CN106582692B - The ethylbenzene dehydrogenation catalyst with low water ratio of high activity - Google Patents
The ethylbenzene dehydrogenation catalyst with low water ratio of high activity Download PDFInfo
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Abstract
The present invention relates to ethylbenzene dehydrogenation catalyst with low water ratio of high activity 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% CaO；0.5~8% PbO2；0.5~5% heavy rare-earth oxide；0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；The heavy rare-earth oxide is selected from Er2O3、Tm2O3Or Yb2O3At 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 production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation of high activity.
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
Move, influence catalyst from power of regeneration and stability, realize that 10% or less low potassium content is catalyst for phenylethylene dehydrogenation exploitation
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 new catalyst for ethyl benzene dehydrogenation preparation of styrene, which uses
Have the characteristics that in ethylbenzene dehydrogenation reaction 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: the low water ratio ethylbenzene of high activity is de-
Hydrogen catalyst 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% CaO；
(f) 0.5~8% PbO2；
(g) 0.5~5% heavy rare-earth oxide；
(h) 0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；
The middle rare earth is selected from Er2O3、Tm2O3Or Yb2O3At least one.
In above-mentioned technical proposal, the heavy rare-earth oxide preferably includes Er simultaneously2O3And Tm2O3Or Er2O3And Yb2O3,
Or Tm2O3And Yb2O3, described two heavy rare-earth oxides are about activity with binary synergistic effect；More preferably include simultaneously
Er2O3、Tm2O3And Yb2O3, have the effect of trielement synergistic about activity at this time.
In above-mentioned technical proposal, PbO2Content is preferably 1~7%.
In above-mentioned technical proposal, PbO2Content is preferably 2~5%.
In above-mentioned technical proposal, heavy rare-earth oxide 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, Ca, Pb, need to add
The binder and perforating agent and water of the heavy rare-earth oxide 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 30~160 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 30~70 DEG C dryings 2
~4 hours, then 80~160 DEG C drying 0.5~4 hour.
In above-mentioned technical proposal, optional 300~1000 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 300~
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；Ca used is with the addition of oxide, hydroxide or calcium salt forms；Pb 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-calcium treating system by adding lead oxide and being selected from heavy rare-earth oxide Er2O3、
Tm2O3Or Yb2O3At 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 40% to 1.4
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
73.1%, conversion ratio only declines 0.2% after operation 500 hours, hence it is evident that improves work of the low potassium catalyst under low-water ratio conditions
Property and stability, achieve 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 CeO2Cerous acetate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of CaO
Calcium hydroxide, 3.16 parts of PbO2, 1.68 parts of Er2O3And 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,
940 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 1.4 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 PbO2And Er2O3In 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 CeO2Cerous acetate, be equivalent to 2.71 parts of WO3Ammonium tungstate, be equivalent to 1.18 parts of CaO
Calcium 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, 940 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 PbO2In 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 CeO2Cerous acetate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of CaO
Calcium hydroxide, 1.73 parts of Er2O3And 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, 940 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 Tm2O3Substitute Er2O3In 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 CeO2Cerous acetate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of CaO
Calcium hydroxide, 3.16 parts of PbO2, 1.68 parts of Tm2O3And 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,
940 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 PbO2In 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 CeO2Cerous acetate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of CaO
Calcium hydroxide, 1.73 parts of Tm2O3And 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, 940 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 Yb2O3Substitute Er2O3In 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 CeO2Cerous acetate, be equivalent to 2.58 parts of WO3Ammonium tungstate, be equivalent to 1.12 parts of CaO
Calcium hydroxide, 3.16 parts of PbO2, 1.68 parts of Yb2O3And 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,
940 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 PbO2In 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 CeO2Cerous acetate, be equivalent to 2.66 parts of WO3Ammonium tungstate, be equivalent to 1.16 parts of CaO
Calcium hydroxide, 1.73 parts of Yb2O3And 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, 940 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 Er2O3With 0.84 part
Tm2O3Substitute 1.68 parts of Er2O3。
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 Er2O3With 0.84 part
Yb2O3Substitute 1.68 parts of Er2O3。
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 Tm2O3With 0.84 part
Yb2O3Instead of 1.68 parts of Er2O3。
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 Er2O3, 0.56 part
Tm2O3With 0.56 part of b2O3Substitute 1.68 parts of Er2O3。
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 CeO2Cerous acetate, be equivalent to 4.13 parts of WO3Ammonium tungstate, be equivalent to 3.35 parts of CaO
Calcium hydroxide, 3.5 parts of PbO2, 0.85 part of Er2O3, 0.49 part of TiO2And 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,
940 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 1.4 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.4, test result is listed in table 2.
[embodiment 9]
It will be equivalent to 52.83 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 10.75 parts of CeO2Cerous acetate, be equivalent to 1.21 parts of WO3Ammonium tungstate, be equivalent to 4.95 parts
The calcium hydroxide of CaO, 7.8 parts of PbO2, 4.25 parts of Er2O3, 0.51 part of MoO2And 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, 940 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 1.4 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.4, test result is listed in table 2.
[embodiment 10]
It will be equivalent to 55.06 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 CeO2Cerous acetate, be equivalent to 4.62 parts of WO3Ammonium tungstate, be equivalent to 1.03 parts of CaO
Calcium hydroxide, 0.72 part of PbO2, 4.88 parts of Er2O3, 3.1 parts of cement and 3.95 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, 940 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 1.4 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 60.73 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 CeO2Cerous acetate, be equivalent to 2.03 parts of WO3Ammonium tungstate, be equivalent to 0.55 part of CaO
Calcium hydroxide, 5.05 parts of PbO2, 2.02 parts of Er2O3And 4.62 parts of graphite stir 1.5 hours in kneader, addition accounts for catalysis
The deionized water of agent 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, puts
Enter 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, 940 DEG C of roastings 3
Hour obtains finished catalyst, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.4 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 1.4, test result is listed in table 2.
[comparative example 5]
In addition to CeO2Substitute other than cerous acetate, 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 CaO calcium hydroxide,
3.16 part PbO2, 1.68 parts of Er2O3And 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, 940 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 lead oxide in iron-potassium-cerium-tungsten-calcium treating system and is selected from heavy rare-earth oxide
Er2O3、Tm2O3Or Yb2O3At 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 ethylbenzene dehydrogenation catalyst with low water ratio of high activity 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% CaO；
(f) 0.5~8% PbO2；
(g) 0.5~5% heavy rare-earth oxide；
(h) 0~4% binder, binder are selected from one kind of kaolin, diatomite or cement；
The heavy rare-earth oxide is selected from Er2O3、Tm2O3Or Yb2O3At least two.
2. catalyst according to claim 1, it is characterised in that PbO2Content is 1~7%.
3. catalyst according to claim 2, it is characterised in that PbO2Content is 2~5%.
4. catalyst according to claim 1, it is characterised in that heavy rare-earth oxide 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 acetate.
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,
Ca, Pb, the binder of the heavy rare-earth oxide 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 30~160 DEG C.
9. preparation method according to claim 7, it is characterised in that maturing temperature is 300~1000 DEG C.
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| CN1032119A (en) * | 1987-06-29 | 1989-04-05 | 国际壳牌研究有限公司 | Dehydrogenation catalyst |
| CN1981929A (en) * | 2005-12-14 | 2007-06-20 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst |
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| CN1032119A (en) * | 1987-06-29 | 1989-04-05 | 国际壳牌研究有限公司 | Dehydrogenation catalyst |
| CN1981929A (en) * | 2005-12-14 | 2007-06-20 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst |
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