst and selective on the other hand, because rare earth element is to the stabilization of framework of molecular sieve aluminium, thereby suppressed the generation of framework of molecular sieve dealuminzation, improved the activity stability of catalyst, reached the purpose of extending catalyst regeneration period.At last, crucial is that the employing high-temperature vapor was processed before catalyst of the present invention used, and had further improved the hydrothermal stability of catalyst, had improved the water repelling property of catalyst under reaction condition.In a word, the present invention adopts nano molecular sieve, adopts alkaline earth and rare-earth element modified catalyst, high-temperature vapor to process the method that the three combines, when carrying out benzene and ethylene alkylation take the catalytic cracked dry gas that contains 18.9% (body) ethene, 1.5% (body) propylene as raw material, at reaction pressure 0.9MPa, weight ethylene air speed 0.8 hour
-1, under the condition of benzene/ethylene molar ratio 8, conversion of ethylene can reach 99.5%, and ethyl selectively can reach 99.0%, and the catalyst regeneration cycle reached more than 1 year, had obtained preferably technique effect.
Give further instruction below by embodiment to the present invention.
The specific embodiment
[embodiment 1]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.1 % by weight magnesia and 1.5 % by weight lanthanas 110 ℃ of bakings; After normal pressure, 560 ℃ were processed 6 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 2]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.3 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 30 milliliter of 0.01 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 1.5 % by weight magnesia and 0.2 % by weight lanthana 110 ℃ of bakings; After normal pressure, 580 ℃ were processed 5 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 3]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 110 nanometers and the magnesium nitrate aqueous solution of 50 milliliter of 0.5 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 30 milliliter of 0.05 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 65: 35, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 3.0 % by weight magnesia and 0.5 % by weight lanthana 110 ℃ of bakings; After normal pressure, 600 ℃ were processed 4 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 4]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 110 nanometers and the lanthanum nitrate aqueous solution of 50 milliliter of 0.5 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned magnesium nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.02 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 60: 40, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.3 % by weight magnesia and 3.0 % by weight lanthanas 110 ℃ of bakings; After normal pressure, 650 ℃ were processed 3 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 5]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=50, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.1 % by weight magnesia and 1.5 % by weight lanthanas 110 ℃ of bakings; After normal pressure, 525 ℃ were processed 7 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 6]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=200, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.1 % by weight magnesia and 1.5 % by weight lanthanas 110 ℃ of bakings; After normal pressure, 500 ℃ were processed 8 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 7]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=300, crystal grain diameter is that the ZSM-5 molecular sieve of 250 nanometers and the magnesium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Again the above-mentioned lanthanum nitrate aqueous solution that contains magnesian molecular sieve and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.1 % by weight magnesia and 1.5 % by weight lanthanas 110 ℃ of bakings; After normal pressure, 480 ℃ were processed 9 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[embodiment 8]
With 20 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter is that the ZSM-5 molecular sieve of 200 nanometers and the calcium nitrate aqueous solution of 30 milliliter of 0.02 mol/L at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Contain the molecular sieve of calcium oxide and the cerous nitrate aqueous solution of 35 milliliter of 0.5 mol/L at room temperature flooded 4 hours with above-mentioned again, then 110 ℃ of oven dry, again 550 ℃ of roastings 3 hours; Above-mentioned molecular sieve and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Φ after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight.After 10 hours, again 550 ℃ of roastings 4 hours, obtain containing the catalyst of 0.1 % by weight calcium oxide and 1.5 % by weight cerium oxide 110 ℃ of bakings; After normal pressure, 580 ℃ were processed 5 hours, drying, roasting obtained finished catalyst with above-mentioned catalyzer with water steam.
[comparative example 1]
Identical with [embodiment 1], just adopt the ZSM-5/ZSM-11 eutectic molecular sieve.
[comparative example 2]
Identical with [embodiment 1], just molecular sieve without magnesium nitrate and lanthanum nitrate aqueous solution dipping, catalyst without steam treatment.
[comparative example 3]
Identical with [embodiment 1], catalyst contains 0.1 % by weight magnesia and 1.5 % by weight lanthanas, but without steam treatment.
[comparative example 4]
Identical with [embodiment 1], just catalyst is through steam treatment, but molecular sieve floods without lanthanum nitrate aqueous solution.
[comparative example 5]
Identical with [embodiment 1], catalyst contains 0.1 % by weight magnesia and 1.5 % by weight lanthanas, and just the ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 6]
Identical with [embodiment 1], catalyst contains 0.1 % by weight magnesia and 1.5 % by weight lanthanas, and just the ZSM-5 molecular sieve crystal grain diameter is 550 nanometers.
[comparative example 7]
According to [embodiment 1] disclosed method synthesis of molecular sieve among the document CN200810032814.8, then prepared catalyst according to [embodiment 7] disclosed method, contain the magnesia of 3.8 % by weight and the lanthana of 5.7 % by weight in the gained catalyst.
[embodiment 9]
On the pressurization static bed reaction unit of continuous-flow, estimate the activity stability of [embodiment 1～8], [comparative example 1～7] catalyst, i.e. the regeneration period of catalyst.Reaction condition: 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, benzene/ethene=1.0 (moles/mole), weight ethylene air speed (WHSV)=2.5 hour
-1, the reaction time is 100 hours.Reaction result sees Table 1.
Table 1
As seen the catalyst among the present invention has minimum deactivation rate, shows optimum activity stability.Move at commercial plant, the catalyst regeneration cycle reached more than 1 year.
Claims (8)
1. catalyst that is used for dry gas and producing phenylethane from alkylation of benzene, contain following component by weight percentage:
A) 40～90% crystal grain diameter is 5～500 nanometers, silica alumina ratio SiO
2/ Al
2O
3It is 30～400 ZSM-5 molecular sieve;
B) 9～59% binding agent aluminium oxide or silica;
C) 0.1～10% alkaline earth oxide and 0.1～10% rare-earth oxide;
Described catalyst is processed through high-temperature vapor, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is for being under 400～800 ℃ of conditions in normal pressure, temperature, steam treatment 1～20 hour.
2. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 1, the crystal grain diameter that it is characterized in that ZSM-5 molecular sieve is 10～450 nanometers.
3. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 2 is characterized in that the crystal grain diameter of ZSM-5 molecular sieve is＞100～400 nanometers.
4. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 1 is characterized in that ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Be 50～300.
5. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 1, it is characterized in that used catalyst by weight percentage the consumption of ZSM-5 molecular sieve be 55～85%, the consumption of binding agent is 14～44%, the consumption of alkaline earth oxide is 0.1～3.0%, and the consumption of rare-earth oxide is 0.1～3.0%.
6. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 1 is characterized in that described alkaline earth oxide is selected from magnesia, calcium oxide or beryllium oxide, and described rare-earth oxide is selected from lanthana, cerium oxide or praseodymium oxide.
7. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 6 is characterized in that described alkaline earth oxide is selected from magnesia, and described rare-earth oxide is selected from lanthana.
8. the catalyst for dry gas and producing phenylethane from alkylation of benzene according to claim 1 is characterized in that the steam treatment condition is that normal pressure, temperature are 480～650 ℃, steam treatment 3～10 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106244224A (en) * | 2015-06-12 | 2016-12-21 | 中国石油化工股份有限公司 | Dry gas produces the method for gasoline mediation component |
| CN106281433A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | Oil refinery dry gas produces the method for gasoline mediation component |
| RU2608037C1 (en) * | 2015-09-21 | 2017-01-12 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method of producing catalyst, catalyst and method for alkylation of benzene with ethylene using said method |
| CN106944129A (en) * | 2017-03-07 | 2017-07-14 | 中国科学院大连化学物理研究所 | Preparation method for dry gas and the molecular sieves of 11@Silicalite of benzene alkylation reaction nucleocapsid ZSM 2 |
| RU2812584C1 (en) * | 2023-05-15 | 2024-01-30 | Общество с ограниченной ответственностью "Газпром нефтехим Салават" | Method of producing catalyst, catalyst and method of alkylation of benzene with ethylene using its |
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| CN1508105A (en) * | 2002-12-17 | 2004-06-30 | 中国石油化工股份有限公司上海石油化 | Method for preparing ethylbenzene by liquid phase alkylation of ethylene |
| CN101485993A (en) * | 2008-01-18 | 2009-07-22 | 上海师范大学 | Novel nano molecular sieve catalyst for benzene alkylation as well as preparation method and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106244224A (en) * | 2015-06-12 | 2016-12-21 | 中国石油化工股份有限公司 | Dry gas produces the method for gasoline mediation component |
| CN106281433A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | Oil refinery dry gas produces the method for gasoline mediation component |
| CN106281433B (en) * | 2015-06-12 | 2018-02-13 | 中国石油化工股份有限公司 | The method of oil refinery dry gas production gasoline mediation component |
| RU2608037C1 (en) * | 2015-09-21 | 2017-01-12 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method of producing catalyst, catalyst and method for alkylation of benzene with ethylene using said method |
| CN106944129A (en) * | 2017-03-07 | 2017-07-14 | 中国科学院大连化学物理研究所 | Preparation method for dry gas and the molecular sieves of 11@Silicalite of benzene alkylation reaction nucleocapsid ZSM 2 |
| RU2812584C1 (en) * | 2023-05-15 | 2024-01-30 | Общество с ограниченной ответственностью "Газпром нефтехим Салават" | Method of producing catalyst, catalyst and method of alkylation of benzene with ethylene using its |
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