CN106582685B - Low-temperature ethyl benzene dehydrogenation catalyst and preparation method thereof - Google Patents
Low-temperature ethyl benzene dehydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to low-temperature ethyl benzene dehydrogenation catalysts and preparation method thereof, mainly solve the problems, such as that the potassium in catalyst present in conventional art is easy migration in ethyl benzene dehydrogenation preparation of styrene reaction process and loss, poor catalyst stability, the influence device cycle of operation and low potassium catalyst are active low under cryogenic.The present invention includes following component: 68~79% Fe by using low-temperature ethyl benzene dehydrogenation catalyst by weight percentage2O3；4~7% K2O；6~12% CeO2；0.5~5% WO3；0.5~5% SrO；2~8% HfO2；The technical solution of 0.5~7% light rare earth oxide except cerium, preferably solves the problems, such as this, can be used in the industrial production of ethyl benzene dehydrogenation preparation of styrene.
Description
Technical field
The present invention relates to low-temperature ethyl benzene dehydrogenation catalysts of low potassium content and preparation method thereof.
Background technique
It is well known that industrial about 90% styrene is made by ethylbenzene catalytic dehydrogenation, the key of this method first is that urging
Agent.The catalyst of patent report is divided to two classes: one kind is Fe-K-Cr series, such as published United States Patent (USP) 4134858,
4152300,4144197, Chinese patent 87100517, although the activity and stability of such catalyst are preferable, due to containing
The chromium less friendly to environment, has been eliminated.It is another kind of be Fe-K-Ce-Mo series, such as published United States Patent (USP) 4804799,
European patent 0502510A1,0297685A1,0305020A1, such catalyst not only use Ce, Mo instead of Cr, but also are catalyzed
The activity and stability of agent have raising by a relatively large margin compared with the former, are used by production of styrene producer, various countries, it is existing main
Wanting problem is reaction temperature height, generally all at 620 DEG C or more, so that production energy consumption is high.Currently, ethylbenzene dehydrogenation produces benzene
Ethylene technology is quite mature, and latest development trend is made an issue of on reducing raw materials consumption and raising efficiency.
It is mainly to help to urge that dehydrogenation of ethylbenzene to styrene 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, strives for the mainstream that low potassium content is catalyst for phenylethylene dehydrogenation exploitation at present.
The commercial plant scale overwhelming majority that ethylbenzene dehydrogenation generates styrene in the world reacts temperature at 100,000 tons/year or more
Degree is high, and generally all at 620 DEG C or more, by-product is more, and energy consumption is high, is always the problem for perplexing production of styrene producer, and dehydrogenation is anti-
Temperature is answered as can reducing by 5 DEG C or even 10 DEG C, for commercial plant, not change any equipment, is not required to increase investment, 1 year just
The overspending that water vapour, electricity aspect can be saved, runs at low temperature additionally, due to dehydrogenation reaction, for extending the catalyst longevity
Life reduces the requirement of equipment material high temperature resistant, also there is positive effect.Therefore, a kind of low-temperature dehydrogenation catalyst is found, is greatly lowered
Energy consumption is always the interested project of researcher.
Summary of the invention
The first technical problem to be solved by the present invention is potassium in catalyst present in conventional art in ethylbenzene dehydrogenation
It is easy migration in preparation of styrene reaction process and loss, poor catalyst stability and low potassium catalyst are active under cryogenic
Low disadvantage provides a kind of new catalyst for ethyl benzene dehydrogenation preparation of styrene.The catalyst potassium content is low, is used for ethylbenzene
Dehydrogenation reaction has better low temperature active and stability, can effectively reduce energy consumption, extends the device cycle of operation, reduces catalyst
Update cost and the production loss as caused by frequently more catalyst changeout.
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 catalyst for phenylethylene dehydrogenation.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: low-temperature ethyl benzene dehydrogenation catalyst, with
Weight percent meter includes following component:
(a) 68~79% Fe2O3；
(b) 4~7% K2O；
(c) 6~12% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% SrO；
(f) 2~8% HfO2；
(g) the light rare earth oxide other than 0.5~7% cerium.
In above-mentioned technical proposal, the light rare earth oxide preferably is selected from La2O3、Pr2O3Or Nd2O3At least one.
In above-mentioned technical proposal, (g) 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；
(g) 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, light rare earth oxide content except cerium is preferably 1.5~6%.
In above-mentioned technical proposal, HfO2Content is preferably 4~6%.
It is the two of the above-mentioned technology of solution, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, comprising the following steps:
After mixing by the Fe, K weighed according to the ratio, Ce, W, Sr, Hf, light rare earth oxide and perforating agent, add water to mediate, through extrusion,
Dry and roasting obtains the catalyst.
In above-mentioned technical proposal, drying temperature is not particularly limited, such as 60~150 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 60~80 DEG C dryings 2
~4 hours, then 120~150 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~
600 DEG C roast 1~4 hour, then roast 1~4 hour at 800~1000 DEG C.
In above-mentioned technical proposal, Fe is added preferably in the form of iron oxide red and iron oxide yellow, its more preferable weight proportion
For Fe2O3: Fe2O3·H2O=2.0~3.2:1.
In above-mentioned technical proposal, Ce is added preferably in the form of cerium oxide or cerous carbonate.
In above-mentioned technical proposal, binder can not be 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；Sr used is with oxide shape
Formula is added；Hf used is added in the form of an oxide；Remaining element is added with its salt or oxide form；In system of the invention
During standby, perforating agent should also be added in addition to catalyst body ingredient, perforating agent can be from graphite, polystyrene microsphere or carboxymethyl
It is selected in sodium cellulosate, additional amount is the 2~6% of total catalyst weight.
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%.
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 be internal diameter 1 " stainless steel tube, can load 100 milli
Liter, 3 millimeters of partial size of catalyst.The reactant of reactor outflow it is water cooled it is solidifying after with its composition of chromatographic.
Conversion of ethylbenzene, selectivity of styrene calculate as follows:
At least one additional of the present invention by the addition hafnium oxide in iron-potassium-cerium-tungsten-strontium system and except cerium is light
Rare earth oxide is co-catalyst, while not adding binder, on the one hand reduces the loss and migration of potassium component, stablizes and divides
On the other hand the active phase for having dissipated catalyst improves the electron transmission channel of active interdigit, it is thus also avoided that inefficient substance draws
Enter, hence it is evident that improve the activity and stability of low potassium catalyst under cryogenic, catalyst is small in normal pressure, ethylbenzene air speed 1.0
When- 1, 600 DEG C and 580 DEG C of reaction temperature, under the conditions of water ratio (weight ratio) 2.0, conversion of ethylbenzene respectively reaches 74.2% He
63.9%, conversion ratio is kept at 73.8% and 63.6% after operation 2000 hours, 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 47.94 parts of Fe2O3Iron oxide red, be equivalent to 23.97 parts of Fe2O3Iron oxide yellow, be equivalent to 6.28
Part K2The potassium carbonate of O is equivalent to 0.8 part of WO3Ammonium tungstate, 7.5 parts of CeO2, 3.98 parts of SrO, 5.86 parts of HfO2, 3.6 parts of Pr2O3
And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, the water for accounting for total catalyst weight 25.8% are added, then mix and stir
0.5 hour, it is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, dries 2.5 hours, 138 DEG C and dry 2 hours in 75 DEG C,
It is subsequently placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, gained catalyst
Composition be 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) 2.0, evaluation result is listed in table 2.
[comparative example 1]
In addition to HfO is not added2And Pr2O3Outside, method for preparing catalyst and evaluation condition be with embodiment 1, specifically:
It will be equivalent to 53.0 parts of Fe2O3Iron oxide red, be equivalent to 26.5 parts of Fe2O3Iron oxide yellow, be equivalent to 6.94 parts
K2The potassium carbonate of O is equivalent to 0.88 part of WO3Ammonium tungstate, 8.28 parts of CeO2, 4.4 parts of SrO and 5.8 part of sodium carboxymethylcelluloses exist
It is stirred 1 hour in kneader, the water for accounting for total catalyst weight 25.8% is added, then mix and stir 0.5 hour, be extruded into 3 millimeters of diameter, length
The particle of 6 millimeters of degree, is put into baking oven, dries 2.5 hours, 138 DEG C and dries 2 hours in 75 DEG C, is subsequently placed in muffle furnace, in 550 DEG C
It roasts 1.5 hours within roasting 1.5 hours, 920 DEG C and obtains finished catalyst, the composition of gained catalyst is listed in table 1.Evaluation result column
In table 2.
[comparative example 2]
In addition to Pr is not added2O3Outside, method for preparing catalyst and evaluation condition be with embodiment 1, specifically:
It will be equivalent to 49.78 parts of Fe2O3Iron oxide red, be equivalent to 24.89 parts of Fe2O3Iron oxide yellow, be equivalent to 6.51
Part K2The potassium carbonate of O is equivalent to 0.83 part of WO3Ammonium tungstate, 7.78 parts of CeO2, 4.13 parts of SrO, 6.08 parts of HfO2And 5.8 parts of carboxylics
Sodium carboxymethylcellulose pyce stirs 1 hour in kneader, the water for accounting for total catalyst weight 25.8% is added, then mix and stir 0.5 hour, squeezes
At 3 millimeters of diameter, the particle of 6 millimeters of length, it is put into baking oven, dries 2.5 hours, 138 DEG C and dries 2 hours in 75 DEG C, be subsequently placed in horse
In good fortune furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, the composition of gained catalyst is listed in
Table 1.Evaluation result is listed in table 2.
[comparative example 3]
In addition to HfO is not added2Outside, method for preparing catalyst and evaluation condition be with embodiment 1, specifically:
It will be equivalent to 50.97 parts of Fe2O3Iron oxide red, be equivalent to 25.49 parts of Fe2O3Iron oxide yellow, be equivalent to 6.67
Part K2The potassium carbonate of O is equivalent to 0.85 part of WO3Ammonium tungstate, 7.97 parts of CeO2, 4.23 parts of Sr, 3.82 parts of Pr2O3And 5.8 parts of carboxylics
Sodium carboxymethylcellulose pyce stirs 1 hour in kneader, the water for accounting for total catalyst weight 25.8% is added, then mix and stir 0.5 hour, squeezes
At 3 millimeters of diameter, the particle of 6 millimeters of length, it is put into baking oven, dries 2.5 hours, 138 DEG C and dries 2 hours in 75 DEG C, be subsequently placed in horse
In good fortune furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, the composition of gained catalyst is listed in
Table 1.Evaluation result is listed in table 2.
[embodiment 2]
In addition to La2O3Replace Pr2O3Outside, method for preparing catalyst and evaluation condition be with embodiment 1, specifically:
It will be equivalent to 47.94 parts of Fe2O3Iron oxide red, be equivalent to 23.97 parts of Fe2O3Iron oxide yellow, be equivalent to 6.28
Part K2The potassium carbonate of O is equivalent to 0.8 part of WO3Ammonium tungstate, 7.5 parts of CeO2, 3.98 parts of SrO, 5.86 parts of HfO2, 3.6 parts of La2O3
And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, the water for accounting for total catalyst weight 25.8% are added, then mix and stir
0.5 hour, it is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, dries 2.5 hours, 138 DEG C and dry 2 hours in 75 DEG C,
It is subsequently placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, gained catalyst
Composition be listed in table 1.Evaluation result is listed in table 2.
[embodiment 3]
In addition to Nd2O3Replace Pr2O3Outside, method for preparing catalyst and evaluation condition be with embodiment 1, specifically:
It will be equivalent to 47.94 parts of Fe2O3Iron oxide red, be equivalent to 23.97 parts of Fe2O3Iron oxide yellow, be equivalent to 6.28
Part K2The potassium carbonate of O is equivalent to 0.8 part of WO3Ammonium tungstate, 7.5 parts of CeO2, 3.98 parts of SrO, 5.86 parts of HfO2, 3.6 parts of Nd2O3
Niobium and 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, the water for accounting for total catalyst weight 25.8% are added, then mix
With 0.5 hour, be extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, be put into baking oven, dried in 75 DEG C dry within 2.5 hours, 138 DEG C it is 2 small
When, it is subsequently placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, gained is urged
The composition of agent is listed in table 1.Evaluation result is listed in table 2.
[embodiment 4]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 1.8 parts of La2O3With 1.8 parts
Nd2O3Replace 3.6 parts of Pr2O3。
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 1.8 parts of Pr2O3With 1.8 parts
Nd2O3Replace 3.6 parts of Pr2O3。
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 1.8 parts of Pr2O3With 1.8 parts
La2O3Replace 3.6 parts of Pr2O3。
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 1.2 parts of La2O3, 1.2 parts
Pr2O3With 1.2 parts of Nd2O3Replace 3.6 parts of Pr2O3。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 respectively.
[embodiment 8]
It will be equivalent to 51.0 parts of Fe2O3Iron oxide red, be equivalent to 25.5 parts of Fe2O3Iron oxide yellow, be equivalent to 6.67 parts
K2The potassium carbonate of O is equivalent to 0.85 part of WO3Ammonium tungstate, 7.97 parts of CeO2, 4.23 parts of SrO, 2.5 parts of HfO2, 1.28 parts
Pr2O3And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, and the water for accounting for total catalyst weight 25.8% is added, then
It mixes and stirs 0.5 hour, is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, it is small to dry 2 within baking 2.5 hours, 138 DEG C in 75 DEG C
When, it is subsequently placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, gained is urged
The composition of agent 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) 2.0, test result is listed in table 2.
[embodiment 9]
It will be equivalent to 45.33 parts of Fe2O3Iron oxide red, be equivalent to 22.67 parts of Fe2O3Iron oxide yellow, be equivalent to 5.0
Part K2The potassium carbonate of O is equivalent to 3.0 parts of WO3Ammonium tungstate, 11.0 parts of CeO2Cerium oxide, 3.0 parts of SrO, 7.1 parts of HfO2、2.9
Part Pr2O3And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, and the water for accounting for total catalyst weight 25.8% is added,
It mixes and stirs again 0.5 hour, is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, dried in 75 DEG C 2.5 hours, 138 DEG C and dry 2
Hour, it is subsequently placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, gained
The composition of catalyst 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) 2.0, test result is listed in table 2.
[embodiment 10]
It will be equivalent to 46.47 parts of Fe2O3Iron oxide red, be equivalent to 23.23 parts of Fe2O3Iron oxide yellow, be equivalent to 6.8
Part K2The potassium carbonate of O is equivalent to 4.6 parts of WO3Ammonium tungstate, be equivalent to 6.0 parts of CeO2Cerium hydroxide, 5.0 parts of SrO, 2.0 parts
HfO2, 2.9 parts of Pr2O3, 3.0 parts of MoO3And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, addition accounts for catalyst
The water of total weight 25.8%, then mix and stir 0.5 hour, it is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, in 75 DEG C
It dries 2.5 hours, 138 DEG C and dries 2 hours, be subsequently placed in muffle furnace, roast 1.5 hours, 920 DEG C and obtain in 550 DEG C for roasting 1.5 hours
To finished catalyst, the composition of gained catalyst 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) 2.0, test result is listed in table 2.
[embodiment 11]
It will be equivalent to 48.67 parts of Fe2O3Iron oxide red, be equivalent to 24.33 parts of Fe2O3Iron oxide yellow, be equivalent to 6.0
Part K2The potassium carbonate of O is equivalent to 2.25 parts of WO3Ammonium tungstate, 8.5 parts of CeO2, 2.0 parts of SrO, 4.85 parts of HfO2, 2.9 parts of Pr2O3、
0.5 part of cement and 5.8 parts of sodium carboxymethylcellulose stir 1 hour in kneader, and addition accounts for total catalyst weight 25.8%
Water, then mix and stir 0.5 hour, be extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, be put into baking oven, in 75 DEG C of bakings 2.5 hours, 138
DEG C dry 2 hours, be subsequently placed in muffle furnace, roasted in 550 DEG C 1.5 hours, 920 DEG C of roastings obtain finished catalyst within 1.5 hours,
The composition of gained catalyst 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) 2.0, test result is listed in table 2.
[embodiment 12]
It will be equivalent to 52.0 parts of Fe2O3Iron oxide red, be equivalent to 26.0 parts of Fe2O3Iron oxide yellow, be equivalent to 4.0 parts
K2The potassium carbonate of O is equivalent to 1.0 parts of WO3Ammonium tungstate, 6.0 parts of CeO2, 0.5 part of SrO, 3.0 parts of HfO2, 7.5 parts of Pr2O3And 5.8
Part sodium carboxymethylcellulose stir 1 hour in kneader, and addition accounts for the water of total catalyst weight 25.8%, then to mix and stir 0.5 small
When, it is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, dries 2.5 hours, 138 DEG C and dry 2 hours in 75 DEG C, then set
In muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, the composition of gained catalyst
It 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) 2.0, test result is listed in table 2.
[embodiment 13]
It will be equivalent to 52.5 parts of Fe2O3Iron oxide red, be equivalent to 17.5 parts of Fe2O3Iron oxide yellow, be equivalent to 5.8 parts
K2The potassium carbonate of O is equivalent to 1.7 parts of WO3Ammonium tungstate, 10.0 parts of CeO2, 2.5 parts of SrO, 5.0 parts of HfO2, 5.0 parts of Pr2O3And
5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, the water for accounting for total catalyst weight 25.8% are added, then mix and stir 0.5
Hour, be extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, be put into baking oven, in 75 DEG C dry 2.5 hours, 138 DEG C dry 2 hours, then
It is placed in muffle furnace, is roasted 1.5 hours within roasting 1.5 hours, 920 DEG C in 550 DEG C and obtain finished catalyst, the group of gained catalyst
In column 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) 2.0, test result is listed in table 2.
[embodiment 14]
It will be equivalent to 48.68 parts of Fe2O3Iron oxide red, be equivalent to 24.34 parts of Fe2O3Iron oxide yellow, be equivalent to 5.61
Part K2The potassium carbonate of O is equivalent to 2.87 parts of WO3Ammonium tungstate, 8.63 parts of CeO2, 2.33 parts of SrO, 4.73 parts of HfO2, 1.8 parts
Pr2O3, 1.01 parts of ScO2And 5.8 parts of sodium carboxymethylcelluloses stir 1 hour in kneader, addition accounts for total catalyst weight
25.8% water, then mix and stir 0.5 hour, it is extruded into the particle of 3 millimeters of diameter, 6 millimeters of length, is put into baking oven, it is small to dry 2.5 in 75 DEG C
When, 138 DEG C dry 2 hours, be subsequently placed in muffle furnace, roasted in 550 DEG C 1.5 hours, 920 DEG C of roastings obtain finished product within 1.5 hours
Catalyst, the composition of gained catalyst are 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) 2.0, test result is listed in table 2.
The weight percent of 1 catalyst of table forms (continued)
The weight percent of 1 catalyst of table forms (Continued)
The comparison of 2 catalyst performance of table
Above embodiments explanation, adds hafnium oxide and light in addition to cerium oxide in iron-potassium-cerium-tungsten-strontium catalyst system
Rare earth oxide is co-catalyst, not adding additives, hence it is evident that improves the low temperature active and stability of low potassium catalyst, catalyst
Broad application temperature range, stability is good, is recommendable novel low-temperature energy-saving type catalyst.
Claims (8)
1. the low-temperature ethyl benzene dehydrogenation catalyst of low potassium content includes following component by weight percentage:
(a) 68~79% Fe2O3；
(b) 4~7% K2O；
(c) 6~12% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% SrO；
(f) 2~8% HfO2；
(g) 0.5~7% light rare earth oxide except cerium, the light rare earth oxide are selected from La2O3、Pr2O3Or Nd2O3's
It is at least one.
2. low-temperature ethyl benzene dehydrogenation catalyst according to claim 1, it is characterised in that by weight percentage, except cerium
Another light rare earth oxide, content are 1.5~6%.
3. low-temperature ethyl benzene dehydrogenation catalyst according to claim 1, it is characterised in that HfO2Content be 4~6%.
4. the preparation method of catalyst described in claim 1, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W,
Sr, Hf, light rare earth oxide and perforating agent after mixing, add water to mediate, and obtain the catalysis through extrusion, drying and roasting
Agent.
5. the preparation method according to claim 4, it is characterised in that drying temperature is 60~150 DEG C.
6. the preparation method according to claim 4, it is characterised in that maturing temperature is 500~1000 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,
Its weight proportion is Fe2O3: 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 oxide or cerous carbonate.
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| CN115487819B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof, and method for preparing alkyl alkenyl benzene by dehydrogenation of alkylbenzene |
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| AU698764B2 (en) * | 1994-12-14 | 1998-11-05 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst and process |
| CN100430133C (en) * | 2005-12-14 | 2008-11-05 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst |
| CN101279263B (en) * | 2007-04-04 | 2010-07-21 | 中国石油化工股份有限公司 | Catalyst for preparation of styrene by ethylbenzene dehydrogenation |
| CN101279266B (en) * | 2007-04-04 | 2010-07-21 | 中国石油化工股份有限公司 | Energy-saving catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene |
| CN101422735B (en) * | 2007-11-01 | 2010-12-15 | 中国石油天然气股份有限公司 | Effective styrene preparation catalyst by dehydrogenation of ethyl benzene and preparation method thereof |
| CN101733113B (en) * | 2008-11-18 | 2012-05-30 | 中国石油天然气股份有限公司 | Catalyst used for dehydrogenation of ethyl benzene for preparing styrene and method for preparing same |
| CN103537292B (en) * | 2012-07-12 | 2015-09-09 | 中国石油化工股份有限公司 | For the preparation of cinnamic dehydrogenation |
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