CN106582678A - High-activity and low-water-ratio ethylbenzene dehydrogenation catalyst - Google Patents
High-activity and low-water-ratio ethylbenzene dehydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to a high-activity and low-water-ratio ethylbenzene dehydrogenation catalyst and a preparation method thereof and mainly solves the problems that a low-potassium catalyst is poor in stability and low in activity under the low water ratio condition in the prior art. The technical scheme is as follows: the high-activity and low-water-ratio ethylbenzene dehydrogenation catalyst is prepared from components in percentage by weight as follows: 66%-79% of Fe2O3, 4%-9% of K2O, 6%-11% of CeO2, 1%-5% of WO3, 0.5%-5% of BaO, 0.5%-8% of SnO2, 0.5%-5% of heavy rare earth oxide and 0-4% of a binder, wherein the binder is selected from one of kaolin, diatomite and cement; the heavy rare earth oxide is selected from at least one of Sm2O3, Eu2O3 and Gd2O3, so that the problem is better solved, and the catalyst can be applied to industrial production of preparation of styrene through ethylbenzene dehydrogenation under the low water ratio condition.
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 technology
The primary response of ethylbenzene dehydrogenation is C6H5-C2H5→C6H5CH=CH2+H2+124KJ/mol.From thermodynamically, reduce
Ethylbenzene partial pressure is favourable to balancing, therefore is industrially usually added into water vapour, promotes to react to product direction and moves.Ethylbenzene dehydrogenation
Production styrene technology latest development trend is to reduce raw materials consumption and improve efficiency.The latent heat of vaporization of water is very big, styrene
Production process consumes a large amount of superheated vapours and causes as dehydrogenation medium that the process energy consumption is big, production cost remains high.Exploitation
Water is operated less than the low water ratio catalyst of 1.6 (weight), so as to reduce commercial plant suitable for water ratio isotherm formula fixed bed
Than become styrene device, particularly large-scale styrene device in the urgent need to.
Industrial dehydrogenation of ethylbenzene to styrene is generally used with ferrum oxide as main active component, potassium oxide is mainly to help
The Fe-series catalyst of catalyst, usual potassium content are more than 15%, but potassium washes away lower easy loss and migration in high-temperature water vapor,
Affect catalyst from regeneration capacity and stability, realize that low potassium content within 10% is the master of catalyst for phenylethylene dehydrogenation exploitation
Stream.Generally accepted potash is maximally effective anti-carbon deposit auxiliary agent, and low potassium catalyst is operated under low water ratio, and catalyst surface is special
Easy carbon deposit, stability are poor, it is therefore necessary to try to strengthen the ability of the resistance to low water ratio of low potassium catalyst.
In this regard, according to relevant reported in literature so far, people had made many trials.European patent 0177832 is reported
After adding the magnesium oxide of 1.8～5.4% (weight) in the catalyst, show in the case where water ratio is less than 2.0 (weight) excellent
Stability, but the potassium content of the catalyst is higher, more than 20%.As ZL95111761.0 has been reported in Fe-K-Cr
Multimetal oxide and Ludox are added in system, obtained catalyst is suitable to run under low water ratio, but the catalyst contains
Pollution environment, the Cr being eliminated.
With the maximization of styrene device scale, energy-conservation seems more and more important.Therefore, the use bar to dehydrogenation
Part makees small improvement, is not required to change any equipment, is not required to increase investment, can just make manufacturing enterprise obtain huge economic effect
Benefit.Exploitation one kind is suitable under low-water ratio conditions operation, with higher active low potassium catalyst, always research worker effort
Direction.
The content of the invention
One of the technical problem to be solved is that low potassium catalyst present in conventional art is stable under low-water ratio conditions
Property poor, the low problem of activity, there is provided a kind of catalyst of new high activity low-water ratio ethylbenzene dehydrogenation, the catalyst are used for ethylbenzene
Dehydrogenation reaction with low-water ratio conditions stability inferior it is good, it is active high the characteristics of.
The two of the technical problem to be solved be to provide it is a kind of with solve the corresponding low water of high activity of one of technical problem
Than the preparation method of catalyst for phenylethylene dehydrogenation.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：High activity low-water ratio ethylbenzene dehydrogenation is urged
Agent, by weight percentage including following component：
The Fe of (a) 66～79%2O3；
The K of (b) 4～9%2O；
The CeO of (c) 6～11%2；
The WO of (d) 1～5%3；
The BaO of (e) 0.5～5%；
The SnO of (f) 0.5～8%2；
The middle rare earth of (g) 0.5～5%；
The binding agent of (h) 0～4%, the one kind of binding agent selected from Kaolin, kieselguhr 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 Eu2O3, or Sm2O3And Gd2O3, or
Eu2O3And Gd2O3, described two middle rare earths are with regard to activity with binary synergism；More preferably include Sm simultaneously2O3、
Eu2O3And Gd2O3, now there is the effect of trielement synergistic with regard to activity.
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 preferably added with Sedemesis. or cerous acetate form.
In above-mentioned technical proposal, molybdenum oxide in catalyst, is not preferably contained.
In above-mentioned technical proposal, by weight percentage, Fe2O3Iron oxide red and iron oxide yellow are preferred from, its proportioning is excellent
Elect iron oxide red as：Iron oxide yellow=2.5～4.5:1.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, comprises the following steps：By by proportioning weigh Fe, K, Ce, W, Ba, Sn,
The middle rare earth that need to be added and the binding agent and perforating agent of non-imposed addition, and water mix homogeneously, it is extruded, dry
Dry, roasting obtains the catalyst.It is preferred that water of the addition of water for catalyst raw material gross weight 15～35%.
In above-mentioned technical proposal, baking temperature is not particularly limited, such as 40～160 DEG C, and drying time is optional 0.5～8 hour.
In above-mentioned technical proposal, as preferably selecting, drying progressively heats up, and such as but not limited to 40～70 DEG C dryings 2～
4 hours, then 80～160 DEG C of dryings 0.5～4 hour.
In above-mentioned technical proposal, sintering temperature is optional 350～1000 DEG C, and roasting time is optional 2～8 hours.
In above-mentioned technical proposal, as preferably roasting condition, sintering temperature is stepped up, such as but not limited to 350～600 DEG C
Roasting 2～4 hours, then roasting 2～4 hours at 900～1000 DEG C.
Raw material used by catalyst component according to the present invention is as follows：
Fe used2O3Added with iron oxide red and iron oxide yellow form；K used is added with potassium as potassium carbonate；W used is with it
Salt or oxide form add；Ba used is added with oxide, hydroxide or barium salt；Sn used is with oxide
Or nitrate salts are added；Remaining element is added in the form of an oxide.In the preparation process of the present invention, except catalyst master
Should also add perforating agent, perforating agent select from graphite, polystyrene microsphere or sodium carboxymethyl cellulose outside body composition, its
Addition for total catalyst weight 2～6%.
Obtained catalyst carries out activity rating in isotherm formula fixed bed as stated above, and ethyl benzene dehydrogenation preparation of styrene is catalyzed
For agent activity rating, process is summarized as follows：
Sub- water and ethylbenzene difference Jing dosing pump input preheating mixers are will be disengaged from, preheating enters reactor after being mixed into gaseous state, instead
Answer device to adopt electric-heating-wire-heating, make up to predetermined temperature.Reactor inside diameter be 1 " stainless steel tube, 100 milliliters of interior filling,
The catalyst that 3 millimeters of particle diameter.After being coagulated by the reactant of reactor outflow is water cooled, with chromatographic, which constitutes.
Conversion of ethylbenzene, selectivity of styrene are calculated as follows：
The present invention is by adding stannum oxide and being selected from middle rare earth Sm in ferrum-potassium-cerium-tungsten-barium catalyst system and catalyzing2O3、Eu2O3
Or Gd2O3At least one, on the one hand, enhance the electron transmission ability of active phase, be conducive to obtaining higher activity,
On the other hand the alkalescence of system is improve, active phase that is stable and having disperseed catalyst accelerates water vapour and catalyst surface
Carbon deposit occur water gas reaction speed, enhance catalyst from regeneration capacity.The catalyst prepared using the present invention is being waited
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 check and rate under the conditions of reducing by 35% to 1.3 (weight) by common 2.0 (weight), turn
Rate is up to 72.5%, and after running 500 hours, conversion ratio is basically unchanged, hence it is evident that improve low potassium catalyst in low-water ratio conditions
Under activity and stability, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated：
Specific embodiment
[embodiment 1]
Will be equivalent to 57.47 parts of Fe2O3Iron oxide red, equivalent to 18.18 parts of Fe2O3Iron oxide yellow, equivalent to 8.6
Part K2The potassium carbonate of O, equivalent to 7.21 parts of CeO2Sedemesis., equivalent to 2.58 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.12 parts of BaO, 3.16 parts of SnO2, 1.68 parts of Sm2O3And 5.69 parts of sodium carboxymethyl cellulose are in kneader
Middle stirring 1.5 hours, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, squeezes
Into 3 millimeters of diameter, long 6 millimeters granule, baking oven is put into, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in
In muffle furnace, in 550 DEG C of roastings 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 loaded into reactors, in 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]
Except without SnO2And Sm2O3In addition, the relative scale relation of remaining component, method for preparing catalyst and catalyst
Appreciation condition is same as Example 1, specially：
Will be equivalent to 60.39 parts of Fe2O3Iron oxide red, equivalent to 19.11 parts of Fe2O3Iron oxide yellow, equivalent to 9.04
Part K2The potassium carbonate of O, equivalent to 7.58 parts of CeO2Sedemesis., equivalent to 2.71 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.18 parts of BaO and 5.69 parts of sodium carboxymethyl cellulose are stirred in kneader 1.5 hours, and 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 granule,
Baking oven is put into, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in muffle furnace, in 550 DEG C of roastings 3 hours, 920 DEG C
Roasting obtains finished catalyst for 3 hours, and catalyst composition is listed in table 1.Test result is listed in table 2.
[comparative example 2]
Except without SnO2In addition, the relative scale relation of remaining component, method for preparing catalyst and evaluating catalyst condition are equal
It is same as Example 1, specially：
Will be equivalent to 59.35 parts of Fe2O3Iron oxide red, equivalent to 18.77 parts of Fe2O3Iron oxide yellow, equivalent to 8.88
Part K2The potassium carbonate of O, equivalent to 7.45 parts of CeO2Sedemesis., equivalent to 2.66 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.16 parts of BaO, 1.73 parts of Sm2O3And 5.69 parts of sodium carboxymethyl cellulose that 1.5 are stirred in kneader is little
When, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, be extruded into 3 millimeters of diameter,
Long 6 millimeters granule, 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, in 550 DEG C
Roasting 3 hours, 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.
[embodiment 2]
Except with Eu2O3Substitute Sm2O3In addition, method for preparing catalyst and evaluating catalyst condition are same as Example 1,
Specially：
Will be equivalent to 57.47 parts of Fe2O3Iron oxide red, equivalent to 18.18 parts of Fe2O3Iron oxide yellow, equivalent to 8.6
Part K2The potassium carbonate of O, equivalent to 7.21 parts of CeO2Sedemesis., equivalent to 2.58 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.12 parts of BaO, 3.16 parts of SnO2, 1.68 parts of Eu2O3And 5.69 parts of sodium carboxymethyl cellulose are in kneader
Middle stirring 1.5 hours, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, squeezes
Into 3 millimeters of diameter, long 6 millimeters granule, baking oven is put into, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in
In muffle furnace, in 550 DEG C of roastings 3 hours, 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]
Except without SnO2In addition, the relative scale relation of remaining component, method for preparing catalyst and evaluating catalyst condition are equal
It is same as Example 2, specially：
Will be equivalent to 59.35 parts of Fe2O3Iron oxide red, equivalent to 18.77 parts of Fe2O3Iron oxide yellow, equivalent to 8.88
Part K2The potassium carbonate of O, equivalent to 7.45 parts of CeO2Sedemesis., equivalent to 2.66 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.16 parts of BaO, 1.73 parts of Eu2O3And 5.69 parts of sodium carboxymethyl cellulose are stirred in kneader 1.5 hours,
Addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, length
6 millimeters of granule, 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, in 550 DEG C
Roasting 3 hours, 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.
[embodiment 3]
Except with Gd2O3Substitute Sm2O3In addition, method for preparing catalyst and evaluating catalyst condition are same as Example 1,
Specially：
Will be equivalent to 57.47 parts of Fe2O3Iron oxide red, equivalent to 18.18 parts of Fe2O3Iron oxide yellow, equivalent to 8.6
Part K2The potassium carbonate of O, equivalent to 7.21 parts of CeO2Sedemesis., equivalent to 2.58 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.12 parts of BaO, 3.16 parts of SnO2, 1.68 parts of Gd2O3And 5.69 parts of sodium carboxymethyl cellulose are in kneader
Middle stirring 1.5 hours, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, squeezes
Into 3 millimeters of diameter, long 6 millimeters granule, baking oven is put into, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in
In muffle furnace, in 550 DEG C of roastings 3 hours, 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]
Except without SnO2In addition, the relative scale relation of remaining component, method for preparing catalyst and evaluating catalyst condition are equal
It is same as Example 3, specially：
Will be equivalent to 59.35 parts of Fe2O3Iron oxide red, equivalent to 18.77 parts of Fe2O3Iron oxide yellow, equivalent to 8.88
Part K2The potassium carbonate of O, equivalent to 7.45 parts of CeO2Sedemesis., equivalent to 2.66 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.16 parts of BaO, 1.73 parts of Gd2O3And 5.69 parts of sodium carboxymethyl cellulose are stirred in kneader 1.5 hours,
Addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, length
6 millimeters of granule, 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, in 550 DEG C
Roasting 3 hours, 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.
[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]
Will be equivalent to 53.88 parts of Fe2O3Iron oxide red, equivalent to 17.05 parts of Fe2O3Iron oxide yellow, equivalent to 7.85
Part K2The potassium carbonate of O, equivalent to 8.9 parts of CeO2Sedemesis., equivalent to 4.13 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 3.35 parts of BaO, 3.5 parts of SnO2, 0.85 part of Sm2O3, 0.49 part of ZrO2And 4.62 parts of graphite are being mediated
Stir 1.5 hours in machine, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, take out extrusion,
It is extruded into 3 millimeters of diameter, long 6 millimeters granule, is put into baking oven, 60 DEG C is dried 2 hours, and 130 DEG C are dried 3 hours, are then put
In muffle furnace, in 550 DEG C of roastings 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 loaded into reactors, in 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]
Will be equivalent to 52.73 parts of Fe2O3Iron oxide red, equivalent to 13.45 parts of Fe2O3Iron oxide yellow, equivalent to 4.25
Part K2The potassium carbonate of O, equivalent to 10.85 parts of CeO2Sedemesis., equivalent to 1.21 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 4.95 parts of BaO, 7.8 parts of SnO2, 4.25 parts of Sm2O3, 0.51 part of MoO3And 4.62 parts of graphite are being mediated
Stir 1.5 hours in machine, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, take out extrusion,
It is extruded into 3 millimeters of diameter, long 6 millimeters granule, is put into baking oven, 60 DEG C is dried 2 hours, and 130 DEG C are dried 3 hours, are then put
In muffle furnace, in 550 DEG C of roastings 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 loaded into reactors, in 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]
Will be equivalent to 55.36 parts of Fe2O3Iron oxide red, equivalent to 17.42 parts of Fe2O3Iron oxide yellow, equivalent to 5.71
Part K2The potassium carbonate of O, equivalent to 7.46 parts of CeO2Sedemesis., equivalent to 4.62 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 1.03 parts of BaO, 0.72 part of SnO2, 4.58 parts of Sm2O3, 3.1 parts of cement and 4.95 parts of carboxymethyl celluloses
Sodium is stirred in kneader 1.5 hours, and addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes
Go out extrusion, be extruded into 3 millimeters of diameter, long 6 millimeters granule, be put into baking oven, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours,
It is subsequently placed in muffle furnace, in 550 DEG C of roastings 3 hours, 920 DEG C of roastings obtained finished catalyst, catalyst composition for 3 hours
It is listed in table 1.
100 milliliters of catalyst are loaded into reactors, in 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]
Will be equivalent to 60.63 parts of Fe2O3Iron oxide red, equivalent to 17.42 parts of Fe2O3Iron oxide yellow, equivalent to 6.05
Part K2The potassium carbonate of O, equivalent to 6.15 parts of CeO2Sedemesis., equivalent to 2.03 parts of WO3Ammonium tungstate, equivalent to
The barium hydroxide of 0.55 part of BaO, 5.15 parts of SnO2, 2.02 parts of Sm2O3And 4.95 parts of sodium carboxymethyl cellulose are in kneader
Middle stirring 1.5 hours, addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, squeezes
Into 3 millimeters of diameter, long 6 millimeters granule, baking oven is put into, 60 DEG C are dried 2 hours, and 130 DEG C are dried 3 hours, are subsequently placed in
In muffle furnace, in 550 DEG C of roastings 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 loaded into reactors, in 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]
Except with CeO2Substitute beyond Sedemesis., method for preparing catalyst and evaluating catalyst condition are same as Example 1,
Specially：
Will be equivalent to 57.47 parts of Fe2O3Iron oxide red, equivalent to 18.18 parts of Fe2O3Iron oxide yellow, equivalent to 8.6
Part K2The potassium carbonate of O, 7.21 parts of CeO2, equivalent to 2.58 parts of WO3Ammonium tungstate, equivalent to the hydrogen of 1.12 parts of BaO
Barium monoxide, 3.16 parts of SnO2, 1.68 parts of Sm2O3And 5.69 parts of sodium carboxymethyl cellulose are stirred in kneader 1.5 hours,
Addition accounts for the deionized water of catalyst raw material gross weight 25%, mixes and stirs 0.5 hour, takes out extrusion, is extruded into 3 millimeters of diameter, length
6 millimeters of granule, 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, in 550 DEG C
Roasting 3 hours, 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.
The weight percent composition of table 1 (continued) catalyst
The weight percent composition of 1 (Continued) catalyst of table
2 catalyst performance of table is contrasted
Above example illustrates, adds stannum oxide and be selected from middle rare earth Sm in ferrum-potassium-cerium-tungsten-barium catalyst system and catalyzing2O3、
Eu2O3Or Gd2O3At least one, improve low potassium catalyst under low-water ratio conditions activity and stability, with notable
Energy-saving effect, can be used under low-water ratio conditions in the commercial production of ethyl benzene dehydrogenation preparation of styrene.
Claims (9)
1. the catalyst of high activity low-water ratio ethylbenzene dehydrogenation, by weight percentage including following component：
The Fe of (a) 66～79%2O3；
The K of (b) 4～9%2O；
The CeO of (c) 6～11%2；
The WO of (d) 1～5%3；
The BaO of (e) 0.5～5%；
The SnO of (f) 0.5～8%2；
The middle rare earth of (g) 0.5～5%；
The binding agent of (h) 0～4%, the one kind of binding agent selected from Kaolin, kieselguhr 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 with Sedemesis. or cerous carbonate form.
6. catalyst according to claim 1, it is characterised in that molybdenum oxide is not contained in catalyst.
7. the preparation method of catalyst described in claim 1, comprises the following steps：By by proportioning weigh Fe, K, Ce, W,
The binding agent and perforating agent of Ba, Sn, the middle rare earth that need to be added and non-imposed addition, and water mix homogeneously,
Extruded, dry and roasting obtains the catalyst.
8. preparation method according to claim 7, it is characterised in that baking temperature is 40～160 DEG C.
9. preparation method according to claim 7, it is characterised in that sintering temperature is 350～1000 DEG C.
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| CN109569637A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method |
| 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 |
| CN113877593A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | High-strength alkyl aromatic dehydrogenation catalyst, preparation method and application thereof, and alkyl aromatic dehydrogenation method |
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