CN106582693B - 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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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% MgO；Light rare earth oxide other than 0.5~5% cerium；0.5~5% heavy rare-earth oxide；A kind of 0.5~3.5% technical solution of the oxide selected from Nb or Hf, 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.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst, with
Weight percent meter includes following component:
(a) 66~76% Fe2O3；
(b) 6~11% K2O；
(c) 6~11% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% MgO；
(f) the light rare earth oxide other than 0.5~5% cerium；
(g) 0.5~5% heavy rare-earth oxide；
(h) 0.5~3.5% a kind of oxide selected from Nb or Hf.
In above-mentioned technical proposal, the light rare earth oxide preferably is selected from La2O3、Pr2O3Or Nd2O3At least one.
In above-mentioned technical proposal, the heavy rare-earth oxide preferably is selected from Er2O3Or Tm2O3At least one.
In above-mentioned technical proposal, (f) component preferably includes La simultaneously2O3And Pr2O3Or La2O3And Nd2O3Or
Pr2O3And Nd2O3, described two light rare earth oxides are in terms of low potassium catalyst low-temperature activity raising with binary synergistic effect；
(f) component preferably includes La simultaneously2O3、Pr2O3And Nd2O3, three kinds of light rare earth oxides are in low potassium catalyst at this time
Low temperature active, which improves aspect, has trielement synergistic effect.
In above-mentioned technical proposal, (g) component preferably includes Er simultaneously2O3And Tm2O3, described two heavy rare-earth oxides exist
Low potassium catalyst low-temperature activity, which improves aspect, has binary synergistic effect.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the technical side of one of technical problem
The preparation method of catalyst described in case, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W, Mg, rare earth element, Nb
Oxide or Hf oxide and perforating agent after mixing, add water to mediate, obtain the catalysis through extrusion, drying and roasting
Agent.
The additional amount of water is not particularly limited, and those skilled in the art can rationally grasp humidity to squeeze out needs,
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 80~150 DEG C, drying time optional 0.55~8
Hour.
In above-mentioned technical proposal, as preferably selecting, drying gradually heats up, such as, but not limited to 80~100 DEG C dryings 2
~4 hours, then 130~150 DEG C drying 0.5~4 hour.
In above-mentioned technical proposal, optional 500~1000 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 500~
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.
Binder can be added or not added in above-mentioned technical proposal, 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；Mg used with oxide or
Hydroxide form is added；Remaining element is added with its salt or oxide form；In preparation process of the invention, except urging
Perforating agent should also be added outside agent bulk composition, perforating agent can be selected from graphite, polystyrene microsphere, sodium carboxymethylcellulose
It selects, additional amount is the 2~6% of total catalyst weight.
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 is by being selected from La using addition is at least one in iron-potassium-cerium-tungsten-magnesium system2O3、Pr2O3Or Nd2O3's
Light rare earth oxide and at least one are selected from Er2O3Or Tm2O3Heavy rare-earth oxide, while being added a kind of selected from Nb's or Hf
Oxide, adding additives, on the one hand do not reduce the introducing of inefficient substance, improve the alkalinity of system, stablize and have dispersed to urge
On the other hand the active phase of agent improves the electron transmission channel of active interdigit, hence it is evident that improve low potassium catalyst in low temperature
Under the conditions of activity, catalyst was at normal pressure, ethylbenzene air speed 1.0 hours-1, 600 DEG C and 580 DEG C of reaction temperature, water/ethylbenzene weight ratio
Under the conditions of 2.0, conversion of ethylbenzene respectively reaches 73.2% and 62.6%, achieves preferable technical effect.
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 MgO
Magnesium hydroxide, 2.94 parts of La2O3, 1.98 parts of Er2O3, 1.56 parts of Nb2O5It 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, 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 550 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, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, evaluation result is listed in table 2.
[comparative example 1]
In addition to La is not added2O3、Er2O3And Nb2O5Outside, method for preparing catalyst and evaluating catalyst condition are the same as embodiment 1, tool
Body 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 MgO
Magnesium hydroxide and 5.2 parts of graphite stirred in kneader 2 hours, be added account for catalyst raw material gross weight 26.5% disengaging son
Water 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 oven, and 95 DEG C are dried 3.0 hours,
140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 960 DEG C of roastings obtain finished product catalysis for 3 hours
Agent, catalyst composition are listed in table 1.Evaluation result is listed in table 2.
[comparative example 2]
In addition to Er is not added2O3And Nb2O5Outside, 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 MgO
Magnesium hydroxide, 3.05 parts of La2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material gross weight
26.5% deionized water 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 oven, and 95
DEG C dry 3.0 hours, 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roast 3 hours in 550 DEG C, 960 DEG C roasting 3 hours
To finished catalyst, catalyst composition is listed in table 1.Evaluation result is listed in table 2.
[comparative example 3]
In addition to Nb is not added2O5Outside, 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 MgO
Magnesium hydroxide, 2.99 parts of La2O3, 2.01 parts of Er2O3It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst
The deionized water of 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 particle, puts
Enter baking oven, 95 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 550 DEG C 3 hours, 960 DEG C of roastings
It burns and obtains within 3 hours finished catalyst, catalyst composition is listed in table 1.Evaluation result is listed in table 2.
[embodiment 2]
In addition to Pr2O3Replace La2O3Outside, 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 MgO
Magnesium hydroxide, 2.94 parts of Pr2O3, 1.98 parts of Er2O3, 1.56 parts of Nb2O5It 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, 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 550 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 3]
In addition to Nd2O3Replace La2O3Outside, 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 MgO
Magnesium hydroxide, 2.94 parts of Nd2O3, 1.98 parts of Er2O3, 1.56 parts of Nb2O5It 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, 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 550 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 4]
In addition to Tm2O3Replace Er2O3Outside, 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 MgO
Magnesium hydroxide, 2.94 parts of La2O3, 1.98 parts of Tm2O3, 1.56 parts of Nb2O5It 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, 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 550 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]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 1.47 parts of La2O3With 1.47 parts
Pr2O3Replace 2.94 parts of La2O3。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 6]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 1.47 parts of La2O3With 1.47 parts
Nd2O3Replace 2.94 parts of La2O3, with 0.99 part of Er2O3With 0.99 part of Tm2O3Replace 1.98 parts of Er2O3。
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 0.98 part of La2O3, 0.98 part
Pr2O3With 0.98 part of Nd2O3Replace 2.94 parts of La2O3, with 0.99 part of Er2O3With 0.99 part of Tm2O3Replace 1.98 parts of Er2O3。
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 MgO
Magnesium hydroxide, 0.97 part of La2O3, 0.97 part of Pr2O3, 0.97 part of Nd2O3, 0.98 part of Er2O3, 0.98 part of Tm2O3, 1.55 parts
HfO2, 0.85 part of CuO and 5.2 part of graphite stirred in kneader 2 hours, the disengaging for accounting for catalyst raw material gross weight 26.5% is added
Sub- water 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 oven, and 95 DEG C are dried 3.0 hours,
140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 960 DEG C of roastings obtain finished product catalysis for 3 hours
Agent, catalyst composition are listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, 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 MgO's
Magnesium hydroxide, 2.9 parts of La2O3, 1.95 parts of Er2O3, 1.54 parts of Nb2O5, 1.52 parts of cement and 5.2 parts of graphite stir in kneader
2 hours, the deionized water for accounting for catalyst raw material gross weight 26.5% is added, mixes and stirs 1.5 hours, take out extrusion, is extruded into 3 milli of diameter
Rice, long 6 millimeters of particle are put into baking oven, and 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, in 550
DEG C roasting 3 hours, 960 DEG C of roastings obtained finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, 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 MgO
Magnesium hydroxide, 0.94 part of La2O3, 3.98 parts of Er2O3, 3.56 parts of Nb2O5It 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, 95 DEG C are dried 3.0 hours, and 140 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, small in 550 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, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, 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 the hydroxide of 0.52 part of MgO
Magnesium, 6.9 parts of La2O3, 1.98 parts of Er2O3, 0.6 part of Nb2O5It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst
The deionized water of 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 particle, puts
Enter baking oven, 95 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 550 DEG C 3 hours, 960 DEG C of roastings
It burns and obtains within 3 hours finished catalyst, catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, 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 magnesium hydroxide of MgO, 0.38 part of La2O3, 0.59 part of Er2O3, 0.35 part of Nb2O5It is small that 2 are stirred in kneader with 5.2 parts of graphite
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 95 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 550 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, ethylbenzene liquid volume air speed 1.0 hours- 1, 600 DEG C and 580
DEG C, carry out activity rating under the conditions of water ratio (weight) 2.0, 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 is added at least one selected from La in iron-potassium-cerium-tungsten-magnesium catalyst system2O3、Pr2O3Or
Nd2O3Light rare earth oxide and at least one be selected from Er2O3Or Tm2O3Heavy rare-earth oxide, while being added a kind of selected from Nb
Or the oxide of Hf, hence it is evident that the low temperature active for improving low potassium catalyst can reduce catalyst on commercial plant using temperature
Degree, energy saving；The broad application temperature range of catalyst simultaneously, is recommendable novel low-temperature energy-saving type catalyst.
Claims (7)
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% MgO；
(f) the light rare earth oxide other than 0.5~5% cerium is La2O3、Pr2O3And Nd2O3；
(g) 0.5~5% heavy rare-earth oxide is Er2O3And Tm2O3；
(h) 0.5~3.5% a kind of oxide selected from Nb or Hf.
2. the preparation method of catalyst described in claim 1, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W,
Mg, rare earth element, the oxide of Nb or Hf oxide and perforating agent after mixing, add water to mediate, through extrusion, drying and roasting
Burning obtains the catalyst.
3. preparation method according to claim 2, it is characterised in that drying temperature is 80~150 DEG C.
4. preparation method according to claim 2, it is characterised in that maturing temperature is 500~1000 DEG C.
5. preparation method according to claim 2, 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.
6. preparation method according to claim 2, it is characterised in that Ce is added in the form of cerium oxalate or cerous carbonate.
7. preparation method according to claim 2, it is characterised in that do not add binder in catalyst preparation process.
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| 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 |
| CN111420673A (en) * | 2020-03-19 | 2020-07-17 | 湖南城市学院 | Preparation method of catalyst for alkyl aromatic dehydrogenation |
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