CN102274746B - Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene - Google Patents
Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 22
- 230000029936 alkylation Effects 0.000 title claims abstract description 19
- 239000012808 vapor phase Substances 0.000 title claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- 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 33
- 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 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 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
- 235000019441 ethanol Nutrition 0.000 description 22
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 rare earth salt Chemical class 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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
- 230000008901 benefit Effects 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
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene and mainly solves problems of catalysts for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene. The problems are all undisclosed in previous literatures. The catalyst provided by the invention comprises the following components of: by weight, a) 40-90% of a ZSM-5 molecular sieve with the silica alumina mol ratio SiO2/Al2O3 being 30-400 and the crystal diameter being 5-350 nm; b) 9-59% of a binder alumina or silicon dioxide; and c) 0.1-10% of rare-earth oxide. The catalyst successively undergoes high-temperature vapor and phosphoric acid processing before use. The technical scheme greatly solves the problem. In addition, the catalyst provided by the invention can be used in the industrial production for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene.
Description
Technical field
The present invention relates to a kind of catalyst for ethanol and benzene producing ethyl benzene through alkylation in gas phase.
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, mainly contains traditional AlCl
3Liquid-phase alkylation method and molecular sieve alkylation process two large classes, wherein molecular sieve alkylation production technology has obtained very ten-strike.The eighties in 20th century, Mobil and Badger company have successfully released molecular sieve producing ethyl benzene through alkylation in gas phase technique, this process using ZSM-5 zeolite is catalyst, have the simple and heat energy recovery rate advantages of higher of, flow process pollution-free without burn into, US Patent No. 3751504, US3751506, US4016218 and US4547605 all are described in detail this.Early 1990s, Lummus and Uop Inc. have released molecular sieve preparing ethylbenzene by liquid phase alkylation technique, and this process using β and y-type zeolite are catalyst, the advantage such as have that reaction temperature is low, processing ease and accessory substance are few.US4891458, US5227558 and ZL02151177.2 all are described in detail this.
No matter this shows, be traditional AlCl
3Liquid-phase alkylation method or molecular sieve alkylation process all adopt take ethene and benzene as raw material.Grow continuously and fast along with socioeconomic, people are to the demand expanding day of base stock-oil of producing ethene, the gesture that causes oil to be petering out.Along with the growing tension of world petroleum resource and the energy, people on the one hand advocate energetically and encourage frugality resource and the energy actively seek and explore the utilization of renewable resource on the other hand.Living beings ethanol is green renewable raw materials, and along with continuous progress and the maturation of biology ethanol technology processed, the price of ethanol is expected to significant decline.Therefore, adopt ethanol to substitute ethene process route direct and benzene alkylation reaction production ethylbenzene and have stronger competitiveness.But the key technology of this process route is catalyst, and the catalyst of preparation will satisfy the needs of industrial production long-term operation, and long regeneration period and service life namely will be arranged; Simultaneously, guaranteeing on the basic bases that all transform of ethanol that catalyst will have good selective, reduces the generation of the impurity such as dimethylbenzene as far as possible, at present, not yet sees relevant report both domestic and external.
Summary of the invention
Technical problem to be solved by this invention is all unexposed catalyst for ethanol and benzene producing ethyl benzene through alkylation in gas phase of previous literature, and a kind of new catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase is provided.When this catalyst is used for ethanol and the reaction of benzene vapor-phase alkylation production ethylbenzene, have the ethanol conversion height, ethyl is selectively high, and the good characteristics of catalyst stability.
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 ethanol and benzene producing ethyl benzene through alkylation in gas phase, contain following component by weight percentage:
A) 40～90% silica alumina ratio SiO
2/ Al
2O
3Be 30～400, crystal grain diameter is the ZSM-5 molecular sieve of 5～350 nanometers;
B) 9～59% binding agent aluminium oxide or silica;
C) 0.1～10% rare-earth oxide;
Described catalyst is processed with steam and phosphoric acid successively, and then drying, roasting obtain required finished product; Wherein the steam treatment condition is normal pressure, 400～800 ℃ of temperature, steam treatment 1～20 hour; The phosphoric acid treatment conditions are to use the phosphoric acid solution of concentration 0.05～15.0 mol/L 5～95 ℃ of lower processing 1～20 hour of temperature, and the weight ratio of phosphoric acid solution and catalyst is 1～20.
In the technique scheme, the crystal grain diameter preferable range of ZSM-5 molecular sieve is 10～250 nanometers, and more preferably scope is 20～200 nanometers.ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2O
3Preferable range is 50～300.The consumption preferable range of ZSM-5 molecular sieve is 55～85% by weight percentage, and the consumption preferable range of binding agent is 14～44%, and the consumption preferable range of rare-earth oxide is 0.1～2.0%.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 normal pressure, 480～650 ℃ of temperature, steam treatment 3～10 hours.Phosphoric acid treatment conditions preferred version is to use the phosphoric acid solution of concentration 0.1～2.5 mol/L 30～95 ℃ of lower processing 3～16 hours of temperature, and the weight ratio of phosphoric acid solution and catalyst is 2～10.
Ethanol described in the present invention can be the ethanol of 95 % by weight, also can be absolute ethyl alcohol.
Catalyst of the present invention prepares in accordance with the following methods:
1) with silica alumina ratio SiO
2/ Al
2O
3The ZSM-5 molecular sieve that be 30～400, crystal grain diameter is 5～350 nanometers 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 rare-earth oxide.The rare 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 ℃, the weight ratio of rare earth salt aqueous solution and HZSM-5 molecular sieve is 0.5～10, then oven dry, roasting obtains containing the HZSM-5 molecular sieve of rare earth.The immersion condition preferred version is that rare earth salt aqueous solution concentration is 0.05～1.0 mol/L, and the weight ratio of 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 rare earth and aluminium oxide or Ludox moulding, extrusion becomes the bar shaped catalyst of 1.8 millimeters of Φ.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 is through 400～800 ℃ of steam treatment 1～20 hour, to improve the hydrothermal stability of catalyst.
5) phosphoric acid is processed.Catalyst after steam treatment, with concentration be the phosphoric acid solution of 0.05～15.0 mol/L 5～95 ℃ of lower processing 1～20 hour of temperature, the weight ratio of phosphoric acid solution and catalyst is 1～20.
6) obtain required finished product finally by dry, roasting.
In the catalytic reaction process of benzene and ethanol vapor phase alkylation ethylbenzene processed, dehydration at first occurs and generates ethene and water in ethanol under the effect of catalyst; Then alkylated reaction generation ethylbenzene occurs in ethene and benzene under the effect of same catalyst.Therefore, can produce a large amount of water in the course of reaction, water can produce adverse influence to the activity stability of catalyst under reaction condition.Adopting high-temperature vapor to process among the present invention is exactly in order to improve the hydrothermal stability of catalyst, to improve the water repelling property of catalyst under reaction condition.Adopting rare-earth element modified among the present invention also is for the hydrothermal stability that improves catalyst and selective, because rare earth element is to the stabilization of framework of molecular sieve aluminium, delay the aluminium atom and under the high-temperature vapor reaction condition, come off from skeleton, can keep for a long time the acidity-chain carrier of catalyst.Use phosphoric acid solution that catalyst is processed among the present invention, on the one hand can be to Acidity, the B acid of molecular sieve catalyst, L is sour and certain regulating action is played in the distribution of strong and weak acid, increases the total amount of B acid, reduces the intensity of acid.Can remove on the other hand amorphous substance in the molecular sieve pore passage or remove the materials such as non-framework aluminum that get off from framework of molecular sieve, play the modification to molecular sieve pore passage; Simultaneously, can further increase the adhesion of alumina key in the molecular sieve, thereby suppress the generation of framework of molecular sieve dealuminzation, improve the activity stability of catalyst, reach the purpose in extending catalyst regeneration period and service life.
Use catalyst of the present invention, 390 ℃ of reaction temperatures, reaction pressure 1.2MPa, ethanol weight space velocity (WHVS) 0.8 hour
-1, under the condition of benzene/ethanol mol ratio 6.5, ethanol conversion can reach 99.9%, and ethyl selectively can reach 99.0%, and xylene content is below 800ppm in the product ethylbenzene, and the catalyst regeneration cycle has reached half a year, has obtained preferably technique effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
200 gram silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter be the ZSM-5 molecular sieve of 200 nanometers with 2 liters 85 ℃ exchanges of the hydrochloric acid of 0.1 mol/L three times, with the deionized water washing to without the chlorine root, 110 ℃ of oven dry, for subsequent use after 4 hours 580 ℃ of roastings again.
The lanthanum nitrate aqueous solution of above-mentioned molecular sieve 20 grams and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 2 hours.Itself 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, 550 ℃ of roastings 4 hours, the catalyst that obtains contained La again 110 ℃ of bakings
2O
32.0 % by weight.
Above-mentioned catalyzer with water steam was processed 2 hours 580 ℃ of normal pressures, processed 5 hours under 50 ℃ with the phosphoric acid solution of 1.5 mol/L, phosphoric acid solution is 3 with the ratio of the weight of catalyst, and is dry rear 500 ℃ of lower roastings 3 hours, obtains finished catalyst.
[embodiment 2～11]
[embodiment 1] is identical together, just changes the SiO of ZSM-5 molecular sieve
2/ Al
2O
3Proportioning, the catalyst of mol ratio, crystal grain diameter, molecular sieve and aluminium oxide contain La
2O
32.0 amount, steam treatment and phosphoric acid treatment conditions.Specifically see Table 1.
[comparative example 1]
Identical with [embodiment 1], just catalyst is processed without lanthanum nitrate aqueous solution dipping, steam treatment and phosphoric acid.
[comparative example 2]
Identical with [embodiment 1], catalyst contains La
2O
32.0 % by weight, but process without steam treatment and phosphoric acid.
[comparative example 3]
Identical with [embodiment 1], just catalyst is processed through steam treatment and phosphoric acid, but floods without lanthanum nitrate aqueous solution.
[comparative example 4]
Identical with [embodiment 1], catalyst contains La
2O
32.0 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 2 nanometers.
[comparative example 5]
Identical with [embodiment 1], catalyst contains La
2O
32.0 % by weight.Just the ZSM-5 molecular sieve crystal grain diameter is 500 nanometers.
[embodiment 12]
Identical with [embodiment 1], just catalyst contains Ce
2O
32.0 % by weight.
[embodiment 13]
On the fixing pressurization static bed reaction unit of continuous-flow, carry out benzene and ethanol vapor phase alkylation ethylbenzene process processed.Estimate the reactivity of [embodiment 1～12], [comparative example 1～5] catalyst with selective.Reaction condition: 390 ℃ of reaction temperatures, reaction pressure 1.2MPa, benzene/ethanol 6.5 (moles/mole), ethanol weight space velocity 0.8 hour
-1, reaction result sees Table 1.
Table 1
[embodiment 14]
On the pressurization static bed reaction unit of continuous-flow, estimate the activity stability of [embodiment 1～12], [comparative example 1～5] catalyst, i.e. the regeneration period of catalyst.Reaction condition: 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, benzene/ethanol=1.0 (moles/mole), ethanol weight space velocity (WHSV)=3.0 hour
-1, the reaction time is 100 hours.Reaction result sees Table 2.
Table 2
As seen catalyst of the present invention has minimum deactivation rate, shows optimum activity stability.
Claims (2)
1. catalyst that is used for ethanol and benzene producing ethyl benzene through alkylation in gas phase, described method for preparing catalyst is as follows: 200 restrain silica alumina ratio SiO
2/ Al
2O
3=100, crystal grain diameter be the ZSM-5 molecular sieve of 200 nanometers with 2 liters 85 ℃ exchanges of the hydrochloric acid of 0.1 mol/L three times, with the deionized water washing to without the chlorine root, 110 ℃ of oven dry, for subsequent use after 4 hours 580 ℃ of roastings again; The lanthanum nitrate aqueous solution of above-mentioned molecular sieve 20 grams and 35 milliliter of 0.5 mol/L was at room temperature flooded 4 hours, then 110 ℃ of oven dry, again 550 ℃ of roastings 2 hours; Itself and alumina binder were mixed by 70: 30, and add that extruded moulding is 1.8 millimeters of Ф after the dilute nitric acid solution kneading of 2% sesbania powder and 10 % by weight; After 10 hours, 550 ℃ of roastings 4 hours, the catalyst that obtains contained La again 110 ℃ of bakings
2O
32.0 % by weight; Above-mentioned catalyzer with water steam was processed 2 hours 580 ℃ of normal pressures, processed 5 hours under 50 ℃ with the phosphoric acid solution of 1.5 mol/L, phosphoric acid solution is 3 with the ratio of the weight of catalyst, and is dry rear 500 ℃ of lower roastings 3 hours, obtains finished catalyst.
2. one kind is adopted the as claimed in claim 1 method of catalyst synthesizing ethyl benzene, on the fixing pressurization static bed reaction unit of continuous-flow, carry out benzene and ethanol vapor phase alkylation ethylbenzene processed, reaction temperature is 390 ℃, reaction pressure is 1.2MPa, and the ethanol weight space velocity is 0.8 hour
-1, benzene/ethanol mol ratio is 6.5, and ethanol conversion is 99.5%, and ethyl selectively is 99.6%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102000205A CN102274746B (en) | 2010-06-11 | 2010-06-11 | Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene |
| US13/158,709 US8519208B2 (en) | 2010-06-11 | 2011-06-13 | Processes for synthesizing ethylbenzene from ethanol and benzene |
| BRPI1103071-2A BRPI1103071B1 (en) | 2010-06-11 | 2011-06-13 | ETHYL BENZEN SYNTHESIS PROCESS FROM ETHANOL AND BENZENE |
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| CN2010102000205A CN102274746B (en) | 2010-06-11 | 2010-06-11 | Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene |
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| CN102274746B true CN102274746B (en) | 2013-04-10 |
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| CN103418419B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of alkylation to prepare ethylbenzene |
| CN110743605B (en) | 2018-07-23 | 2021-07-27 | 中国科学院大连化学物理研究所 | A kind of catalyst for preparing ethylbenzene from ethanol and benzene and its preparation and application |
| CN110882715B (en) * | 2018-09-07 | 2021-03-26 | 中国科学院大连化学物理研究所 | A kind of catalyst for preparing ethylbenzene by gas-phase alkylation of ethanol and benzene and its preparation and application |
| CN114073976B (en) * | 2020-08-10 | 2023-04-07 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
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| CN101279283A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof |
| CN101584993A (en) * | 2009-06-19 | 2009-11-25 | 中国科学院大连化学物理研究所 | Catalyst for producing ethylbenzene by alkylation of dilute ethylene and benzene and preparation method thereof |
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