CN113877596B - Ethylbenzene dehydrogenation catalyst and preparation method and application thereof - Google Patents

Ethylbenzene dehydrogenation catalyst and preparation method and application thereof Download PDF

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CN113877596B
CN113877596B CN202010633440.6A CN202010633440A CN113877596B CN 113877596 B CN113877596 B CN 113877596B CN 202010633440 A CN202010633440 A CN 202010633440A CN 113877596 B CN113877596 B CN 113877596B
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catalyst
weight
rare earth
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CN113877596A (en
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宋磊
朱敏
缪长喜
张征湃
徐永繁
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—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
    • 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
    • C07C2523/889—Manganese, technetium or rhenium

Abstract

The invention relates to the technical field of catalyst preparation, and discloses an ethylbenzene dehydrogenation catalyst, a preparation method and application thereof, wherein the catalyst contains Fe 2 O 3 、K 2 O、CeO 2 、WO 3 MnO and Al 2 O 3 And heavy rare earth oxides; fe based on the total amount of the catalyst 2 O 3 The content of K is 66-79 wt% 2 O content is 4.5-8 wt%, ceO 2 Is contained in an amount of 6 to 11 wt.%, WO 3 The content of (2) is 1-5 wt%, the content of MnO is 0.5-5 wt%, and Al 2 O 3 The content of the rare earth oxide is 0.5-8 wt%, and the content of the heavy rare earth oxide is 0.5-5 wt%. The catalyst of the invention has better anti-reduction capability, still has better stability, catalytic activity and selectivity under the conditions of low weight ratio of water to ethylbenzene and high mass airspeed, and effectively reduces the carbon deposit amount of the catalyst.

Description

Ethylbenzene dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to an ethylbenzene dehydrogenation catalyst and a preparation method and application thereof.
Background
The main reaction of ethylbenzene dehydrogenation is C 6 H 5 -C 2 H 5 →C 6 H 5 CH＝CH 2 +H 2 +124KJ/mol. Thermodynamically, lowering the ethylbenzene partial pressure is advantageous for equilibrium, so it is common in industry to add steam to drive the reaction toward the product. The latest development trend of the technology for producing styrene by ethylbenzene dehydrogenation is energy saving and consumption reduction. The vaporization latent heat of water is great, and a great amount of superheated steam is consumed in the styrene production process as a dehydrogenation medium, so that the process has high energy consumption and high production cost. Meanwhile, in order to obtain as many styrene products as possible by digging the potential of the styrene device, reduce the production cost and maximize the benefit, the ethylbenzene feeding amount of many styrene devices is above 110% of the design value, and high requirements are put on the high airspeed resistance of the catalyst. The development of a low water ratio and high space velocity catalyst suitable for isothermal fixed beds with water ratio lower than 1.0 (weight) can obtain as much styrene product as possible, reduce unit consumption and energy consumption, and maximize benefits, and is an urgent need for various styrene devices, especially large-scale styrene devices, at home and abroad.
Iron-based catalysts using iron oxide as a main active component and potassium oxide as a main promoter are widely used in the industrial ethylbenzene dehydrogenation to produce styrene. Normally, the potassium content is more than 12%, but the potassium is not stable enough, is easy to run off and migrate under the flushing of high-temperature steam, influences the self-regeneration capacity and stability of the catalyst, and realizes that the low potassium content within 9% is the main stream of ethylbenzene dehydrogenation catalyst development. It is generally accepted that potash is the most effective anti-coking aid, low-potassium catalysts operate at low water ratios, and the catalyst surface is particularly prone to coking and poor in stability, and therefore must seek to enhance the low water ratio resistance of low-potassium catalysts.
During the reaction process of ethylbenzene dehydrogenation to styrene, a large amount of hydrogen is generated, the reduction of the reaction atmosphere is enhanced due to the reduction of the water vapor consumption under the condition of low water ratio, the catalyst is more easily reduced, the activity is reduced, and the stability is poor. Carbon deposition is also one of the important reasons for the deactivation of the ethylbenzene dehydrogenation catalyst, and research shows that after the ethylbenzene dehydrogenation catalyst is used, micropores with the pore diameter of less than 50nm are totally blocked by carbon deposition, and macropores are less in carbon deposition.
In this regard, many attempts have been made according to the reports of the related literature so far. CN1923364A reports that adding Cu-La combination as promoter in Fe-K-Ce-Mo-Mg system, the catalyst is suitable for running at low water ratio, but the suitable water ratio is still higher than 1.3 (weight), and the mass space velocity is 0.6 h -1 Lower. For example, US4134858A, US4152300a discloses mining on the basis of iron, potassium and chromium as main components, and adding other elements to reduce the water ratio. But the selectivity is generally low, not exceeding 94%.
With the large-scale of styrene units, energy conservation is becoming more and more important. Therefore, the use condition of the dehydrogenation catalyst is slightly improved, any equipment is not required to be changed, and investment is not required to be increased, so that a manufacturing enterprise can obtain great economic benefit. It has been a direction of researchers to develop a low potassium catalyst suitable for operation at low water to high space velocity with higher activity and better stability.
Disclosure of Invention
The invention aims to solve the problems of poor stability, easy reduction in activity and high carbon deposit of a catalyst under the conditions of low water ratio and high mass airspeed in the prior art, and provides an ethylbenzene dehydrogenation catalyst and a preparation method and application thereof.
In order to achieve the above object, the present invention provides, in one aspect, an ethylbenzene dehydrogenation catalyst comprising Fe 2 O 3 、K 2 O、CeO 2 、WO 3 MnO and Al 2 O 3 And heavy rare earth oxides;
fe based on the total amount of the catalyst 2 O 3 The content of K is 66-79 wt% 2 O content is 4.5-8 wt%, ceO 2 Is contained in an amount of 6 to 11 wt.%, WO 3 The content of (2) is 1-5 wt%, the content of MnO is 0.5-5 wt%, and Al 2 O 3 The content of (C) is 0.5-8 wt%,the content of heavy rare earth oxide is 0.5-5 wt%.
In a second aspect, the present invention provides a method for preparing the ethylbenzene dehydrogenation catalyst according to the first aspect, which comprises the following steps: the Fe source, K source, ce source, W source, mn source, al source, and heavy rare earth source are mixed with the porogen and solvent, and then optionally dried and calcined.
In a third aspect, the present invention provides an ethylbenzene dehydrogenation catalyst prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides the use of an ethylbenzene dehydrogenation catalyst according to the first or third aspect in ethylbenzene dehydrogenation reactions.
In a fifth aspect, the present invention provides a process for the dehydrogenation of ethylbenzene comprising: ethylbenzene is reacted under ethylbenzene dehydrogenation conditions by contacting it with an ethylbenzene dehydrogenation catalyst according to the first or third aspect.
The catalyst of the invention is prepared by mixing Fe 2 O 3 、K 2 O、CeO 2 、WO 3 MnO and Al 2 O 3 The catalyst has better reduction resistance, better stability, catalytic activity and selectivity under the conditions of lower water ratio and higher mass airspeed, has better carbon deposit resistance (lower carbon deposit quantity), can meet the requirement of treating more raw materials in the styrene market, has obvious energy-saving effect, is beneficial to the cost reduction and synergy of a styrene device, and can be well used in the industrial production of preparing styrene by ethylbenzene dehydrogenation under the conditions of lower water ratio and higher mass airspeed. For example, the catalyst prepared by the invention is used for performance evaluation in a fixed bed, and the catalyst is used for a common time of 1h at-50 kPa and a mass space velocity -1 Raise to 1.5h -1 The test at 625 ℃ under the condition that the water ratio is reduced by 65 to 0.7 percent (weight) from the normal 2 percent (weight), the result shows that after 100 hours of operation, the ethylbenzene conversion rate is up to 77.6 percent, the styrene selectivity is up to 96.2 percent, after 1200 hours of operation, the ethylbenzene conversion rate is only reduced by 0.4 percent, the styrene selectivity is increased to 96.3 percent, and the catalyst detached after the reaction is analyzed by an elemental analyzer, the carbon deposit amount is only 1.19 percent by weight, and the carbon deposit amount is obviously improvedThe stability, catalytic activity and selectivity of the low-potassium catalyst under the condition of low water ratio and high space velocity are good.
Drawings
FIG. 1 is a catalyst H prepared in example 1 of the present invention 2 -TPR profile.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventors of the present invention found through studies that Fe of the catalyst 2 O 3 、K 2 O、CeO 2 、WO 3 、MnO、Al 2 O 3 The catalyst has high stability, catalytic activity and selectivity under the conditions of low water ratio and high mass space velocity, and has high carbon deposit resistance (low carbon deposit amount).
In the present invention, the water ratio refers to the weight ratio of water to ethylbenzene without specific description.
In a first aspect, the present invention provides an ethylbenzene dehydrogenation catalyst comprising Fe 2 O 3 、K 2 O、CeO 2 、WO 3 MnO and Al 2 O 3 And heavy rare earth oxides;
fe based on the total amount of the catalyst 2 O 3 The content of K is 66-79 wt% 2 O content is 4.5-8 wt%, ceO 2 Is contained in an amount of 6 to 11 wt.%, WO 3 The content of (2) is 1-5 wt%, the content of MnO is 0.5-5 wt%, and Al 2 O 3 The content of the rare earth oxide is 0.5-8 wt%, and the content of the heavy rare earth oxide is 0.5-5 wt%.
According to the inventionObviously, preferably, fe is based on the total amount of the catalyst 2 O 3 The content of K is 70-78 wt% 2 The content of O is 6.5-7.5 wt%, ceO 2 Is contained in an amount of 7 to 9 wt.%, WO 3 The content of (2.5-4.5 wt.%), mnO (1-3.5 wt.%) and Al 2 O 3 The content of (C) is 0.8-5.2 wt%, and the content of heavy rare earth oxide is 0.8-4 wt%.
Preferably, based on the total amount of catalyst, fe 2 O 3 The content of (c) is 70-78 wt%, and may be, for example, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, or any value between any two values.
Preferably, K is based on the total amount of catalyst 2 The content of O is 6.5-7.5 wt%, and may be, for example, 6.5 wt%, 6.7 wt%, 6.9 wt%, 7.1 wt%, 7.3 wt%, 7.5 wt%, or any value between any two values.
Preferably, ceO is based on the total amount of catalyst 2 The content of (c) is 7 to 9 wt%, and may be, for example, 7 wt%, 7.2 wt%, 7.4 wt%, 7.6 wt%, 7.8 wt%, 8 wt%, 8.2 wt%, 8.4 wt%, 8.6 wt%, 8.8 wt%, 9 wt%, or any value between any two values.
Preferably, WO is used on the basis of the total amount of catalyst 3 The content of (c) is 2.5-4.5 wt%, for example, may be 2.5 wt%, 2.7 wt%, 2.9 wt%, 3.1 wt%, 3.3 wt%, 3.5 wt%, 3.7 wt%, 3.9 wt%, 4.1 wt%, 4.3 wt%, 4.5 wt%, and any value between any two values.
Preferably, the MnO content is 1 to 3.5 wt%, based on the total amount of the catalyst, and may be, for example, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, and any value between any two values.
Preferably, al is present in the total amount of catalyst 2 O 3 Is 0.8 in content5.2% by weight, more preferably 1-4% by weight, for example, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, and any value in between.
Preferably, the heavy rare earth oxide is present in an amount of 0.8 to 4 wt.%, based on the total amount of catalyst, and may be, for example, 0.8 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, and any value in between any two.
The composition of the catalyst was measured by X-ray fluorescence spectroscopy.
The kind of the heavy rare earth oxide is not particularly limited in the present invention, and may be a heavy rare earth oxide conventional in the art, and according to a preferred embodiment of the present invention, the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 At least one of them. The stability, catalytic activity and selectivity of the catalyst can be further improved by adopting the preferred embodiment.
More preferably, the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 At least two of them.
It will be appreciated that when the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 In the case of two of the above, the content of the two oxides may be the same or different. When the contents of the two oxides are different, there is no particular limitation on the respective contents of the two oxides, and preferably, the content ratio of the two oxides is selected to be 1, based on the total amount of the heavy rare earth oxides, in terms of oxides: 0.5 to 1.5, more preferably 1:0.8-1.2.
It will be appreciated that when the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 In this case, the contents of the three oxides may be the same or different. When the contents of the three oxides are different, there is no particular case of the respective contents of the three oxidesRestriction, preferably Yb of three oxides, calculated as oxide, based on the total amount of heavy rare earth oxides 2 O 3 、Tm 2 O 3 And Lu 2 O 3 The content ratio is 1:0.5-1.5:0.5 to 1.5, more preferably 1:0.8-1.2:0.8-1.2.
Further preferably, the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 。
In the present invention, when the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 In the case of at least two of (a), the selection range of the content of each component in the heavy rare earth oxide is not particularly limited, and the content of each component may be the same or different.
According to a preferred embodiment of the invention, the catalyst has a complete reduction temperature which is 310-360 ℃, preferably 325-360 ℃ higher than the initial reduction temperature. The complete reduction temperature of the catalyst is 310-360 ℃ higher than the initial reduction temperature, so that on one hand, the active phase of the catalyst is stabilized and dispersed, and the anti-reduction capability is improved; on the other hand, the coking reaction is prevented, the rate of the water gas reaction between the water vapor and the surface area carbon of the catalyst is accelerated, and the anti-coking effect is obvious.
In the present invention, the complete reduction temperature refers to the temperature at which all ferric iron is reduced; the initial reduction temperature refers to the temperature at which ferric iron begins to be reduced.
In the present invention, the change in the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), for example, a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under an atmosphere of He, then cooled to room temperature, and switched to H 2 /N 2 Reducing gas (H) 2 Concentration of 10% by volume) was subjected to temperature programmed reduction, and the temperature was raised to 850 ℃ at a rate of 10 ℃/min, and the difference between the temperature at which the ferric iron began to be reduced and the temperature at which all the ferric iron was reduced was recorded.
According to the present invention, in order to further improve the stability, catalytic activity and selectivity of the catalyst at low water ratio, high mass space velocity, it is preferable that the catalyst does not contain molybdenum oxide.
According to the present invention, preferably, the catalyst does not contain a binder.
According to the present invention, preferably, the binder is at least one selected from the group consisting of cement, kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, for example, at least one selected from the group consisting of kaolin, diatomaceous earth and cement. The inventors of the present invention have found during the course of their studies that the addition of a binder to the catalyst system according to the first aspect of the present invention is disadvantageous in that it is advantageous to improve the stability of the catalyst in the preferred manner described above.
In a second aspect, the present invention provides a method for preparing the ethylbenzene dehydrogenation catalyst according to the first aspect, the method comprising: the Fe source, K source, ce source, W source, mn source, al source, and heavy rare earth source are mixed with the porogen and solvent, and then optionally dried and calcined.
The specific mode of the mixing is not particularly limited in the present invention, as long as the Fe source, K source, ce source, W source, mn source, al source, and heavy rare earth source can be sufficiently mixed with the pore-forming agent and the solvent. For example, the mixing may be performed under stirring conditions, and the stirring time may be 1 to 5 hours.
The mixing may be carried out in a kneader.
The choice of the Fe source is not particularly limited according to the present invention, and may be any one that can be converted into Fe in the subsequent firing process 2 O 3 Iron-containing compounds of (a). Preferably, the Fe source is iron oxide red and/or iron oxide yellow, more preferably iron oxide red and iron oxide yellow. With such preferred embodiments, it is further advantageous to increase the activity, selectivity, stability and strength of the catalyst.
The dosage ratio of the iron oxide red to the iron oxide yellow is wider in the selection range, and preferably, the weight ratio of the iron oxide red to the iron oxide yellow is 3-4:1, for example, may be 3: 1. 3.2: 1. 3.4: 1. 3.6: 1. 3.8: 1. 4:1, and any value between any two values.
The choice of the K source is not particularly limited according to the invention, and can be any source which can be converted into K in the subsequent calcination process 2 Potassium-containing compounds of O. Preferably, the K source is potassium carbonate and/or potassium bicarbonate; more preferably potassium carbonate.
The Ce source is not particularly limited according to the present invention, and may be any source capable of being converted into CeO in the subsequent firing process 2 Cerium-containing compounds of (a). Preferably, the Ce source is cerium acetate and/or cerium carbonate. The adoption of the preferred embodiment not only can meet the environmental protection requirement (the cerium nitrate can release nitrogen-containing gas in the roasting process), but also can further improve the strength of the prepared catalyst.
The choice of the W source is not particularly limited according to the invention, and may be any source which can be converted into WO in the subsequent firing process 3 Preferably, the W source is selected from at least one of ammonium tungstate, ammonium metatungstate, and tungsten trioxide; more preferably ammonium tungstate.
According to the present invention, the Mn source is not particularly limited, and may be any manganese-containing compound capable of being converted into MnO in the subsequent firing process, preferably the Mn source is selected from at least one of manganese oxide, manganese salt and manganese hydroxide, more preferably the Mn source is selected from at least one of manganese oxide, manganese hydroxide and manganese carbonate, and still more preferably manganese oxide.
The Al source is not particularly limited according to the present invention, and may be any one that can be converted into Al in the subsequent firing process 2 O 3 Preferably, the Al source is selected from at least one of aluminum oxide, aluminum hydroxide, and aluminum carbonate; more preferably aluminum oxide.
According to the present invention, the selection of the heavy rare earth source is not particularly limited, and in order to improve the reduction resistance and the soot-preventing effect of the catalyst, and to improve the stability, catalytic activity and selectivity at a low water ratio, high mass space velocity, preferably the heavy rare earth source is an oxide of heavy rare earth, more preferably the heavy rare earth source is at least one selected from ytterbium trioxide, thulium trioxide and lutetium trioxide, more preferably at least two selected from ytterbium trioxide, thulium trioxide and lutetium trioxide, further preferably ytterbium trioxide, thulium trioxide and lutetium trioxide.
It will be appreciated that when the heavy rare earth source is selected from two or three of ytterbium trioxide, thulium trioxide and lutetium trioxide, the amounts of the components are as described above and are not described in detail herein.
According to the present invention, the addition amount of the pore-forming agent is preferably 2 to 6 wt%, preferably 4.5 to 5.5 wt%, of the total addition amount of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source and the heavy rare earth source, and the addition amounts of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source and the heavy rare earth source are all calculated as oxides.
According to the present invention, the kind of the pore-forming agent is not particularly limited, and it may be various pore-forming agents conventionally used in the art. Preferably, the pore-forming agent is selected from at least one of graphite, polystyrene, and cellulose and derivatives thereof. The present invention has a wide selection range of the type of graphite, and may be natural graphite or artificial graphite, and the present invention is not particularly limited thereto.
The cellulose and its derivatives are preferably at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and sodium hydroxymethyl cellulose.
According to a preferred embodiment of the present invention, the pore-forming agent is selected from at least one of graphite, polystyrene (which may be microspheres) and sodium carboxymethyl cellulose.
According to the present invention, the addition amount of the solvent may be selected within a wide range, and preferably, the addition amount of the solvent is 15 to 35 wt%, preferably 20 to 30 wt%, of the total addition amount of the Fe source, the K source, the Ce source, the W source, the Al source, and the heavy rare earth source, and the addition amounts of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source are all calculated as oxides.
According to the present invention, the solvent is widely selected as long as the mixing environment can be provided, and preferably, the solvent is water.
According to the present invention, the shape of the catalyst is not particularly limited, and may be, for example, granular, bar-shaped, etc., and in a preferred embodiment of the present invention, the method further comprises molding the mixed material before the drying. Those skilled in the art can shape the materials into various usable specifications according to the specific requirements in actual production. The embodiment of the present invention is exemplified by extruding particles 3 mm in diameter and 6 mm in length, and the present invention is not limited thereto.
According to the present invention, preferably, the drying conditions include: the temperature is 50-100deg.C, and the time is 2-10h.
According to a particularly preferred embodiment of the invention, the drying conditions comprise: drying at 55-80deg.C for 2-4 hr, heating to 90-100deg.C, and drying for 0.5-4 hr.
According to the present invention, preferably, the conditions of the firing include: the temperature is 630-960 ℃ and the time is 1-10 hours.
According to a particularly preferred embodiment of the present invention, the conditions of the calcination include: roasting at 630-800 deg.c for 2-4 hr, and then raising the temperature to 900-960 deg.c, preferably for 1-3 hr, and roasting for 2-4 hr. The use of such preferred embodiments is more advantageous in improving the stability of the catalyst.
In a third aspect, the present invention provides an ethylbenzene dehydrogenation catalyst prepared by the preparation method described in the second aspect.
In a fourth aspect, the present invention provides the use of an ethylbenzene dehydrogenation catalyst according to the first or third aspect in ethylbenzene dehydrogenation reactions. The catalyst provided by the invention has higher catalytic activity, selectivity and stability even under the conditions of low water ratio and high space velocity in ethylbenzene dehydrogenation reaction.
In a fifth aspect, the present invention provides a process for the dehydrogenation of ethylbenzene comprising: ethylbenzene is reacted under ethylbenzene dehydrogenation conditions by contacting it with an ethylbenzene dehydrogenation catalyst according to the first or third aspect.
According to the present invention, preferably, the ethylbenzene dehydrogenation conditions include: temperature (temperature)600-650 ℃, preferably 615-635 ℃; the mass airspeed is 1-2.5h -1 Preferably 1.3-2h -1 More preferably 1.5-2h -1 The method comprises the steps of carrying out a first treatment on the surface of the The weight ratio of water to ethylbenzene is 0.6-1.5, more preferably 0.6-1; the pressure is from-90 kPa to-10 kPa, preferably from-70 kPa to-20 kPa.
According to the invention, the ethylbenzene dehydrogenation temperature can be chosen within a wide range, preferably the ethylbenzene dehydrogenation temperature is 600-650 ℃, preferably 615-635 ℃, for example 615 ℃, 620 ℃, 625 ℃, 630 ℃, 635 ℃ and any value between any two values.
According to the invention, the ethylbenzene dehydrogenation catalyst still has good stability and high catalytic activity when used for ethylbenzene dehydrogenation catalysis under high mass space velocity, and preferably, the mass space velocity is 1-2.5h -1 Preferably 1.3-2h -1 More preferably 1.5-2h -1 For example, it may be 1.5h -1 、1.6h -1 、1.7h -1 、1.8h -1 、1.9h -1 、2h -1 And any value between any two values.
According to the invention, the ethylbenzene dehydrogenation catalyst still has better stability, higher catalytic activity and selectivity when used for ethylbenzene dehydrogenation catalytic reaction at a lower weight ratio of water to ethylbenzene, preferably the weight ratio of water to ethylbenzene is 0.6-1.5, more preferably 0.6-1, such as 0.6-0.7, for example, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, and any value between any two values.
The ethylbenzene dehydrogenation pressure according to the present invention may be selected within a wide range, preferably, the pressure is from-90 kPa to-10 kPa, preferably from-70 kPa to-20 kPa, more preferably from-60 kPa to-40 kPa, and for example, may be from-60 kPa to-58 kPa to-56 kPa to 54kPa to 52kPa to 50kPa to 48kPa to 46kPa to 44kPa to 42kPa to 40kPa, and any value between any two values.
In the invention, the performance of the catalyst is characterized by ethylbenzene conversion rate, styrene selectivity and stability, and the catalyst is specifically evaluated in an isothermal fixed bed, and the process is briefly described as follows: deionized water and ethylbenzene are respectively input into a preheating mixer through a metering pump, preheated and mixed into a gaseous state, and then enter into a reactor, and the reactor is heated by an electric heating wire to reach a preset temperature. The reactor was filled with 100 ml of catalyst in a stainless steel tube having an inner diameter of 1 inch. The reaction product flowing out of the reactor is condensed and analyzed by a gas chromatograph for ethylbenzene concentration (weight%) and styrene concentration (weight%);
ethylbenzene conversion% = (initial ethylbenzene concentration in reaction mass (wt%) -ethylbenzene concentration in reaction product (wt%));
Styrene selectivity% = styrene concentration in reaction product (wt%)/(initial ethylbenzene concentration in reaction mass (wt%) -ethylbenzene concentration in reaction product (wt%));
in the present invention, the amount of carbon deposit in the catalyst can be measured by a method conventional in the art, for example, by using an ALario EL III element analyzer of Elementar, germany.
The present invention will be described in detail by examples. In the following examples of the present invention,
the carbon deposit amount refers to the carbon deposit amount in the catalyst removed from the reactor after the reaction for 1200 hours;
iron oxide red, iron oxide yellow, graphite and sodium carboxymethyl cellulose are commercial products meeting national standard requirements.
Example 1
1) 58.05 parts by weight of Fe 2 O 3 Iron oxide red 18.7 parts by weight based on Fe 2 O 3 Iron oxide yellow, 7.4 parts by weight based on K 2 Potassium carbonate, 7.31 parts by weight of CeO 2 Calculated as cerium acetate, 2.58 parts by weight of WO 3 Calculated as ammonium tungstate, 1.12 parts by weight of MnO and 3.16 parts by weight of Al 2 O 3 1.68 parts by weight of Yb 2 O 3 And 5.23 parts by weight of sodium carboxymethylcellulose (commercially available from Shanghai long light corporation, special grade food product, hereinafter the same) were stirred in a kneader for 1.5 hours, and deionized water was then added thereto to remove impurities The addition amount of the ionized water is iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO and Al calculated by oxide 2 O 3 And Yb 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, taken out and extruded into a strip with a diameter of 3 mm and a length of 6 mm, put into an oven, baked at 75 ℃ for 2 hours, then heated to 95 ℃ for 3 hours, then put into a muffle furnace, baked at 635 ℃ for 3 hours, then heated to 920 ℃ for 2.5 hours, and baked for 3 hours to obtain the finished catalyst, the catalyst composition of which is shown in Table 1.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. H of the catalyst 2 The TPR diagram is shown in fig. 1, and it can be seen from fig. 1 that the initial reduction temperature and the full reduction temperature differ by 330 ℃.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h -1 The results of the tests conducted at 625℃and 0.7 weight ratio of water to ethylbenzene for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Comparative example 1
The procedure is as in example 1, except that Al is not added in step 1) 2 O 3 And Yb 2 O 3 The roasting method is different. The method comprises the following steps:
1) 61 parts by weight of Fe 2 O 3 Iron oxide red 19.65 parts by weight of Fe 2 O 3 Iron oxide yellow, 7.78 parts by weight based on K 2 Potassium carbonate, 7.68 parts by weight in terms of CeO, calculated as O 2 Calculated as cerium acetate, 2.71 parts by weight of WO 3 The calculated ammonium tungstate, 1.18 parts by weight of MnO and 5.23 parts by weight of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, deionized water is added, and deionized water is addedThe amount of the catalyst is 25 weight percent of the total amount of iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate and MnO (all calculated as oxides), the mixture is stirred and mixed for 0.5 hour, extruded strips are taken out, extruded into particles with the diameter of 3 mm and the length of 6 mm, the particles are put into an oven, baked for 2 hours at 75 ℃, then heated to 95 ℃ and baked for 3 hours, then put into a muffle furnace and baked for 3 hours at 635 ℃, and then heated to 920 ℃ for 0.5 hour, and the finished catalyst is obtained after baking for 3 hours.
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Comparative example 2
The procedure is as in example 1, except that Al is not added in step 1) 2 O 3 The roasting conditions are different. The method comprises the following steps:
1) 59.94 parts by weight of Fe 2 O 3 Iron oxide red 19.31 parts by weight of Fe 2 O 3 Iron oxide yellow, 7.64 parts by weight based on K 2 Potassium carbonate, 7.55 parts by weight of CeO 2 Calculated as cerium acetate, 2.66 parts by weight of WO 3 Calculated as ammonium tungstate, 1.16 parts by weight of MnO and 1.73 parts by weight of Yb 2 O 3 And 5.23 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, deionized water is added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO and Yb are added in terms of oxide 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then baked at 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 3.5 hours, and baked for 3 hours to give the final catalyst, the catalyst composition being shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 2
The procedure of example 1 was followed, except that Yb was used 2 O 3 Replaced by equivalent Tm 2 O 3 The roasting condition is that roasting is carried out for 3 hours at 635 ℃, then heating to 920 ℃ for 1.5 hours, and roasting for 3 hours to obtain the finished catalyst.
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Comparative example 3
The procedure is as in example 2, except that Al is not added in step 1) 2 O 3 . The method comprises the following steps: 1) 59.94 parts by weight of Fe 2 O 3 Iron oxide red 19.31 weight parts of Fe 2 O 3 Iron oxide yellow, 7.64 parts by weight based on K 2 Potassium carbonate, 7.55 parts by weight of CeO 2 Calculated as cerium acetate, 2.66 parts by weight of WO 3 Calculated as ammonium tungstate, 1.16 parts by weight MnO, 1.73 parts by weight Tm 2 O 3 And 5.23 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, and then deionized water was added in such amounts that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO and Tm as oxides 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 1.5 hours, and baked for 3 hours to give the final catalyst, the catalyst composition of which is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 3
The procedure of example 1 was followed, except that Yb was used 2 O 3 Replaced by equal amounts of Lu 2 O 3 。
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Comparative example 4
The procedure is followed as in example 3, except that Al is not added in step 1) 2 O 3 The method specifically comprises the following steps: 1) 59.94 parts by weight of Fe 2 O 3 Iron oxide red 19.31 weight parts of Fe 2 O 3 Iron oxide yellow, 7.64 parts by weight based on K 2 Potassium carbonate, 7.55 parts by weight of CeO 2 Calculated as cerium acetate, 2.66 parts by weight of WO 3 Calculated as ammonium tungstate, 1.16 parts by weight of MnO, 1.73 parts by weight of Lu 2 O 3 And 5.23 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, and then deionized water is added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, al are added as oxides 2 O 3 And Lu 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 2.5 hours, and baked for 3 hours to give the final catalyst, the catalyst composition of which is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 4
A catalyst was prepared and tested as in example 1, except that 1.68 parts by weight of Yb 2 O 3 Replacement with 0.84 parts by weight of Yb 2 O 3 And 0.84 parts by weight of Tm 2 O 3 。
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 5
A catalyst was prepared and tested as in example 1, except that 1.68 parts by weight of Yb 2 O 3 Replacement with 0.84 parts by weight of Yb 2 O 3 And 0.84 parts by weight of Lu 2 O 3 。
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 6
A catalyst was prepared and tested as in example 1, except that 1.68 parts by weight of Yb 2 O 3 Tm in place of 0.84 parts by weight 2 O 3 And 0.84 parts by weight of Lu 2 O 3 。
The catalyst composition is shown in Table 1. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 7
A catalyst was prepared and a catalyst was tested in the same manner as in example 1, except that 1.12 parts by weight of Yb 2 O 3 Tm in place of 0.56 parts by weight 2 O 3 And 0.56 parts by weight of Lu 2 O 3 。
The catalyst composition is shown in Table 2. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 8
1) 53.75 parts by weight of Fe 2 O 3 Iron oxide red 17.18 parts by weight based on Fe 2 O 3 Iron oxide yellow, 7.85 parts by weight based on K 2 Potassium carbonate calculated by O and 8.9 parts by weight of CeO 2 Calculated as cerium acetate, 4.13 parts by weight of WO 3 Calculated as ammonium tungstate, 3.35 parts by weight of MnO and 3.5 parts by weight of Al 2 O 3 0.85 part by weight of Yb 2 O 3 0.49 part by weight of TiO 2 And 4.62 parts of graphite were stirred in a kneader for 1.5 hours, and deionized water was then added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, and Al were added as oxide 2 O 3 、Yb 2 O 3 And TiO 2 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 2 hours, and baked for 3 hours to give the final catalyst, the catalyst composition being shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h -1 The results of the tests conducted at 625℃and 0.7 weight ratio of water to ethylbenzene for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 9
1) 52.73 parts by weight of Fe 2 O 3 Iron oxide red 13.45 parts by weight based on Fe 2 O 3 Iron oxide yellow, 4.55 parts by weight based on K 2 10.55 parts by weight of potassium carbonate calculated as O and calculated as CeO 2 Calculated as cerium acetate, 1.21 parts by weight of WO 3 Calculated as ammonium tungstate, 4.95 parts by weight of MnO and 7.65 parts by weight of Al 2 O 3 4.4 parts by weight of Yb 2 O 3 0.51 part by weight of MoO 3 And 4.62 parts by weight of graphite in a kneader for 1.5 hours, and deionized water was added in an amount of iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, al as oxides 2 O 3 、Yb 2 O 3 And MoO 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 1.2 hours, and baked for 3 hours to give the final catalyst, the catalyst composition of which is shown in Table 2.
2) The change in the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, and was measured in He gasHeating to 400 ℃ under the atmosphere, then cooling to room temperature, and switching to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 10
1) 55.36 parts by weight of Fe 2 O 3 Iron oxide red 17.42 parts by weight based on Fe 2 O 3 Calculated as iron oxide yellow, 5.71 parts by weight of K 2 Potassium carbonate, 7.46 parts by weight in terms of CeO, calculated as O 2 Calculated as cerium acetate, 4.82 parts by weight of WO 3 Calculated as ammonium tungstate, 1.83 parts by weight of MnO and 0.72 parts by weight of Al 2 O 3 4.58 parts by weight of Yb 2 O 3 2.1 parts by weight of cement and 4.95 parts by weight of sodium carboxymethylcellulose are stirred in a kneader for 1.5 hours, and deionized water is added in such amounts that the addition amount of the deionized water is iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO and Al calculated as oxides 2 O 3 、Yb 2 O 3 And 25% by weight of the total cement (all calculated as oxides) were stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75 ℃ for 2 hours, then heated to 95 ℃ for 3 hours, then placed in a muffle furnace, baked at 635 ℃ for 3 hours, then heated to 920 ℃ for 2.5 hours, and baked for 3 hours to obtain the final catalyst, the catalyst composition being shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 Concentration of 10% by volume) reducing gas was subjected to temperature programmed reduction at 10 °c +The min rate was raised to 850 ℃. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 11
1) 60.6 parts by weight of Fe 2 O 3 Iron oxide red 17.45 parts by weight based on Fe 2 O 3 Iron oxide yellow, 6.05 parts by weight based on K 2 Potassium carbonate calculated by O and 6.15 parts by weight of CeO 2 Calculated as cerium acetate, 2.03 parts by weight of WO 3 Calculated as ammonium tungstate, 0.55 part by weight of MnO and 5.15 parts by weight of Al 2 O 3 2.02 parts by weight of Yb 2 O 3 And 4.95 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, and then deionized water is added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, al are added as oxides 2 O 3 And Yb 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 2.5 hours, and baked for 3 hours to give the final catalyst, the catalyst composition of which is shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa,Space velocity of mass 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 12
A catalyst and a test catalyst were prepared as in example 1, except that 7.31 parts by weight of CeO was used 2 The calculated cerium acetate was replaced with 7.31 parts by weight of CeO 2 。
The catalyst composition is shown in Table 2. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Example 13
The catalyst was prepared and tested as in example 1, except that the catalyst was prepared as Fe 2 O 3 The iron oxide red was used in an amount of 50.25 parts by weight in terms of Fe 2 O 3 The amount of iron oxide yellow to be used was 26.5 parts by weight. The total amount of iron oxide, the catalyst preparation method, the catalyst evaluation conditions, the reduction resistance measurement of the catalyst, and the char analysis were the same as in example 1, except that the ratio of iron oxide red to iron oxide yellow was different.
The catalyst composition is shown in Table 2. The difference between the initial reduction temperature and the complete reduction temperature, the test results and the carbon deposit amount results are shown in Table 3.
Comparative example 5
1) 54.75 parts by weight of Fe 2 O 3 Iron oxide red 17.18 parts by weight based on Fe 2 O 3 Iron oxide yellow, 8.85 parts by weight based on K 2 Potassium carbonate 11.2 weight portions calculated by O and CeO 2 Calculated as cerium acetate, 1.55 parts by weight of WO 3 Calculated as ammonium tungstate, 3.12 parts by weight of MnO and 2.5 parts by weight of Al 2 O 3 0.85 part by weight of Yb 2 O 3 And 4.62 parts of graphite were stirred in a kneader for 1.5 hours, and deionized water was then added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, and Al were added as oxide 2 O 3 And Yb 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 0.75 hour, and baked for 3 hours to give the final catalyst, the catalyst composition being shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 14
1) 55.36 parts by weight of Fe 2 O 3 Iron oxide red 17.42 parts by weight based on Fe 2 O 3 Calculated as iron oxide yellow, 5.78 parts by weight of K 2 Potassium carbonate, 9.88 parts by weight, calculated as CeO 2 Calculated as cerium acetate, 3.85 parts by weight of WO 3 Calculated as ammonium tungstate, 2.12 parts by weight of MnO and 0.92 part by weight of Al 2 O 3 Tm of 4.67 parts by weight 2 O 3 And 4.95 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, and then deionized water is added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, al are added as oxides 2 O 3 And Tm 2 O 3 25% by weight of the total amount (calculated by oxide) is stirred and mixed for 0.5 hour, extruded strips are taken out, extruded into strips with the diameter of 3 mm and the length of 6 mm, put into a baking oven, baked for 2 hours at the temperature of 75 ℃, and then heated to the temperature of 95 ℃ and baked for 3 hoursThen, the mixture was placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 2.5 hours, and baked for 3 hours to obtain a finished catalyst, the composition of which is shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The difference between the initial reduction temperature and the complete reduction temperature is shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
Example 15
1) 52.36 parts by weight of Fe 2 O 3 Iron oxide red 16.42 parts by weight based on Fe 2 O 3 Iron oxide yellow, 7.92 parts by weight based on K 2 Potassium carbonate 9.46 parts by weight calculated as CeO 2 Calculated as cerium acetate, 4.82 parts by weight of WO 3 Calculated as ammonium tungstate, 3.83 parts by weight of MnO and 1.85 parts by weight of Al 2 O 3 3.34 parts by weight of Lu 2 O 3 And 4.95 parts by weight of sodium carboxymethylcellulose in a kneader for 1.5 hours, and then deionized water is added in such an amount that iron oxide red, iron oxide yellow, potassium carbonate, cerium acetate, ammonium tungstate, mnO, al are added as oxides 2 O 3 And Lu 2 O 3 25% by weight of the total amount (each calculated as oxide) was stirred and mixed for 0.5 hour, extruded strips were taken out, extruded into strips of 3 mm diameter and 6 mm length, placed in an oven, baked at 75℃for 2 hours, then heated to 95℃for 3 hours, then placed in a muffle furnace, baked at 635℃for 3 hours, then heated to 920℃over 2.5 hours, and baked for 3 hours to give the final catalyst, the catalyst composition of which is shown in Table 2.
2) The change of the reduction temperature of the catalyst was observed by Temperature Programmed Reduction (TPR), a 50mg sample of the catalyst was placed in a U-tube quartz reactor, heated to 400℃under He atmosphere, then cooled to room temperature, and switched to H 2 /N 2 (H 2 The concentration is 10% by volume) of the reducing gas is subjected to temperature programmed reduction, and the temperature is increased to 850 ℃ at a rate of 10 ℃/min. The yield values for the initial reduction temperature and the full reduction temperature are shown in Table 3.
3) 100 ml of the catalyst obtained in step 1) were charged into a reactor at-50 kPa, mass space velocity of 1.5h - 1. The results of the tests conducted at 625℃and a weight ratio of water to ethylbenzene of 0.7 for 100 hours and 1200 hours are shown in Table 3. The catalyst after the reaction was analyzed by an elemental analyzer, and the results of the carbon deposit amount are shown in Table 3.
TABLE 1
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TABLE 2
TABLE 3 Table 3
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As can be seen from the results in the above table, an appropriate amount of aluminum oxide and Yb selected from heavy rare earth oxides is added to the Fe-K-Ce-W-Mn catalytic system 2 O 3 、Tm 2 O 3 And Lu 2 O 3 The catalyst has high stability, catalytic activity and selectivity under the conditions of low weight ratio of water to ethylbenzene and high quality airspeed, has high carbon deposit resistance (i.e. low carbon deposit quantity), can meet the requirement of treating more raw materials when the styrene market is good, has remarkable energy-saving effect, is beneficial to the cost reduction and efficiency improvement of a styrene device, and can be well used in the industrial production of preparing styrene by ethylbenzene dehydrogenation under the conditions of low weight ratio of water to ethylbenzene and high quality airspeed.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (23)

1. An ethylbenzene dehydrogenation catalyst, characterized in that the catalyst contains Fe 2 O 3 、K 2 O、CeO 2 、WO 3 MnO and Al 2 O 3 And heavy rare earth oxides;
fe based on the total amount of the catalyst 2 O 3 The content of K is 66-79 wt% 2 O content is 4.5-8 wt%, ceO 2 Is contained in an amount of 6 to 11 wt.%, WO 3 The content of (2) is 1-5 wt%, the content of MnO is 0.5-5 wt%, and Al 2 O 3 The content of the rare earth oxide is 0.5-8 wt%, and the content of the heavy rare earth oxide is 0.5-5 wt%;
the heavy rare earth oxide is selected from Yb 2 O 3 、Tm 2 O 3 And Lu 2 O 3 At least one of them.
2. The catalyst according to claim 1, wherein Fe is based on the total amount of the catalyst 2 O 3 The content of K is 70-78 wt% 2 The content of O is 6.5-7.5 wt%, ceO 2 Is contained in an amount of 7 to 9 wt.%, WO 3 The content of (2.5-4.5 wt.%), mnO (1-3.5 wt.%) and Al 2 O 3 The content of (C) is 0.8-5.2 wt%, and the content of heavy rare earth oxide is 0.8-4 wt%.
3. The catalyst of claim 1 or 2, wherein the catalyst has a full reduction temperature that is 310-360 ℃ higher than the initial reduction temperature.
4. A catalyst according to claim 3, wherein the catalyst has a complete reduction temperature that is 325-360 ℃ higher than the initial reduction temperature.
5. The catalyst according to claim 1 or 2, wherein the catalyst does not contain molybdenum oxide;
and/or the catalyst does not contain a binder.
6. The catalyst of claim 5, wherein the binder is selected from at least one of cement, kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, and bentonite.
7. A process for preparing an ethylbenzene dehydrogenation catalyst as claimed in any one of claims 1 to 6 which comprises: the Fe source, K source, ce source, W source, mn source, al source, and heavy rare earth source are mixed with the porogen and solvent, and then optionally dried and calcined.
8. The method of claim 7, wherein the Ce source is cerium acetate and/or cerium carbonate;
and/or the Fe source is iron oxide red and/or iron oxide yellow.
9. The method of claim 8, wherein the Fe sources are red iron oxide and yellow iron oxide.
10. The method of claim 9, wherein the weight ratio of red iron oxide to yellow iron oxide, on an oxide basis, is 3-4:1.
11. the method of claim 7, wherein the K source is potassium carbonate and/or potassium bicarbonate;
and/or, the W source is selected from at least one of ammonium tungstate, ammonium metatungstate and tungsten trioxide;
and/or the Mn source is selected from at least one of manganese oxide, manganese hydroxide and manganese carbonate;
and/or, the Al source is selected from at least one of aluminum oxide, aluminum hydroxide and aluminum carbonate;
and/or the heavy rare earth source is selected from at least one of ytterbium trioxide, thulium trioxide and lutetium trioxide.
12. The method of claim 7, wherein the pore-forming agent is added in an amount of 2-6 wt% of the total of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source, and the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source are added in amounts of oxide.
13. The method of claim 12, wherein the pore-forming agent is added in an amount of 4.5-5.5 wt% based on the total addition of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source, and the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source are all added in terms of oxides.
14. The method of claim 7, wherein the pore-forming agent is selected from at least one of graphite, polystyrene, and cellulose and derivatives thereof.
15. The method according to claim 7, wherein the solvent is added in an amount of 15 to 35 wt% of the total addition amount of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source, and the addition amounts of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source are all calculated as oxides.
16. The method of claim 15, wherein the solvent is added in an amount of 20-30 wt% of the total addition of the Fe source, the K source, the Ce source, the W source, the Mn source, the Al source, and the heavy rare earth source, each calculated as an oxide.
17. The method of claim 7, wherein the solvent is water.
18. The method of claim 7, further comprising shaping the mixed material prior to said drying;
and/or, the drying conditions include: the temperature is 50-100 ℃ and the time is 2-10h;
and/or, the roasting conditions include: the temperature is 630-960 ℃ and the time is 1-10 hours.
19. The method of claim 18, wherein the drying conditions comprise: drying at 55-80deg.C for 2-4 hr, heating to 90-100deg.C, and drying for 0.5-4 hr;
and/or, the roasting conditions include: roasting at 630-800 deg.c for 2-4 hr, heating to 900-960 deg.c and roasting for 2-4 hr.
20. An ethylbenzene dehydrogenation catalyst prepared by the preparation process as claimed in any one of claims 7 to 19.
21. Use of the ethylbenzene dehydrogenation catalyst of any one of claims 1-6 and 20 in ethylbenzene dehydrogenation reactions.
22. A process for the dehydrogenation of ethylbenzene, comprising: contacting ethylbenzene with the ethylbenzene dehydrogenation catalyst of any one of claims 1-6 and 20 under ethylbenzene dehydrogenation conditions to react;
the B isThe benzene dehydrogenation conditions include: the temperature is 600-650 ℃, and the mass airspeed is 1-2.5h -1 The weight ratio of water to ethylbenzene is 0.6-1.5 and the pressure is-90 kPa to-10 kPa.
23. The ethylbenzene dehydrogenation process according to claim 22 wherein the ethylbenzene dehydrogenation conditions comprise: the temperature is 615-635 ℃, and the mass airspeed is 1.3-2h -1 The weight ratio of water to ethylbenzene is 0.6-1 and the pressure is-70 kPa to-20 kPa.
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