CN106582678B - The catalyst of high activity low-water ratio ethylbenzene dehydrogenation - Google Patents
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Abstract
The present invention relates to catalyst of high activity low-water ratio ethylbenzene dehydrogenation and preparation method thereof, mainly solve the problems, such as that low potassium catalyst present in conventional art is poor, active low in low-water ratio conditions stability inferior.The present invention includes following component: 66~79% Fe by using high activity ethylbenzene dehydrogenation catalyst with low water ratio by weight percentage2O3；4~9% K2O；6~11% CeO2；1~5% WO3；0.5~5% BaO；0.5~8% SnO2；0.5~5% middle rare earth；0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；The middle rare earth is selected from Sm2O3、Eu2O3Or Gd2O3At least one technical solution, preferably solve the problems, such as this, can be used under low-water ratio conditions in the industrial production of ethyl benzene dehydrogenation preparation of styrene.
Description
Technical field
The present invention relates to a kind of high activity production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation and preparation method thereof.
Background technique
The main reaction of ethylbenzene dehydrogenation is C6H5-C2H5→C6H5CH=CH2+H2+124KJ/mol.From thermodynamically, reduce
Ethylbenzene partial pressure is advantageous to balancing, therefore is industrially usually added into water vapour, promotes reaction mobile to product direction.Ethylbenzene dehydrogenation is raw
Producing styrene technology latest development trend is to reduce raw materials consumption and raising efficiency.The latent heat of vaporization of water is very big, and styrene is raw
Production process consumes a large amount of superheated vapours and makes that the process energy consumption is big, production cost remains high as dehydrogenation medium.Exploitation is suitable
For water ratio in isotherm formula fixed bed lower than 1.6 (weight) low water ratio catalyst, to reduce commercial plant operation water liken to
For styrene device, particularly large-scale styrene device there is an urgent need to.
What industrial dehydrogenation of ethylbenzene to styrene generallyd use is using iron oxide as based on main active component, potassium oxide
The Fe-series catalyst of co-catalyst is wanted, usual potassium content is greater than 15%, but potassium washes away lower easy loss and move in high-temperature water vapor
It moves, influence catalyst is that catalyst for phenylethylene dehydrogenation is developed from low potassium content within power of regeneration and stability, realization 10%
Mainstream.Generally accepted potash is most effective anti-carbon deposit auxiliary agent, and low potassium catalyst operates under low water ratio, and catalyst surface is special
It is easy carbon deposit, stability is poor, it is therefore necessary to try to enhance the ability of the low resistance to low water ratio of potassium catalyst.
In this regard, people had made much to attempt according to related reported in literature so far.European patent 0177832 is reported
It is excellent lower than being shown under 2.0 (weight) in water ratio after the magnesia of 1.8~5.4% (weight) is added in road in the catalyst
Stability, but the potassium content of the catalyst is higher, is greater than 20%.As ZL95111761.0 has been reported in Fe-K-Cr system
Middle addition Multimetal oxide and silica solution, catalyst obtained is suitable for running under low water ratio, but the catalyst contains pollution
Environment, the Cr being eliminated.
With the enlargement of styrene device scale, energy conservation is become more and more important.Therefore, to the use of dehydrogenation
Condition makees small improvement, is not required to change any equipment, is not required to increase investment, and manufacturing enterprise can be made to obtain huge economic effect
Benefit.It develops one kind to be suitable for operation under low-water ratio conditions, there is higher active low potassium catalyst, is always what researcher made great efforts
Direction.
Summary of the invention
The first technical problem to be solved by the present invention is low potassium catalyst present in conventional art in low-water ratio conditions
The problem that stability inferior is poor, activity is low, provides a kind of catalyst of new high activity low-water ratio ethylbenzene dehydrogenation, which is used for
Ethylbenzene dehydrogenation reaction has the characteristics that good, active high in low-water ratio conditions stability inferior.
The second technical problem to be solved by the present invention is to provide a kind of corresponding with one of technical problem is solved high living
The preparation method of property ethylbenzene dehydrogenation catalyst with low water ratio.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: high activity low-water ratio ethylbenzene dehydrogenation
Catalyst, by weight percentage include following component:
(a) 66~79% Fe2O3；
(b) 4~9% K2O；
(c) 6~11% CeO2；
(d) 1~5% WO3；
(e) 0.5~5% BaO；
(f) 0.5~8% SnO2；
(g) 0.5~5% middle rare earth；
(h) 0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；
The middle rare earth is selected from Sm2O3、Eu2O3Or Gd2O3At least one.
In above-mentioned technical proposal, the middle rare earth preferably includes Sm simultaneously2O3And Eu2O3Or Sm2O3And Gd2O3,
Or Eu2O3And Gd2O3, described two middle rare earths are about activity with binary synergistic effect；More preferably include simultaneously
Sm2O3、Eu2O3And Gd2O3, have the effect of trielement synergistic about activity at this time.
In above-mentioned technical proposal, SnO2Content is preferably 1~7%.
In above-mentioned technical proposal, SnO2Content is preferably 2~5%.
In above-mentioned technical proposal, middle rare earth content is preferably 0.8~4%.
In above-mentioned technical proposal, Ce is added preferably in the form of cerium oxalate or cerous acetate.
In above-mentioned technical proposal, molybdenum oxide is not preferably contained in catalyst.
In above-mentioned technical proposal, by weight percentage, Fe2O3It is preferred from iron oxide red and iron oxide yellow, is matched excellent
It is selected as iron oxide red: iron oxide yellow=2.5~4.5:1.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the skill of one of above-mentioned technical problem
The preparation method of catalyst described in art scheme, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W, Ba, Sn, need to add
The binder and perforating agent and water of the middle rare earth and non-imposed addition that enter are uniformly mixed, through extrusion, drying, roasting
Burning obtains the catalyst.It is preferred that the additional amount of water is the water of catalyst raw material gross weight 15~35%.
In above-mentioned technical proposal, drying temperature is not particularly limited, such as 40~160 DEG C, drying time optional 0.5~8
Hour.
In above-mentioned technical proposal, as preferably selecting, drying gradually heats up, such as, but not limited to 40~70 DEG C dryings 2
~4 hours, then 80~160 DEG C drying 0.5~4 hour.
In above-mentioned technical proposal, optional 350~1000 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 350~
600 DEG C roast 2~4 hours, then roast 2~4 hours at 900~1000 DEG C.
Raw material used in catalyst component of the present invention is as follows:
Fe used2O3It is added in the form of iron oxide red and iron oxide yellow；K used is added with potassium as potassium carbonate；W used is with it
Salt or oxide form be added；Ba used is with the addition of oxide, hydroxide or barium salt；Sn used is with oxide or nitre
Acid salts are added；Remaining element is added in the form of an oxide.In preparation process of the invention, catalyst body ingredient is removed
Perforating agent should also be added outside, perforating agent can be selected from graphite, polystyrene microsphere or sodium carboxymethylcellulose, and 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 in iron-potassium-cerium-tungsten-barium catalyst system by adding tin oxide and being selected from middle rare earth Sm2O3、
Eu2O3Or Gd2O3At least one, on the one hand, enhance the electron transmission ability of active phase, help to obtain higher activity,
On the other hand the alkalinity of system is improved, stablizes and has dispersed the active phase of catalyst, accelerate water vapour and catalyst surface
The rate of water gas reaction occurs for carbon deposit, enhance catalyst from power of regeneration.It is being waited using catalyst prepared by the present invention
Warm formula fixed bed carries out activity rating, in normal pressure, ethylbenzene liquid volume air speed by common 1.0 hours- 1Increase by 50% to 1.5
Hour- 1, 620 DEG C, water ratio checked and rated under the conditions of reducing by 35% to 1.3 (weight) by common 2.0 (weight), high conversion rate reaches
72.5%, operation 500 hours after conversion ratio be basically unchanged, hence it is evident that improve low potassium catalyst under low-water ratio conditions activity and
Stability 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 57.47 parts of Fe2O3Iron oxide red, be equivalent to 18.18 parts of Fe2O3Iron oxide yellow, be equivalent to 8.6
Part K2The potassium carbonate of O is equivalent to 7.21 parts of CeO2Cerium oxalate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of BaO
Barium hydroxide, 3.16 parts of SnO2, 1.68 parts of Sm2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader,
The deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, roasted 3 hours in 550 DEG C,
920 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 1.5 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.3, test result is listed in table 2.
[comparative example 1]
In addition to not having to SnO2And Sm2O3In addition, relative scale relationship, method for preparing catalyst and the catalyst of remaining component
Evaluation condition is same as Example 1, specifically:
It will be equivalent to 60.39 parts of Fe2O3Iron oxide red, be equivalent to 19.11 parts of Fe2O3Iron oxide yellow, be equivalent to 9.04
Part K2The potassium carbonate of O is equivalent to 7.58 parts of CeO2Cerium oxalate, be equivalent to 2.71 parts of WO3Ammonium tungstate, be equivalent to 1.18 parts of BaO
Barium hydroxide and 5.69 parts of sodium carboxymethylcelluloses stirred in kneader 1.5 hours, addition account for catalyst raw material gross weight
25% deionized water mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking oven, and 60 DEG C
It dries 2 hours, 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 920 DEG C of roastings obtain finished product in 3 hours
Catalyst, catalyst composition are listed in table 1.Test result is listed in table 2.
[comparative example 2]
In addition to not having to SnO2In addition, the relative scale relationship of remaining component, method for preparing catalyst and evaluating catalyst item
Part is same as Example 1, specifically:
It will be equivalent to 59.35 parts of Fe2O3Iron oxide red, be equivalent to 18.77 parts of Fe2O3Iron oxide yellow, be equivalent to 8.88
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of BaO
Barium hydroxide, 1.73 parts of Sm2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader, addition accounts for catalyst
The deionized water of raw material gross weight 25% mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 920 DEG C of roastings 3 are small
When obtain finished catalyst, catalyst composition is listed in table 1.Test result is listed in table 2.
[embodiment 2]
In addition to Eu2O3Substitute Sm2O3In addition, method for preparing catalyst and evaluating catalyst condition with 1 phase of embodiment
Together, specifically:
It will be equivalent to 57.47 parts of Fe2O3Iron oxide red, be equivalent to 18.18 parts of Fe2O3Iron oxide yellow, be equivalent to 8.6
Part K2The potassium carbonate of O is equivalent to 7.21 parts of CeO2Cerium oxalate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of BaO
Barium hydroxide, 3.16 parts of SnO2, 1.68 parts of Eu2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader,
The deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, roasted 3 hours in 550 DEG C,
920 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Test result is listed in table 2.
[comparative example 3]
In addition to not having to SnO2In addition, the relative scale relationship of remaining component, method for preparing catalyst and evaluating catalyst item
Part is same as Example 2, specifically:
It will be equivalent to 59.35 parts of Fe2O3Iron oxide red, be equivalent to 18.77 parts of Fe2O3Iron oxide yellow, be equivalent to 8.88
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of BaO
Barium hydroxide, 1.73 parts of Eu2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader, addition accounts for catalyst
The deionized water of raw material gross weight 25% mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 920 DEG C of roastings 3 are small
When obtain finished catalyst, catalyst composition is listed in table 1.Test result is listed in table 2.
[embodiment 3]
In addition to Gd2O3Substitute Sm2O3In addition, method for preparing catalyst and evaluating catalyst condition with 1 phase of embodiment
Together, specifically:
It will be equivalent to 57.47 parts of Fe2O3Iron oxide red, be equivalent to 18.18 parts of Fe2O3Iron oxide yellow, be equivalent to 8.6
Part K2The potassium carbonate of O is equivalent to 7.21 parts of CeO2Cerium oxalate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of BaO
Barium hydroxide, 3.16 parts of SnO2, 1.68 parts of Gd2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader,
The deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, roasted 3 hours in 550 DEG C,
920 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.Test result is listed in table 2.
[comparative example 4]
In addition to not having to SnO2In addition, the relative scale relationship of remaining component, method for preparing catalyst and evaluating catalyst item
Part is same as Example 3, specifically:
It will be equivalent to 59.35 parts of Fe2O3Iron oxide red, be equivalent to 18.77 parts of Fe2O3Iron oxide yellow, be equivalent to 8.88
Part K2The potassium carbonate of O is equivalent to 7.45 parts of CeO2Cerium oxalate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of BaO
Barium hydroxide, 1.73 parts of Gd2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader, addition accounts for catalyst
The deionized water of raw material gross weight 25% mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 920 DEG C of roastings 3 are small
When obtain finished catalyst, catalyst composition is listed in table 1.Test result is listed in table 2.
[embodiment 4]
Catalyst and test catalyst are prepared as described in Example 1, except that with 0.84 part of Sm2O3With 0.84 part
Eu2O3Substitute 1.68 parts of Sm2O3。
The composition of catalyst is shown in Table 1, and test result is listed in table 2.
[embodiment 5]
Catalyst and test catalyst are prepared as described in Example 1, except that with 0.84 part of Sm2O3With 0.84 part
Gd2O3Substitute 1.68 parts of Sm2O3。
The composition of catalyst is shown in Table 1, and test result is listed in table 2.
[embodiment 6]
Catalyst and test catalyst are prepared as described in Example 1, except that with 0.84 part of Eu2O3With 0.84 part
Gd2O3Substitute 1.68 parts of Sm2O3。
The composition of catalyst is shown in Table 1, and test result is listed in table 2.
[embodiment 7]
Catalyst and test catalyst are prepared as described in Example 1, except that with 0.56 part of Sm2O3, 0.56 part
Eu2O3With 0.56 part of Gd2O3Substitute 1.68 parts of Sm2O3。
The composition of catalyst is shown in Table 1, and test result is listed in table 2.
[embodiment 8]
It will be equivalent to 53.88 parts of Fe2O3Iron oxide red, be equivalent to 17.05 parts of Fe2O3Iron oxide yellow, be equivalent to 7.85
Part K2The potassium carbonate of O is equivalent to 8.9 parts of CeO2Cerium oxalate, be equivalent to 4.13 parts of WO3Ammonium tungstate, be equivalent to 3.35 parts of BaO
Barium hydroxide, 3.5 parts of SnO2, 0.85 part of Sm2O3, 0.49 part of ZrO2And 4.62 parts of graphite stir 1.5 hours in kneader,
The deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, roasted 3 hours in 550 DEG C,
920 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 1.5 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.3, test result is listed in table 2.
[embodiment 9]
It will be equivalent to 52.73 parts of Fe2O3Iron oxide red, be equivalent to 13.45 parts of Fe2O3Iron oxide yellow, be equivalent to 4.25
Part K2The potassium carbonate of O is equivalent to 10.85 parts of CeO2Cerium oxalate, be equivalent to 1.21 parts of WO3Ammonium tungstate, be equivalent to 4.95 parts
The barium hydroxide of BaO, 7.8 parts of SnO2, 4.25 parts of Sm2O3, 0.51 part of MoO3And that 1.5 are stirred in kneader is small for 4.62 parts of graphite
When, the deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6
The particle of millimeter is put into baking oven, and 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, small in 550 DEG C of roastings 3
When, 920 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 1.5 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.3, test result is listed in table 2.
[embodiment 10]
It will be equivalent to 55.36 parts of Fe2O3Iron oxide red, be equivalent to 17.42 parts of Fe2O3Iron oxide yellow, be equivalent to 5.71
Part K2The potassium carbonate of O is equivalent to 7.46 parts of CeO2Cerium oxalate, be equivalent to 4.62 parts of WO3Ammonium tungstate, be equivalent to 1.03 parts of BaO
Barium hydroxide, 0.72 part of SnO2, 4.58 parts of Sm2O3, 3.1 parts of cement and 4.95 parts of sodium carboxymethylcelluloses stir in kneader
It mixes 1.5 hours, the deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, take out extrusion, be extruded into 3 milli of diameter
Rice, long 6 millimeters of particle are put into baking oven, and 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C
It burns 3 hours, 920 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 1.5 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.3, test result is listed in table 2.
[embodiment 11]
It will be equivalent to 60.63 parts of Fe2O3Iron oxide red, be equivalent to 17.42 parts of Fe2O3Iron oxide yellow, be equivalent to 6.05
Part K2The potassium carbonate of O is equivalent to 6.15 parts of CeO2Cerium oxalate, be equivalent to 2.03 parts of WO3Ammonium tungstate, be equivalent to 0.55 part of BaO
Barium hydroxide, 5.15 parts of SnO2, 2.02 parts of Sm2O3And 4.95 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader,
The deionized water for accounting for catalyst raw material gross weight 25% is added, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, 6 millimeters of length
Particle, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, roasted 3 hours in 550 DEG C,
920 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 1.5 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.3, test result is listed in table 2.
[comparative example 5]
In addition to CeO2Substitute other than cerium oxalate, method for preparing catalyst and evaluating catalyst condition with 1 phase of embodiment
Together, specifically:
It will be equivalent to 57.47 parts of Fe2O3Iron oxide red, be equivalent to 18.18 parts of Fe2O3Iron oxide yellow, be equivalent to 8.6
Part K2The potassium carbonate of O, 7.21 parts of CeO2, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of BaO barium hydroxide,
3.16 part SnO2, 1.68 parts of Sm2O3And 5.69 parts of sodium carboxymethylcelluloses stir 1.5 hours in kneader, addition accounts for catalyst
The deionized water of raw material gross weight 25% mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 920 DEG C of roastings 3 are small
When obtain finished catalyst, catalyst composition is listed in table 1.Test 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 tin oxide in iron-potassium-cerium-tungsten-barium catalyst system and is selected from middle rare earth
Sm2O3、Eu2O3Or Gd2O3At least one, improve activity and stability of the low potassium catalyst under low-water ratio conditions, have
Significant energy-saving effect can be used under low-water ratio conditions in the industrial production of ethyl benzene dehydrogenation preparation of styrene.
Claims (9)
1. the catalyst of high activity low-water ratio ethylbenzene dehydrogenation includes following component by weight percentage:
(a) 66~79% Fe2O3；
(b) 4~9% K2O；
(c) 6~11% CeO2；
(d) 1~5% WO3；
(e) 0.5~5% BaO；
(f) 0.5~8% SnO2；
(g) 0.5~5% middle rare earth；
(h) 0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；
The middle rare earth is selected from Sm2O3、Eu2O3Or Gd2O3At least one.
2. catalyst according to claim 1, it is characterised in that SnO2Content is 1~7%.
3. catalyst according to claim 2, it is characterised in that SnO2Content is 2~5%.
4. catalyst according to claim 1, it is characterised in that middle rare earth content is 0.8~4%.
5. catalyst according to claim 1, it is characterised in that Ce is added in the form of cerium oxalate or cerous carbonate.
6. catalyst according to claim 1, it is characterised in that do not contain molybdenum oxide in catalyst.
7. the preparation method of catalyst described in claim 1, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W,
Ba, Sn, the binder of the middle rare earth that need to be added and non-imposed addition and perforating agent and water are uniformly mixed, through squeezing
Out, dry and roasting obtains the catalyst.
8. preparation method according to claim 7, it is characterised in that drying temperature is 40~160 DEG C.
9. preparation method according to claim 7, it is characterised in that maturing temperature is 350~1000 DEG C.
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| CN112237922A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN113877593B (en) * | 2020-07-02 | 2024-02-23 | 中国石油化工股份有限公司 | High-strength alkyl aromatic hydrocarbon dehydrogenation catalyst, preparation method and application thereof, and alkyl aromatic hydrocarbon dehydrogenation method |
| CN115957773B (en) | 2021-10-11 | 2024-05-03 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810368A (en) * | 2005-01-26 | 2006-08-02 | 中国石油化工股份有限公司 | Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene |
| CN101279267A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Energy-saving catalyst for phenylethylene dehydrogenation |
| CN101733113A (en) * | 2008-11-18 | 2010-06-16 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN102040466A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN102343269A (en) * | 2010-08-05 | 2012-02-08 | 中国石油天然气股份有限公司 | Ethylbenzene dehydrogenation catalyst taking micron-sized ferric oxide and potassium carbonate as raw materials |
| CN103769151A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | High activity and low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
-
2015
- 2015-10-16 CN CN201510671574.6A patent/CN106582678B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810368A (en) * | 2005-01-26 | 2006-08-02 | 中国石油化工股份有限公司 | Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene |
| CN101279267A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Energy-saving catalyst for phenylethylene dehydrogenation |
| CN101733113A (en) * | 2008-11-18 | 2010-06-16 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN102040466A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN102343269A (en) * | 2010-08-05 | 2012-02-08 | 中国石油天然气股份有限公司 | Ethylbenzene dehydrogenation catalyst taking micron-sized ferric oxide and potassium carbonate as raw materials |
| CN103769151A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | High activity and low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
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