CN110681390B - Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method and application thereof - Google Patents
Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
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- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention relates to a low-water ratio ethylbenzene dehydrogenation catalyst, a preparation method and application thereof, and mainly solves the problems that potassium in the catalyst is easy to migrate and lose in the reaction process of preparing styrene by ethylbenzene dehydrogenation and the catalyst is poor in stability in the prior art. The invention adopts a low water ratio ethylbenzene dehydrogenation catalyst, which comprises the following components in percentage by weight: 66-76% of Fe 2 O 3 (ii) a 4 to 9 percent of K 2 O;4 to 7 percent of K 2 ZnO 2 (ii) a 6 to 12 percent of CeO 2 (ii) a 0.5 to 4.5 percent of WO 3 (ii) a 0.5 to 4.5 percent of MgO;0.5 to 5 percent of SrO; 0.5-5% of medium rare earth oxide, wherein the medium rare earth oxide is selected from Eu 2 O 3 、Gd 2 O 3 Or Tb 2 O 3 At least one of (a); the technical scheme that 0.05-3% of oxide selected from Ge or Pb can be used in industrial production of styrene by ethylbenzene dehydrogenation under the condition of low water ratio.
Description
Technical Field
The invention relates to a catalyst for preparing styrene by ethylbenzene dehydrogenation with a low water ratio, and a preparation method and application thereof.
Background
Ethylbenzene dehydrogenation is a strongly endothermic, molecular-increasing reversible reaction. It is common practice in the industry to use an inert gas as a diluent to reduce the ethylbenzene partial pressure and drive the reaction towards the product. The role of water vapor in styrene production is reflected in:
(1) The reaction raw materials are heated to the required temperature, so that the ethylbenzene is prevented from being directly heated to a higher temperature, and the side reaction is inhibited;
(2) Supplementing heat to avoid temperature reduction due to reaction heat absorption;
(3) Reducing ethylbenzene partial pressure to promote the balance to move towards the styrene direction;
(4) The carbon deposit on the catalyst is continuously removed through the water gas reaction, so that the catalyst is automatically regenerated.
The addition of water vapor is limited by two factors of allowable pressure drop of the reaction system and energy consumption. The production of styrene consumes a large amount of water vapor as a dehydrogenation medium, so that the energy consumption is large, the product condensation amount is large, the cost of process equipment is high, and the production cost is high. The development of a low water ratio catalyst suitable for isothermal fixed beds with a water ratio of less than 1.6 (wt) to reduce the operating water ratio of industrial plants has become an urgent need for styrene plants, particularly large styrene plants.
The styrene catalyst is an iron catalyst which takes ferric oxide as a main active component and potassium oxide as a main cocatalyst. Potassium can increase the activity of iron oxide by orders of magnitude and promote the water gas reaction to remove carbon deposit and automatically regenerate the catalyst, but potassium is easy to migrate and lose in the reaction process, which is an important reason for the deactivation of the catalyst. In general, if the catalyst is subjected to ethylbenzene dehydrogenation reaction at a water ratio (water/ethylbenzene) of less than 2.0 (by weight), the water gas reaction speed is reduced, carbon deposit on the surface of the catalyst is increased, and the catalytic activity is rapidly reduced. In this regard, many attempts have been made by researchers based on literature reports to date. As reported in published European patent 0177832, the catalyst can show stable and excellent performance at a water ratio of less than 2.0% by weight after adding 1.8 to 5.4% by weight of magnesium oxide to the catalyst, but the potassium content of the catalyst is high, more than 20%. As reported in published us patent 4535067, a portion of the potassium in the catalyst was added as a cancrinite double salt, but the catalyst had a conversion of less than 65% at 614 ± 2 ℃, a selectivity of up to 93%, a single yield of less than 60%, was relatively low, and there was no concern about the life of the catalyst.
With the upsizing of styrene devices, energy saving becomes more and more important. Therefore, the use condition of the dehydrogenation catalyst is slightly improved, and the production enterprises can obtain huge economic benefits without changing any equipment or increasing investment. The development of a dehydrogenation catalyst suitable for operation at low water ratios has been a continuing endeavor.
Disclosure of Invention
The invention aims to solve the technical problem that the catalyst in the prior art has poor stability under the condition of low water ratio, and provides a novel low water ratio ethylbenzene dehydrogenation catalyst which is used for the reaction of preparing styrene by ethylbenzene dehydrogenation and has the characteristic of good stability under the condition of low water ratio.
The second technical problem to be solved by the present invention is to provide a method for preparing a low water ratio ethylbenzene dehydrogenation catalyst corresponding to the first technical problem.
The invention aims to solve the third technical problem and provides an application method of a low-water-ratio ethylbenzene dehydrogenation catalyst in preparing styrene by ethylbenzene dehydrogenation, which corresponds to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the low-water ratio ethylbenzene dehydrogenation catalyst comprises the following components in percentage by weight of the total catalyst:
(a) 66-76% of Fe 2 O 3 ；
(b) 4 to 9 percent of K 2 O；
(c) 4 to 7 percent of K 2 ZnO 2 ；
(d) 6 to 12 percent of CeO 2 ；
(e) 0.5 to 4.5 percent of WO 3 ；
(f) 0.5 to 4.5 percent of MgO;
(g) 0.5 to 5 percent of SrO;
(h) 0.5-5% of middle rare earth oxide, wherein the middle rare earth oxide is selected from Eu 2 O 3 、Gd 2 O 3 Or Tb 2 O 3 At least one of (a);
(i) 0.05-3% of an oxide selected from Ge or Pb.
The invention introduces potassium zincate species, compared with the same proportion condition that the total K element percentage content in the catalyst is kept unchanged and the Zn element content is kept unchanged, but the Zn element is introduced in the form of oxide, the stability of the catalyst under low water ratio can be improved. The possible mechanism is that K loss in the catalyst is reduced due to the presence of potassium zincate species.
In the above technical solution, the medium rare earth oxide preferably includes Eu at the same time 2 O 3 And Gd 2 O 3 Or Eu 2 O 3 And Tb 2 O 3 Or Gd 2 O 3 And Tb 2 O 3 The two medium rare earth oxides have a binary synergistic effect in the aspect of improving the stability of the catalyst at a low water ratio; more preferably, the medium rare earth oxide includes Eu at the same time 2 O 3 、Gd 2 O 3 And Tb 2 O 3 At this time, the three kinds of medium rare earth oxides have a ternary synergistic effect in terms of improvement in catalyst stability at a low water ratio.
In the above technical scheme, the content of the component (i) is preferably 0.15 to 1%.
In the above technical scheme, ce is preferably added in the form of cerium nitrate or cerium carbonate.
In the above technical scheme, no binder is preferably added in the catalyst preparation process.
In the above technical solution, the catalyst preferably does not contain molybdenum oxide.
In the above technical scheme, the Fe 2 O 3 Preferably from red iron oxide and yellow iron oxide, more preferably the weight ratio of red iron oxide to yellow iron oxide is 1.0 to 3.2.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a low water ratio ethylbenzene dehydrogenation catalyst according to one of the above technical solutions, comprising the following steps: fe, K and K are weighed according to the mixture ratio 2 ZnO 2 Ce, W, mg, sr, medium rare earth oxide, the oxide of component (i), a pore-forming agent and water are uniformly mixed, and the catalyst is obtained after extrusion, drying and roasting.
In the above technical scheme, the addition amount of water is not particularly limited, and the skilled person can reasonably control the dry humidity for extrusion, for example, but not limited to, the addition amount of water is 20-35% of the total weight of the catalyst raw material.
In the above technical scheme, the drying temperature is not particularly limited, for example, 30 to 160 ℃, and the drying time can be selected from 0.55 to 8 hours.
In the above technical scheme, preferably, the drying is carried out by gradually raising the temperature, for example, but not limited to, drying at 30-70 ℃ for 2-4 hours, and then drying at 80-160 ℃ for 0.5-4 hours.
In the technical scheme, the roasting temperature can be 600-950 ℃, and the roasting time can be 2-8 hours.
In the above technical scheme, as a preferred roasting condition, the roasting temperature is gradually increased, for example, but not limited to, roasting at 600-750 ℃ for 2-4 hours, and then roasting at 800-950 ℃ for 2-4 hours.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: an application of the low water ratio ethylbenzene dehydrogenation catalyst in the preparation of styrene by ethylbenzene dehydrogenation is provided.
In the above technical scheme, the application method is not particularly limited, and those skilled in the art can apply the method in the process of preparing styrene by ethylbenzene dehydrogenation according to the prior art.
The catalyst component of the present invention uses the following raw materials:
fe used 2 O 3 Adding in the form of iron oxide red and iron oxide yellow; the K is added in the form of potassium carbonate and potassium zincate; w used is added in the form of its salt or oxide; the Zn is added in the form of potassium zincate; the Mg is added in the form of oxide or hydroxide; the Sr is added in the form of oxide or strontium carbonate; the remaining elements are added in the form of oxides. In the preparation process of the invention, besides the main components of the catalyst, a pore-forming agent is added, wherein the pore-forming agent can be selected from graphite, polystyrene microspheres or sodium carboxymethylcellulose, and the addition amount of the pore-forming agent is 2-6% of the total weight of the catalyst.
The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed, and for the activity evaluation of the catalyst for preparing styrene by ethylbenzene dehydrogenation, the process is briefly described as follows:
the deionized water and the ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gas state, and then the gas state enters a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reactor was a 1 "internal diameter stainless steel tube filled with 100 ml of a 3 mm diameter catalyst. The composition of the reactants exiting the reactor was analyzed by gas chromatography after condensation of water.
The ethylbenzene conversion and the styrene selectivity are calculated according to the following formulas:
the catalyst stability of the present invention is expressed by the catalyst deactivation rate, and the calculation method is as follows:
catalyst deactivation rate = [ conversion at initial stage of reaction-conversion at final stage of reaction)/reaction time h ] x 100%
The greater the rate of catalyst deactivation, the less stable the catalyst; the lower the catalyst deactivation rate, the better the catalyst stability.
The invention adds partial potassium and medium rare earth oxide Eu in the form of potassium zincate in an iron-potassium-cerium-tungsten-magnesium-strontium catalytic system 2 O 3 、Gd 2 O 3 Or Tb 2 O 3 The active phase of the catalyst is stabilized and dispersed, the stability of potassium is obviously improved, the self-regeneration capability of the catalyst in the reaction process is enhanced, and the stability of the catalyst under the condition of low water ratio is improved.
By adopting the technical scheme of the invention, the activity of the catalyst prepared by the invention is evaluated in an isothermal fixed bed at normal pressure and liquid airspeed of 1.0 hour －1 The ethylbenzene conversion rate is still up to 75.4% after the stable operation for 500 hours, the catalyst deactivation rate is 0.0333%/h, and better technical effects are achieved.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1 ]
Will correspond to 50.2 parts Fe 2 O 3 Red and phase of iron oxideWhen the content is 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.81 parts of K 2 Potassium carbonate of O, 5.73 parts of K 2 ZnO 2 Equivalent to 11.23 parts of CeO 2 Corresponding to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Eu 2 O 3 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and a liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Except for the K element in the catalyst (original K) 2 CO 3 And K 2 ZnO 2 The sum of potassium elements) is kept unchanged, zn is sourced from ZnO, and Eu is not added 2 O 3 In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
equivalent to 51.21 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.39 parts of Fe 2 O 3 Yellow iron oxide of 9.06 parts of K 2 Potassium carbonate of O, 2.71 parts of ZnO, corresponding to 11.46 parts of CeO 2 Corresponding to 0.75 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.36 parts of MgO, 0.87 part of SrO, 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1. The evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
Except for the K element in the catalyst (original K) 2 O and K 2 ZnO 2 Total potassium element) content was maintained, and Zn element was derived from other than ZnO, and the catalyst preparation method and catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 50.2 parts Fe 2 O 3 Iron oxide red of (1), equivalent to 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 8.88 parts of K 2 Potassium carbonate of O, 2.66 parts of ZnO, corresponding to 11.23 parts of CeO 2 Corresponding to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Eu 2 O 3 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1. The evaluation results are shown in Table 2.
[ example 2 ] A method for producing a polycarbonate
Except using Gd 2 O 3 Replacement of Eu 2 O 3 In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 50.2 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.81 parts of K 2 Potassium carbonate of O, 5.73 parts of K 2 ZnO 2 Equivalent to 11.23 parts of CeO 2 Corresponding to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Gd 2 O 3 0.19 part of GeO 2 Stirring 5.4 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out extruded strips, extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, and baking the particles for 3 hours at the temperature of 650 DEG CAnd calcining at 920 ℃ for 3 hours to obtain the finished catalyst, and the composition of the catalyst is shown in Table 1. The evaluation results are shown in Table 2.
[ example 3 ]
Except using Tb 2 O 3 Replacement Eu 2 O 3 In addition, the catalyst preparation method and the catalyst evaluation conditions were the same as in example 1, specifically:
will correspond to 50.2 parts of Fe 2 O 3 Iron oxide red of (1), corresponding to 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.81 parts of K 2 Potassium carbonate of O, 5.73 parts of K 2 ZnO 2 Equivalent to 11.23 parts of CeO 2 Corresponding to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Tb 2 O 3 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the raw materials of the catalyst, stirring for 0.5 hour, taking out the extruded strips, extruding the extruded strips into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles at 60 ℃ for 2 hours and at 130 ℃ for 3 hours, then putting the particles into a muffle furnace, baking the particles at 650 ℃ for 3 hours and at 920 ℃ for 3 hours to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1. The evaluation results are shown in Table 2.
[ example 4 ] A method for producing a polycarbonate
A catalyst and a test catalyst were prepared by the method of example 1 except that 0.99 parts of Eu was used 2 O 3 And 0.99 part of Gd 2 O 3 Replacement of 1.98 parts of Eu 2 O 3 。
The composition of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 5 ]
A catalyst and a test catalyst were prepared by the method of example 1 except that 0.99 parts of Eu was used 2 O 3 And 0.99 part of Tb 2 O 3 Replacement of 1.98 parts of Eu 2 O 3 。
The composition of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 6 ]
The catalyst was prepared and tested as in example 1 exceptWith 0.99 part of Gd 2 O 3 And 0.99 part of Tb 2 O 3 Replacement of 1.98 parts of Eu 2 O 3 。
The composition of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 7 ]
A catalyst and a test catalyst were prepared by the method of example 1 except that 0.66 part Eu was used 2 O 3 0.66 part of Gd 2 O 3 And 0.66 part of Tb 2 O 3 Replacement of 1.98 parts of Eu 2 O 3 。
The composition of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
[ example 8 ]
Will correspond to 39.90 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 32.16 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 4.85 parts of K 2 Potassium carbonate of O, 5.12 parts of K 2 ZnO 2 Equivalent to 7.35 parts of CeO 2 Corresponding to 0.65 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 2.15 parts of MgO, 1.6 parts of SrO, 4.56 parts of Eu 2 O 3 0.84 part of PbO 2 0.82 part of ZrO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ example 9 ]
Will correspond to 42.88 parts of Fe 2 O 3 23.7 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 8.12 parts of K 2 Potassium carbonate of O, 4.66 parts of K 2 ZnO 2 Equivalent to 6.15 parts of CeO 2 Corresponding to 4.25 parts of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 3.72 parts of MgO, strontium carbonate equivalent to 4.59 parts of SrO, 0.85 part of Eu 2 O 3 0.35 part of GeO 2 Equivalent to 0.73 part of MoO 3 Stirring ammonium molybdate and 5.4 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the raw materials of the catalyst, stirring for 0.5 hour, taking out extruded strips, extruding the extruded strips into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles at 60 ℃ for 2 hours and at 130 ℃ for 3 hours, then putting the particles into a muffle furnace, baking the particles at 650 ℃ for 3 hours and baking the particles at 920 ℃ for 3 hours to obtain the finished catalyst, wherein the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ example 10 ]
Will correspond to 56.3 parts of Fe 2 O 3 Iron oxide red of (1), corresponding to 18.96 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 6.12 parts of K 2 Potassium carbonate of O, 4.15 parts of K 2 ZnO 2 Equivalent to 8.01 parts of CeO 2 Corresponding to 1.01 parts of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 0.85 part of MgO, 1.12 parts of SrO, 3.16 parts of Eu 2 O 3 0.32 part of GeO 2 1.25 parts of cement and 5.4 parts of graphite are stirred in a kneader for 1.5 hours, deionized water accounting for 28 percent of the total weight of the catalyst raw materials is added, the mixture is stirred for 0.5 hour, extruded strips are taken out and extruded into particles with the diameter of 3 millimeters and the length of 6 millimeters, the particles are put into an oven and baked for 2 hours at the temperature of 60 ℃ and 3 hours at the temperature of 130 ℃, then the particles are put into a muffle furnace and baked for 3 hours at the temperature of 650 ℃ and baked for 3 hours at the temperature of 920 ℃ to obtain the finished catalyst, and the composition of the catalyst is listed in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ example 11 ]
Will correspond to 50.2 parts Fe 2 O 3 The iron oxide red,Equivalent to 19.95 parts Fe 2 O 3 Iron oxide yellow of (1), corresponding to 7.02 parts of K 2 Potassium carbonate of O, 6.85 parts of K 2 ZnO 2 Equivalent to 9.01 parts of CeO 2 Corresponding to 1.24 parts of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 1.01 parts of MgO, 0.55 parts of SrO, 4.05 parts of Eu 2 O 3 0.12 part of GeO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and a liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
Will correspond to 50.2 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.81 parts of K 2 Potassium carbonate of O, 5.73 parts of K 2 ZnO 2 11.23 parts of CeO 2 Equivalent to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 4.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Eu 2 O 3 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the raw materials of the catalyst, stirring for 0.5 hour, taking out the extruded strips, extruding the extruded strips into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles at 60 ℃ for 2 hours and at 130 ℃ for 3 hours, then putting the particles into a muffle furnace, baking the particles at 650 ℃ for 3 hours and at 920 ℃ for 3 hours to obtain the finished catalyst, wherein the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and a liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
[ COMPARATIVE EXAMPLE 4 ]
Will correspond to 50.2 parts Fe 2 O 3 Iron oxide red of (1), corresponding to 19.0 parts of Fe 2 O 3 Iron oxide yellow of (1), corresponding to 5.81 parts of K 2 Potassium carbonate of O, 8.73 parts of K 2 ZnO 2 Equivalent to 9.23 parts of CeO 2 Corresponding to 0.74 part of WO 3 Ammonium tungstate (D), magnesium hydroxide equivalent to 3.27 parts of MgO, 0.85 part of SrO, 1.98 parts of Eu 2 O 3 0.19 part of GeO 2 And 5.4 parts of graphite in a kneader, stirring for 1.5 hours, adding deionized water accounting for 28 percent of the total weight of the catalyst raw materials, stirring for 0.5 hour, taking out and extruding into particles with the diameter of 3 millimeters and the length of 6 millimeters, putting the particles into an oven, baking the particles for 2 hours at the temperature of 60 ℃, baking the particles for 3 hours at the temperature of 130 ℃, then putting the particles into a muffle furnace, baking the particles for 3 hours at the temperature of 650 ℃, and baking the particles for 3 hours at the temperature of 920 ℃ to obtain a finished catalyst, wherein the composition of the catalyst is shown in Table 1.
100 ml of catalyst was charged into the reactor at atmospheric pressure and liquid space velocity of 1.0 hour －1 The activity and stability were evaluated at 620 ℃ and a water ratio (by weight) of 0.65, and the evaluation results are shown in Table 2.
TABLE 1 weight percent composition of (to be) catalyst
TABLE 1 weight percent composition of (continuous) catalysts
TABLE 2 comparison of catalyst Performance
The above examples illustrate the use of partial potassium additions in the form of potassium zincate and the addition of the rare earth oxide Eu in the iron-potassium-cerium-tungsten-magnesium-strontium catalytic system 2 O 3 、Gd 2 O 3 Or Tb 2 O 3 At least one ofThe carbon deposition resistance of the catalyst is obviously enhanced, the service life under the condition of low water ratio is prolonged, the catalyst has obvious energy-saving effect, and can be used in the industrial production of preparing styrene by ethylbenzene dehydrogenation under the condition of low water ratio.
Claims (10)
1. The low-water ratio ethylbenzene dehydrogenation catalyst comprises the following components in percentage by weight of the total catalyst:
(a) 66-76% of Fe 2 O 3 ；
(b) 4 to 9 percent of K 2 O；
(c) 4 to 7 percent of K 2 ZnO 2 ；
(d) 6 to 12 percent of CeO 2 ；
(e) 0.5 to 4.5 percent of WO 3 ；
(f) 0.5 to 4.5 percent of MgO;
(g) 0.5 to 5 percent of SrO;
(h) 0.5-5% of middle rare earth oxide, wherein the middle rare earth oxide is selected from Eu 2 O 3 、Gd 2 O 3 Or Tb 2 O 3 At least one of (a);
(i) 0.05-3% of an oxide selected from Ge or Pb.
2. The low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein component (i) is present in an amount of 0.15 to 1%.
3. The low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein the Ce is added as cerium nitrate or cerium carbonate.
4. The low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein no binder is added during the catalyst preparation.
5. The low water ratio ethylbenzene dehydrogenation catalyst of claim 1, wherein the catalyst does not contain molybdenum oxide.
6. According to claim 1The low-water ratio ethylbenzene dehydrogenation catalyst is characterized in that the Fe 2 O 3 From red iron oxide and yellow iron oxide.
7. A process for the preparation of a low water ratio ethylbenzene dehydrogenation catalyst as claimed in any one of claims 1 to 6 comprising the steps of: fe, K and K are weighed according to the proportioning equivalent weight 2 ZnO 2 The catalyst comprises Ce, W, mg, sr, middle rare earth oxide, component (i) oxide, pore-forming agent and water, and is prepared by uniformly mixing, extruding, drying and roasting.
8. The method according to claim 7, wherein the drying temperature is 30 to 160 ℃.
9. The method according to claim 7, wherein the calcination temperature is 600 to 950 ℃.
10. Use of a low water ratio ethylbenzene dehydrogenation catalyst according to any of claims 1 to 6 in the dehydrogenation of ethylbenzene to styrene.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018458A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst and process |
| CN106582691A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low-water-to-ethylbenzene-ratio ethylbenzene dehydrogenation catalyst and preparation method therefor |
| CN106582687A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for ethylbenzene dehydrogenation in low water ratio and preparation method thereof |
| CN106582683A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low water ratio ethylbenzene dehydrogenation catalyst |
| CN106582681A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low steam-to-oil ratio ethylbenzene dehydrogenation catalyst |
| CN106582827A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | High activity and low water ratio ethylbenzene dehydrogenation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018458A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst and process |
| CN106582691A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low-water-to-ethylbenzene-ratio ethylbenzene dehydrogenation catalyst and preparation method therefor |
| CN106582687A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for ethylbenzene dehydrogenation in low water ratio and preparation method thereof |
| CN106582683A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low water ratio ethylbenzene dehydrogenation catalyst |
| CN106582681A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low steam-to-oil ratio ethylbenzene dehydrogenation catalyst |
| CN106582827A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | High activity and low water ratio ethylbenzene dehydrogenation catalyst |
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