CN109569638A - Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof - Google Patents
Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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Abstract
The present invention relates to low-temperature alkyl arene dehydrogenating catalysts and preparation method thereof, mainly solve the problems, such as that low potassium catalyst present in conventional art is active low under cryogenic.The present invention includes following component: 66~76% Fe by using low-temperature alkyl arene dehydrogenating catalyst by weight percentage2O3；6~11% K2O；6~11% CeO2；0.5~5% WO3；0.5~5% BaO；The oxide of 0.5~5% at least one group ivb metal；The oxide of 0.5~5% at least one Group VB metal；The technical solution of 0.5~3.5% at least one oxide selected from Sb or Bi, preferably solves the problems, such as this, can be used in the industrial production of dehydrogenating alkyl arene in preparing alkyl alkenyl arene.
Description
Technical field
The present invention relates to one kind for low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof.
Background technique
Industrial alkyl alkenyl arene is mainly made by alkyl aromatics catalytic dehydrogenation, key of this method first is that selecting one
The dehydrogenation that kind activity is high, selectivity is high, stability is good.The catalyst of patent report is divided to two classes: one kind is Fe-K-Cr system
Column, such as published United States Patent (USP) 4134858,4152300,4144197, Chinese patent 87100517, although such catalyst
Activity and stability it is preferable, but due to being eliminated containing the chromium less friendly to environment.Another kind of is Fe-K-Ce-Mo system
Column, such as published United States Patent (USP) 4804799, European patent 0502510A1,0297685A1,0305020A1, such catalyst
Not only with Ce, Mo instead of Cr, but also the activity and stability of catalyst have raising by a relatively large margin compared with the former, by various countries' benzene
Ethylene production producer uses, its existing main problem is reaction temperature height, generally all at 620 DEG C or more, so that production energy consumption
It is high.
It is mainly to help to urge that Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst generallyd use, which is using iron oxide as main active component, potassium oxide,
The Fe-series catalyst of agent.But potassium washes away lower slow loss and migration in high-temperature water vapor, is the master of the irreversible inactivation of catalyst
One of reason is wanted, reduces the mainstream that potassium content is catalyst for phenylethylene dehydrogenation exploitation at present.
For industrial dehydrogenation of ethylbenzene to styrene, annual output is mostly at 100,000 tons/year or more, reaction temperature
Height, by-product is more, and energy consumption is high, is always the problem for perplexing production of styrene producer.Dehydrogenation reaction temperature as can reduce by 5 DEG C or even
10 DEG C, for commercial plant, not change any equipment, be not required to increase investment, can save within 1 year water vapour, electricity aspect
Overspending is run at low temperature additionally, due to dehydrogenation reaction, is wanted for extending catalyst life, reducing equipment material high temperature resistant
It asks, also there is positive effect.Therefore, a kind of low-temperature alkyl arene dehydrogenating catalyst is found, energy consumption is greatly lowered, is always research
The interested project of personnel.
Summary of the invention
The first technical problem to be solved by the present invention be low potassium catalyst present in conventional art under cryogenic
The low problem of activity provides a kind of new catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene.The catalyst is used for
Dehydrogenating alkyl arene in preparing alkyl alkenyl arene has good low temperature active, can use under lower reaction temperature, thus
Energy consumption is effectively reduced, extends the device cycle of operation, reduce catalyst updating expense and the production as caused by frequently more catalyst changeout
Amount loss.
The second technical problem to be solved by the present invention is to provide the corresponding low temperature of one of one kind and solution technical problem
The preparation method of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst.
The third technical problem to be solved by the present invention is to provide the corresponding low temperature of one of one kind and solution technical problem
Application method of the Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst in dehydrogenating alkyl arene in preparing alkyl alkenyl arene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: low-temperature alkyl arene dehydrogenating is catalyzed
Agent includes following component by weight percentage:
(a) 66~76% Fe2O3；
(b) 6~11% K2O；
(c) 6~11% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% BaO；
(f) 0.5~5% a kind of oxide of group ivb metal；
(g) 0.5~5% a kind of oxide of Group VB metal；
(h) 0.5~3.5% a kind of oxide selected from Sb or Bi.
In above-mentioned technical proposal, a kind of oxide of group ivb metal preferably is selected from TiO2、ZrO2Or HfO2One kind.
In above-mentioned technical proposal, a kind of oxide of Group VB metal is selected from V2O5、Nb2O5Or Ta2O5One kind.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of above-mentioned solution technical problem
One of technical solution in any low-temperature alkyl arene dehydrogenating catalyst preparation method, comprising the following steps: will be by matching
Than the oxygen of Fe, K of weighing, Ce, W, Ba, the oxide of Group IV metal, the oxide of Group VB metal, the oxide of Sb or Bi
Compound and perforating agent after mixing, add water to mediate, and obtain the low-temperature alkyl arene dehydrogenating through extrusion, drying and roasting and are catalyzed
Agent.
In above-mentioned technical proposal, the additional amount of the water is not particularly limited, and those skilled in the art are in order to squeeze out needs
Humidity can be rationally grasped, the additional amount of such as, but not limited to water accounts for catalyst raw material gross weight 15~35%.
In above-mentioned technical proposal, drying temperature is not particularly limited, such as 100~150 DEG C, and drying time optional 0.55~
8 hours.
In above-mentioned technical proposal, as preferably selecting, drying gradually heats up, such as, but not limited to 100~120 DEG C of dryings
2~4 hours, then 130~150 DEG C drying 0.5~4 hour.
In above-mentioned technical proposal, optional 600~1000 DEG C of maturing temperature, calcining time optional 2~8 hours.
In above-mentioned technical proposal, as preferably roasting condition, maturing temperature is stepped up, such as, but not limited to 600~
700 DEG C roast 2~4 hours, then roast 2~4 hours at 900~1000 DEG C.
In above-mentioned technical proposal, the Fe is preferred from iron oxide red and iron oxide yellow, more preferable iron oxide red and oxidation
The weight ratio of iron oxide yellow is 2.0~3.2:1.
In above-mentioned technical proposal, Ce is added preferably in the form of cerium oxalate or cerous carbonate.
In above-mentioned technical proposal, binder is not added in catalyst preparation process.
Raw material used in catalyst component of the present invention is as follows:
K used is added with potassium as potassium carbonate；W used is added with its salt or oxide form；Ba used with oxide or
Carbonate form is added；Remaining element is added with its salt or oxide form；In preparation process of the invention, except catalysis
Perforating agent should also be added outside agent bulk composition, perforating agent can be selected from graphite, polystyrene microsphere, sodium carboxymethylcellulose,
Its additional amount is the 2~6% of total catalyst weight.
To solve above-mentioned technical problem three, The technical solution adopted by the invention is as follows: a kind of above-mentioned solution technical problem
One of technical solution in any low-temperature alkyl arene dehydrogenating catalyst in dehydrogenating alkyl arene in preparing alkyl alkenyl arene
Application.
In above-mentioned technical proposal, the application has no ad hoc restriction, and those skilled in the art can be according to prior art work
Skill is applied to catalyst of the present invention.
Catalyst obtained carries out activity rating in isotherm formula fixed bed according to the above method, to ethyl benzene dehydrogenation preparation of styrene
For catalyst activity evaluation, process is summarized as follows:
It will be disengaged from sub- water and ethylbenzene and input preheating mixer through metering pump respectively, preheating enters reaction after being mixed into gaseous state
Device, reactor use electric-heating-wire-heating, make up to predetermined temperature.Reactor inside diameter be 1 " stainless steel tube, it is interior filling 100 milli
Liter, 3 millimeters of partial size of catalyst.With chromatographic, it is formed after being coagulated by the reactant of reactor outflow is water cooled.
Conversion of ethylbenzene, selectivity of styrene calculate as follows:
The present invention by iron-potassium-cerium-tungsten-barium system using the oxide for adding a kind of group ivb metal and a kind of the
The oxide of VB race metal, while a kind of oxide selected from Sb or Bi is added, adding additives, on the one hand do not reduce inefficient object
The introducing of matter improves the alkalinity of system, stablizes and has dispersed the active phase of catalyst, on the other hand improve active interdigit
Electron transmission channel, hence it is evident that improve the activity of low potassium catalyst under cryogenic.
Using technical solution of the present invention, catalyst was at normal pressure, ethylbenzene air speed 1.0 hours-1, 600 DEG C of reaction temperature and 580
DEG C, under the conditions of water/ethylbenzene weight ratio 1.8, conversion of ethylbenzene respectively reaches 72.2% and 61.6%, achieves preferable technology effect
Fruit.
The present invention will be further described below by way of examples:
Specific embodiment
[embodiment 1]
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of TiO2, 1.98 parts of V2O5, 1.56 parts of Sb2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for
The deionized water of catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of
Grain is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roasts 3 hours in 650 DEG C,
960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
[comparative example 1]
In addition to TiO is not added2、V2O5And Sb2O3Outside, method for preparing catalyst and evaluating catalyst condition are with embodiment 1, specifically
Are as follows:
It will be equivalent to 53.45 parts of Fe2O3Iron oxide red, be equivalent to 23.07 parts of Fe2O3Iron oxide yellow, be equivalent to 8.91
Part K2The potassium carbonate of O is equivalent to 7.97 parts of CeO2Cerium oxalate, be equivalent to 2.83 parts of WO3Ammonium tungstate, be equivalent to 3.76 parts of BaO
Barium carbonate and 5.2 parts of graphite stirred in kneader 2 hours, be added and account for the deionized water of catalyst raw material gross weight 26.5%,
It mixes and stirs 1.5 hours, takes out extrusion, be extruded into 3 millimeters of diameter, long 6 millimeters of particle, be put into baking oven, 105 DEG C are dried 3.0 hours, and 140
It DEG C dries 3.0 hours, is subsequently placed in muffle furnace, is roasted in 650 DEG C 3 hours, 960 DEG C of roastings obtain finished catalyst in 3 hours, urge
Agent composition is listed in table 1.Evaluation result is listed in table 2.
[comparative example 2]
In addition to V is not added2O5And Sb2O3Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 51.83 parts of Fe2O3Iron oxide red, be equivalent to 22.37 parts of Fe2O3Iron oxide yellow, be equivalent to 8.64
Part K2The potassium carbonate of O is equivalent to 7.72 parts of CeO2Cerium oxalate, be equivalent to 2.75 parts of WO3Ammonium tungstate, be equivalent to 3.65 parts of BaO
Barium carbonate, 3.05 parts of TiO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material gross weight 26.5%
Deionized water, mix and stir 1.5 hours, take out extrusion, be extruded into 3 millimeters of diameter, long 6 millimeters of particle, be put into baking oven, 105 DEG C of bakings
3.0 hours, 140 DEG C were dried 3.0 hours, were subsequently placed in muffle furnace, were roasted in 650 DEG C 3 hours, 960 DEG C of roastings are obtained into for 3 hours
Product catalyst, catalyst composition are listed in table 1.Evaluation result is listed in table 2.
[comparative example 3]
In addition to Sb is not added2O3Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 50.78 parts of Fe2O3Iron oxide red, be equivalent to 21.92 parts of Fe2O3Iron oxide yellow, be equivalent to 8.46
Part K2The potassium carbonate of O is equivalent to 7.57 parts of CeO2Cerium oxalate, be equivalent to 2.69 parts of WO3Ammonium tungstate, be equivalent to 3.58 parts of BaO
Barium carbonate, 2.99 parts of TiO2, 2.01 parts of V2O5It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material
The deionized water of gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking
Case, 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 650 DEG C 3 hours, 960 DEG C of roastings 3
Hour obtains finished catalyst, and catalyst composition is listed in table 1.Evaluation result is listed in table 2.
[embodiment 2]
In addition to ZrO2Replace TiO2Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of ZrO2, 1.98 parts of V2O5, 1.56 parts of Sb2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for
The deionized water of catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of
Grain is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roasts 3 hours in 650 DEG C,
960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 3]
In addition to HfO2Replace TiO2Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of HfO2, 1.98 parts of V2O5, 1.56 parts of Sb2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for
The deionized water of catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of
Grain is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roasts 3 hours in 650 DEG C,
960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 4]
In addition to Nb2O5Replace V2O5Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of TiO2, 1.98 parts of Nb2O5, 1.56 parts of Sb2O3It stirs 2 hours, is added in kneader with 5.2 parts of graphite
The deionized water for accounting for catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, grows 6 millimeters
Particle is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 650 DEG C of roastings 3
When, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 5]
In addition to Ta2O5Replace V2O5Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of TiO2, 1.98 parts of Ta2O5, 1.56 parts of Sb2O3It stirs 2 hours, is added in kneader with 5.2 parts of graphite
The deionized water for accounting for catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, grows 6 millimeters
Particle is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 650 DEG C of roastings 3
When, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 6]
In addition to Bi2O3Replace Sb2O3Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 49.99 parts of Fe2O3Iron oxide red, be equivalent to 21.58 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of BaO
Barium carbonate, 2.94 parts of TiO2, 1.98 parts of Ta2O5, 1.56 parts of Bi2O3It stirs 2 hours, is added in kneader with 5.2 parts of graphite
The deionized water for accounting for catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, grows 6 millimeters
Particle is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 650 DEG C of roastings 3
When, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 7]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 1.47 parts of TiO2With 1.47 parts
ZrO2Replace 2.94 parts of TiO2, with 0.99 part of V2O5With 0.99 part of Nb2O5Replace 1.98 parts of V2O5。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 8]
It will be equivalent to 56.44 parts of Fe2O3Iron oxide red, be equivalent to 14.52 parts of Fe2O3Iron oxide yellow, be equivalent to 8.26
Part K2The potassium carbonate of O is equivalent to 7.39 parts of CeO2Cerium oxalate, be equivalent to 2.63 parts of WO3Ammonium tungstate, be equivalent to 3.49 parts of BaO
Barium carbonate, 2.94 parts of TiO2, 1.98 parts of V2O5, 1.55 parts of Sb2O3, 0.85 part of CoO and 5.2 part of graphite 2 are stirred in kneader
Hour, be added and account for the deionized water of catalyst raw material gross weight 26.5%, mix and stir 1.5 hours, take out extrusion, be extruded into 3 millimeters of diameter,
Long 6 millimeters of particle is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, in 650 DEG C
Roasting 3 hours, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
[embodiment 9]
It will be equivalent to 37.48 parts of Fe2O3Iron oxide red, be equivalent to 33.0 parts of Fe2O3Iron oxide yellow, be equivalent to 8.2 parts
K2The potassium carbonate of O is equivalent to 7.34 parts of CeO2Cerium oxalate, be equivalent to 2.61 parts of WO3Ammonium tungstate, be equivalent to 3.47 parts of BaO's
Barium carbonate, 2.9 parts of TiO2, 1.95 parts of V2O5, 1.54 parts of Sb2O3, that 1.52 parts of cement and 5.2 parts of graphite stir 2 in kneader is small
When, the deionized water for accounting for catalyst raw material gross weight 26.5% is added, mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, length
6 millimeters of particle is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 650 DEG C
It burns 3 hours, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
[embodiment 10]
It will be equivalent to 54.05 parts of Fe2O3Iron oxide red, be equivalent to 21.52 parts of Fe2O3Iron oxide yellow, be equivalent to 6.33
Part K2The potassium carbonate of O is equivalent to 6.45 parts of CeO2Cerium oxalate, be equivalent to 0.65 part of WO3Ammonium tungstate, be equivalent to 2.52 parts of BaO
Barium carbonate, 0.94 part of TiO2, 3.98 parts of V2O5, 3.56 parts of Sb2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for
The deionized water of catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of
Grain is put into baking oven, and 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roasts 3 hours in 650 DEG C,
960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
[embodiment 11]
It will be equivalent to 51.05 parts of Fe2O3Iron oxide red, be equivalent to 15.52 parts of Fe2O3Iron oxide yellow, be equivalent to
10.33 part K2The potassium carbonate of O, 9.45 parts of CeO2, be equivalent to 3.65 parts of WO3Ammonium tungstate, be equivalent to 0.52 part of BaO barium carbonate,
6.9 parts of TiO2, 1.98 parts of V2O5, 0.6 part of Sb2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material
The deionized water of gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking
Case, 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 650 DEG C 3 hours, 960 DEG C of roastings 3
Hour obtains finished catalyst, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
[embodiment 12]
It will be equivalent to 55.51 parts of Fe2O3Iron oxide red, be equivalent to 18.5 parts of Fe2O3Iron oxide yellow, be equivalent to 9.93
Part K2The potassium carbonate of O is equivalent to 10.84 parts of CeO2Cerium oxalate, be equivalent to 1.57 parts of WO3Ammonium tungstate, be equivalent to 2.33 parts
The barium carbonate of BaO, 0.38 part of TiO2, 0.59 part of V2O5, 0.35 part of Sb2O3It stirs 2 hours, adds in kneader with 5.2 parts of graphite
The deionized water for entering to account for catalyst raw material gross weight 26.5% mixes and stirs 1.5 hours, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 105 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 650 DEG C of roastings 3
When, 960 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, liquid air speed 1.0 hours- 1, 600 DEG C and 580 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.8, evaluation result is listed in table 2.
The weight percent of table 1 (continued) catalyst forms
The weight percent of 1 (Continued) catalyst of table forms
The comparison of 2 catalyst performance of table
Above embodiments explanation, adds a kind of oxide of group ivb metal in iron-potassium-cerium-tungsten-barium catalyst system
With a kind of oxide of Group VB metal, while a kind of oxide selected from Sb or Bi is added, not adding additives, hence it is evident that improve
The low temperature active of low potassium catalyst can reduce catalyst on commercial plant using temperature, energy saving, while catalyst
Broad application temperature range is recommendable novel low-temperature energy-saving type catalyst.
Claims (10)
1. low-temperature alkyl arene dehydrogenating catalyst includes following component by weight percentage:
(a) 66~76% Fe2O3；
(b) 6~11% K2O；
(c) 6~11% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% BaO；
(f) oxide of 0.5~5% at least one group ivb metal；
(g) oxide of 0.5~5% at least one Group VB metal；
(h) 0.5~3.5% at least one oxide selected from Sb or Bi.
2. catalyst according to claim 1, it is characterized in that the oxide of the group ivb metal is selected from TiO2、ZrO2Or
HfO2At least one.
3. catalyst according to claim 1, it is characterized in that the oxide of the Group VB metal is selected from V2O5、Nb2O5Or
Ta2O5At least one.
4. the preparation method of any low-temperature alkyl arene dehydrogenating catalyst in claims 1 to 3, comprising the following steps:
By the Fe, K weighed according to the ratio, Ce, W, Ba, the oxide of Group IV metal, the oxide of Group VB metal, Sb oxide or
The oxide and perforating agent of Bi after mixing, adds water to mediate, and it is de- to obtain the low-temperature alkyl arene through extrusion, drying and roasting
Hydrogen catalyst.
5. the preparation method according to claim 4, it is characterised in that drying temperature is 100~150 DEG C.
6. the preparation method according to claim 4, it is characterised in that maturing temperature is 600~1000 DEG C.
7. the preparation method according to claim 4, it is characterised in that Fe is added in the form of iron oxide red and iron oxide yellow；
It is Fe that it, which is matched,2O3: Fe2O3·H2O=2.0~3.2:1.
8. the preparation method according to claim 4, it is characterised in that Ce is added in the form of cerium oxalate or cerous carbonate.
9. the preparation method according to claim 4, it is characterised in that do not add binder in catalyst preparation process.
10. any low-temperature alkyl arene dehydrogenating catalyst of claims 1 to 3 prepares alkane alkenyl virtue in alkyl aromatics dehydrogenation
Application in hydrocarbon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112239392A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Low temperature alkyl aromatic dehydrogenation method |
| CN112239389A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Process for producing alkalkenyl aromatic hydrocarbon |
| CN113877594A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Process for dehydrogenating alkylaromatic hydrocarbons |
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| CN1230461A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Alkyl arene dehydrogenating catalyst |
| CN106582697A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low rare earth catalyst for dehydrogenation of alkyl aromatics |
| CN106582689A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112239392A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Low temperature alkyl aromatic dehydrogenation method |
| CN112239392B (en) * | 2019-07-16 | 2023-08-29 | 中国石油化工股份有限公司 | Method for dehydrogenating alkyl arene at low temperature |
| CN112239389A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Process for producing alkalkenyl aromatic hydrocarbon |
| CN112239389B (en) * | 2019-07-19 | 2023-04-07 | 中国石油化工股份有限公司 | Process for producing alkalkenyl aromatic hydrocarbon |
| CN113877594A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Process for dehydrogenating alkylaromatic hydrocarbons |
| CN113877594B (en) * | 2020-07-02 | 2023-08-04 | 中国石油化工股份有限公司 | Method for dehydrogenating alkyl aromatic hydrocarbon |
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