CN1134385C - Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process - Google Patents
Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process Download PDFInfo
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- CN1134385C CN1134385C CNB001318136A CN00131813A CN1134385C CN 1134385 C CN1134385 C CN 1134385C CN B001318136 A CNB001318136 A CN B001318136A CN 00131813 A CN00131813 A CN 00131813A CN 1134385 C CN1134385 C CN 1134385C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000004568 cement Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- -1 trace assistant Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 230000007420 reactivation Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical group 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention relates to a catalyst. Fe-K-Ce-Mo-Mg is used as a main system; when trace composite systems are added and a four-stage pulse temperature control activation technology is adopted, the prepared catalyst has the advantages of good performance, high reactivity selectivity at a low water rate and high self regeneration capacity. The catalyst preparation process of the present invention has the advantages of simplicity and high operating flexibility.
Description
The present invention relates to a kind of alkyl aromatics dehydrogenation and produce alkyl alkenyl arene catalyst system therefor and preparation method thereof, be specially adapted to ethylbenzene, diethylbenzene or ethyltoluene dehydrogenation and generate vinylbenzene, divinylbenzene, perhaps the dehydrogenating technology process of vinyl toluene.
For many years, the production of alkenyl arene is mainly undertaken by alkyl aromatics dehydrogenation, and one of key of this production technology is exactly a dehydrogenation catalyst.Dehydrogenation catalyst is by early stage Fe
2O
3System and ZnO are two big classes, differentiation through Fe-K-Cr and Fe-K-Ce-Mo system, developed into Fe-K-Ce-Mo-Mg be main body system the 4th generation catalyzer, as: CN1062678, US4758543 etc. are characterized in potassium compound content height in the catalyzer, generally 10～30%, belong to high potassium type catalyzer, easily cause potassium lost in the use, influence catalyst life, existing in addition catalyzer adopts the single hop activating technology more, and the catalyzer principal crystalline phase is with α-Fe
2O
3Be main, general transformation efficiency is lower than 75%, and selectivity is lower than 94%, and the water ratio of use is 2.0, and use temperature is 620 ℃.WO9710898 etc. also provide the two stage activation technology, with the ferrite that obtains different potassium as catalyzer, as K
2Fe
22O
34The object of the present invention is to provide a kind of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst and preparation method thereof that is used for, not only the preparation method is simple, and catalyzer has very high activity, selectivity and stability.
For achieving the above object, contain active constituent in the composition of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of the present invention: (in the oxide compound of reactive metal, weight percent): Fe
2O
330～75%, be preferably 55～65%, K
2O 5～25%, are preferably 5～15%, Ce
2O
35～30%, be preferably 10～20%, MgO 0.01～10%, is preferably 0.5～10%, MoO
30.1～6%, be preferably 0.5～5%.Pore-creating agent 1～5%, specific surface are 2.0～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K
2Fe
2O
4Be main, as shown in Figure 1.
Fig. 1 is the crystalline phase figure of the catalyzer implementing the present invention and obtain.
The principal crystalline phase that Fig. 2 obtains for Comparative Examples 1 is with Fe
2O
3Be the crystalline phase figure of master's catalyzer.
Preferably also contain in the metal in micro-IB～VIIIB, IIIA～VA family one or more in the composition of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of the present invention as auxiliary agent, as Rb, Sr, Ti, V, W, Mn, Co, Ni, Cu, Zn, Sn, Pb, its consumption is 0～1wt%, and form that can its metal oxide adds.
The reactivity worth of catalyzer mainly is subjected to the influence of potassium content in the catalyzer, potassium and iron are formed the activity of such catalysts center jointly, but the existence of potassium in catalyzer is unsettled often, because the strong heat absorptivity of dehydrogenation reaction, part potassium is moved to the center by the granules of catalyst surface, and, cause catalyst activity reduction and reaction bed resistance drop to increase the work-ing life of having reduced catalyzer by of the migration of reactor inlet high-temperature zone to cold zone.In addition, vapor partial pressure also is an important factor that influences potassium lost, therefore it is assurance catalyzer work-ing life, the content of potassium oxide generally all is not less than 10wt% in the catalyzer, even bring up to more than the 30wt%, high potassium type catalyzer exists potassium lost and causes the active fast shortcoming that descends when using.
Catalyzer among the present invention is because principal crystalline phase is K
2Fe
2O
4, the active centre demonstrates extremely strong activity, and has pind down the migration of K, avoided the loss of K, therefore use the potassium amount very low, under the condition of suitable specific surface, pore volume, pore size distribution, can demonstrate high activity, the catalyzer life cycle is long, active, selectivity is stablized, for cooperating the characteristics of low potassium type, when selecting Ce, its content is higher relatively, to satisfy the needs to catalyst performance.
Also can further improve selectivity of catalyst and stability as containing trace assistant in the catalyzer of the present invention.
Preparation is during catalyzer, and the adding of active ingredient can be the oxide compound of metal, also can be the salt etc. of metal monomer, metal, is the compound that finally obtains metal oxide by certain approach in a word, as Fe
2O
3Can form that roasting makes after the precipitation of hydroxide from molysite and basic solution effect, also can decompose and obtain, can also use Fe by molysite such as vitriol, nitrate, oxalate roasting
2O
3H
2O, Fe
3O
4The adding of K can be KOH, K
2CO
3, Potassium ethanoate; Used cerium can add with vitriol, nitrate, oxalate form; Molybdenum can add with molybdate or its double salt form; Magnesium can add or the like with oxide compound, oxyhydroxide, magnesium salts form.
Pore-creating agent of the present invention can use conventional polystyrene microsphere, graphite, carboxymethyl cellulose; Caking agent can be known cement.
The present invention also provides a kind of method for preparing this catalyzer, has adopted the fairly simple co-precipitation extrusion process of technology.
Preparation of catalysts method of the present invention is:
To add in the container respectively by active ingredient, trace assistant, cement, pore-creating agent, the deionized water of proportioning weighing and stir, extrusion molding, dry in room temperature or drying baker, dried mixture activates in stoving oven, and reactivation process is that four sections pulse temperature controls activate continuously:
One section: 50～100 ℃ of 0.5～2h
Two sections: 100～300 ℃ of 0.5～2h
Three sections: 300～700 ℃ of 3～7h
Four sections: after 700～900 ℃ of 0.5～1h reactivation processs are finished, promptly get catalyzer of the present invention.
Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of the present invention and preparation method thereof, not only the preparation method is simple, and catalyzer has very high activity, selectivity and stability.When using catalyzer of the present invention to be used for ethyl benzene dehydrogenation preparation of styrene, normal pressure, isothermal, 620 ℃, under the condition of water hydrocarbon than (water/ethylbenzene) 2.0,1.0 liters of ethylbenzene of liquid air speed/rise catalyzer hour, conversion of ethylbenzene is the highest can be up to more than 80%, selectivity of styrene is greater than 95%, and the life cycle of catalyzer is 2 years.Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The invention is further illustrated by the following examples, and activity rating of catalyst carries out in the isotherm formula fixed bed, and its evaluation procedure is summarized as follows:
After the deionized water of volume pump output and ethylbenzene enter preheater and carry out preheating and mix, be gaseous state and enter reactor, reactor adopts the nichrome wire heating, temperature control is to preset temperature, reactor is the stainless steel tube of Φ 32mm, apparatus with catalyst inside 100ml, the product after the dehydrogenation use its composition of gas chromatographic analysis after condensation separation.Further describe the present invention with embodiment below.
Embodiment 1:
With ferric oxide 298g, Sodium orthomolybdate 13g, magnesium hydroxide 25g, cement 40g, 100g K
2CO
3, the cerous nitrate of 120g and micro-combined system 2.3g be (by TiO
20.5g, V
2O
50.2g, CoO 0.3g, NiO 0.2g, MnO
20.1g, CuO 0.8g, SnO 0.2g form), deionized water is added in the kneader respectively and stirs, add polystyrene microsphere 5g again and add kneader stirring 0.5 hour, take out the particle that the extrusion pelletizing becomes the long 7～10mm of Φ 3mm, place activation furnace by 850 ℃ of 0.5h of 580 ℃ of 6h of 180 ℃ of 1h of 80 ℃ of 1h, program animation, the finished catalyst specific surface is 2.6～3.4g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K
2Fe
2O
4Be main, as shown in Figure 1.With the 100ml catalyzer isothermal evaluating apparatus of packing into, appreciation condition is: reaction pressure is a normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer hour, 620 ℃ of temperature of reaction, water is than (water/ethylbenzene) 2.0 (weight ratio), evaluation result: conversion of ethylbenzene 80.2%, selectivity of styrene 95.4%.
With ferric oxide 310g, Sodium orthomolybdate 20g, magnesium oxide 15g, cement 35g, 85gK
2CO
3, the Sedemesis of 120g, and minor component system 2.1g is (by ZnO 0.6g, PbO
20.2g, TiO
20.4g, V
2O
50.5g, MnO
20.2, CoO 0.2g forms), deionized water adds kneader respectively and mixes and stir fully, adds pore-creating agent Graphite Powder 99 6g again, back extrusion pelletizing activates with following condition: 90 ° of 1h → 180 ℃ 0.5h → 600 ℃ of 5h → 800 ° 1h.Obtain finished catalyst, specific surface is 2.7～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K
2Fe
2O
4Be main, estimate evaluation result by embodiment 1 method again: conversion of ethylbenzene 80.85%, selectivity of styrene 95.7%.
With ferric oxide 285g, ammonium molybdate 15g, magnesium hydroxide 20g, cement 30g, micro-combined system 2.4g is (by V
2O
50.5g, CoO 0.6g, WO
30.4g, PbO
20.4g, NiO 0.1g, SnO
20.4g form), K
2CO
3110g, 135 cerous nitrate, deionized water add kneader respectively and mix stirring fully, stir fully behind the adding carboxymethyl cellulose 10g, and back extrusion pelletizing activates with following condition: 60 ℃ of 2h → 200 ℃ 2h → 700 ℃ of 4h → 900 ° 0.5h.Obtain finished catalyst, specific surface is 2.2～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K
2Fe
2O
4Be main.Estimate under the normal pressure isothermal condition, 620 ℃ of temperature of reaction, water is than (water/ethylbenzene) 1.3 o'clock, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer, and conversion of ethylbenzene can reach 76.6%, and selectivity of styrene is 95.4%.
With 305g ferric oxide, ammonium molybdate 18g, magnesium hydroxide 10g, cement 35g, micro-combined system 2.2g (0.4%) is (by CoO 0.3g, Li
2O 0.2g, Rb
2O 0.3g, SrO 0.4g, MnO
20.6g, V
2O
50.4g form), K
2CO
3100g, the cerous nitrate of 132g, pore-creating agent carboxymethyl cellulose 88g makes catalyzer by embodiment 1 method, estimates conversion of ethylbenzene 80.65%, selectivity 95.7% by the appreciation condition of embodiment 1.Reduce the water ratio to 1.3 (weight ratios), then conversion of ethylbenzene 76.6%, selectivity 95.9%.According to the appreciation condition of embodiment 1, the steam of cutting off the water continues logical ethylbenzene again, continues water flowing steam after 30 minutes and reacts.Evaluation result: conversion of ethylbenzene 80.15%, selectivity 95.6% illustrates that catalyzer of the present invention is strong from regeneration power.
Embodiment 5
With 340g ferric oxide, ammonium molybdate 22g, magnesium hydroxide 15g, cement 35g, micro-combined system 2.2g (0.4%) is (by CoO 0.3g, Li
2O 0.2g, Rb
2O 0.3g, SrO 0.4g, MnO
20.6g, V
2O
50.4g form), K
2CO
360g, the cerous nitrate of 132g, pore-creating agent Graphite Powder 99 10g makes catalyzer by embodiment 1 method, estimates evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 79.36%, selectivity of styrene 95.25%.
Embodiment 6
With ferric oxide 300g, Sodium orthomolybdate 10g, magnesium hydroxide 25g, cement 35g, 140gK
2CO
3, the cerous nitrate of 100g behind the 150g deionized water dissolving, adds to mix in the kneader and stirred 2 hours, and the 15g Graphite Powder 99 is added, and makes catalyzer, uses the appreciation condition of embodiment 1, evaluation result: conversion of ethylbenzene 76.48%, selectivity 95.7%.
Embodiment 7
Press embodiment 6 prescription, other adds minor component is CoO 1g, makes catalyzer by the method for embodiment 1, estimates evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 76.8%, selectivity 95.4%.
Embodiment 8
Press embodiment 1 prescription, minor component is become 1.5g (by CoO 0.5g, V
2O
50.5g, MnO
20.5g form), make catalyzer by the method for embodiment 1, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 77.26%, selectivity 95.41%.
Embodiment 9
Press embodiment 1 prescription, minor component is become 1.9g (by Li
2O 0.3g, Rb
2O 0.4g, V
2O
50.5g, SrO
20.7g form), make catalyzer by the method for embodiment 1, estimate evaluation result by the appreciation condition of embodiment 1; Conversion of ethylbenzene 77.82%, selectivity 95.6%.Comparative Examples 1
Behind the shaping of catalyst that makes by embodiment 1 prescription, activate by 580 ℃, the condition of 6h, the catalyzer principal crystalline phase that makes is with Fe
2O
3Be main, as shown in Figure 2.Estimate evaluation result again by the appreciation condition of embodiment 1: conversion of ethylbenzene 70.5%, selectivity 95.1%.
Claims (3)
1. Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst is characterized in that containing in the composition of catalyzer: Fe
2O
330～75wt%, K
2O 5～25wt%, Ce
2O
35～30wt%, MgO 0.01～10wt%, MoO
30.1～6wt%, as auxiliary agent, its consumption is 0～1wt%, pore-creating agent 1～5% with among Rb, Sr, Ti, V, W, Mn, Co, Ni, Cu, Zn, Sn, the Pb one or more; Specific surface is 2.0～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is K
2Fe
2O
4
2. catalyzer according to claim 1 is characterized in that containing Fe in the composition of catalyzer
2O
355～65wt%, K
2O 5～15wt%, Ce
2O
310～20wt%, MgO 0.5～10wt%, MoO
30.5～5wt%, as auxiliary agent, its consumption is 0～1wt%, pore-creating agent 1～5% with among Rb, Sr, Ti, V, W, Mn, Co, Ni, Cu, Zn, Sn, the Pb one or more; Specific surface is 2.0～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is K
2Fe
2O
4
3. claim 1 or 2 described Preparation of catalysts methods, it is characterized in that to add in the container respectively by active ingredient, trace assistant, cement, pore-creating agent, caking agent, the deionized water of proportioning weighing and stir, extrusion molding, dry in room temperature or drying baker, dried mixture activates in stoving oven, and reactivation process is that four sections pulse temperature controls activate continuously:
One section: 50～100 ℃ of 0.5～2h
Two sections: 100～300 ℃ of 0.5～2h
Three sections: 300～700 ℃ of 3～7h
Four sections: 700～900 ℃ of 0.5～1h
After reactivation process was finished, the principal crystalline phase of catalyzer was K
2Fe
2O
4, promptly get catalyzer of the present invention.
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| CNB001318136A CN1134385C (en) | 2000-10-18 | 2000-10-18 | Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process |
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| CNB001318136A CN1134385C (en) | 2000-10-18 | 2000-10-18 | Alkylarylhydrocarbon dehydrogenating catalyst and its preparing process |
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| CN1134385C true CN1134385C (en) | 2004-01-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728371A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN102909013B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Preparation method for dehydrogenation catalyst with steam dechlorination and reduction performed simultaneously |
| CN102909017B (en) * | 2011-08-01 | 2014-07-23 | 中国石油化工股份有限公司 | Method for stepwise activating dehydrogenation catalyst by using synthesis gas and CO-containing gas |
| CN103372452B (en) * | 2012-04-24 | 2015-08-19 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN105749934B (en) * | 2014-12-15 | 2018-12-28 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation with low water ratio and preparation method thereof |
| CN105777480B (en) * | 2014-12-15 | 2018-10-16 | 中国石油天然气股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN112237919A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene |
| CN114425359B (en) * | 2020-10-14 | 2023-08-04 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene, preparation method and application thereof and ethylbenzene dehydrogenation method |
| CN115487833B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation in low water ratio environment, preparation method and application thereof and ethylbenzene dehydrogenation method |
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