CN1181918C - Catalyst for alkyl aromatics dehydrogenation - Google Patents
Catalyst for alkyl aromatics dehydrogenation Download PDFInfo
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- CN1181918C CN1181918C CNB021374473A CN02137447A CN1181918C CN 1181918 C CN1181918 C CN 1181918C CN B021374473 A CNB021374473 A CN B021374473A CN 02137447 A CN02137447 A CN 02137447A CN 1181918 C CN1181918 C CN 1181918C
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- catalyst
- catalyzer
- oxide
- oxide compound
- alkyl aromatics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a catalyst for dehydrogenating alkyl aromatic. The present invention mainly solves the problems that the catalyst in the prior art has high potassium content, the potassium can run off easily when the catalyst is in operation; therefore, the crushing strength of catalyst particles is reduced, the service life of the catalyst is influenced, or the catalytic activity of the catalyst is low under the condition of a low potassium content. The present invention favorably solves the problems by the technical scheme that alkali metal lithium oxide and tungsten oxide are added in a ferrum-potassium-cerium-molybdenum system; meanwhile, the catalyst can still have high activity, high crushing resistance and adaptive capability for low-temperature operation under the condition of a low potassium content, and can be used for the industrial production of styrene.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for alkyl aromatics dehydrogenation, particularly about being used for the catalyzer of ethyl benzene dehydrogenation preparation of styrene.
Background technology
Industrial alkenyl arene mainly is to be made by alkyl aromatics dehydrogenation, and therefore selecting a kind of highly active dehydrogenation catalyst is one of its key.At present, the ferripotassium System Catalyst that is used for alkyl aromatics dehydrogenation roughly is divided into two big classes: a class is the catalyzer that high potassium content has greater activity, as CN1047097C, CN1050535C, CN1226462A, CN1298856A.The catalyzer of patent CN1047097C report is under 600 ℃ of conditions, and conversion of ethylbenzene can reach 78.3%, and the vinylbenzene list receives 73.9%, selectivity of styrene 94.4%.The catalyzer of patent CN1050535C is under 620 ℃ of conditions, and conversion of ethylbenzene is 79.1%, and the vinylbenzene list receives 76.0%, selectivity of styrene 96.1%.The catalyzer of patent CN1298856A is under 620 ℃ of conditions, and conversion of ethylbenzene is 80.7%, and the vinylbenzene list receives 77.2%, selectivity of styrene 95.7%.In this type of catalyzer as the K of promotor
2O is up to about 30%.Because the strong absorptive of potassium, when catalyzer places air, the catalyzer that contains a large amount of potassium can absorb moisture, the anti-crushing power of granules of catalyst is reduced, and in dehydrogenation reaction process, potassium can be little by little towards the granule interior migration or move out of granules of catalyst, thereby cause the decline of catalyst performance.Another kind of is the low potassium content catalyzer, as US6191065, US6242379, US6037305.Potassium content decreases in this type of catalyzer, but activity of such catalysts is corresponding lower.The catalyzer of patent US6191065 is in the time of 600 ℃, and conversion of ethylbenzene has only 47.7%, and selectivity of styrene is 97.3%.The catalyzer of patent US6037305 report is in the time of 550 ℃, and conversion of ethylbenzene is 77.5%, but selectivity of styrene has only 90%, and cerium oxide component content is up to 76% in this catalyst component, zirconium white component content is up to 19%, so this catalyzer cost is very high, is difficult to realize industrial application.
Summary of the invention
Technical problem to be solved by this invention is to have potassium content height in the catalyzer in the conventional art, granules of catalyst is on-stream, easily make potassium lost, cause the anti-crushing power of granules of catalyst to reduce, or catalyzer lower problem of catalytic activity under low potassium content, a kind of new catalyzer that is used for alkyl aromatics dehydrogenation is provided.This catalyzer is used for the alkyl aromatics dehydrogenation reaction to have under low potassium content, the catalytic activity height, and the anti-crushing power height of granules of catalyst, and still can keep high aromatics conversion rate and the high characteristics of purpose product yield at a lower temperature.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer that is used for alkyl aromatics dehydrogenation, contain following active constituent by weight percentage:
A) oxide compound of iron is with Fe
2O
3Count 60～90%;
B) oxide compound of potassium is with K
2O counts 5～13%;
C) oxide compound of cerium is with Ce
2O
3Count 3～13%;
D) oxide compound of tungsten is with WO
3Count 0.005～5%;
E) oxide compound of lithium is with Li
2O counts 0.005～5%;
All the other are binding agent, and the amount of binding agent is 0.1～10% of a catalyst weight.
In the technique scheme, the oxide compound of tungsten is with WO by weight percentage
3The meter preferable range is 0.01～2%, and more preferably scope is 0.1～1.0%.The oxide compound of lithium is with Li by weight percentage
2O meter preferable range is 0.01～2.5%, and more preferably scope is 0.1～1.0%; Binding agent is a cement; The catalyzer preferred version is for also contain the oxide compound of active constituent molybdenum in catalyzer, with MoO
3Count 0.1～5%; In catalyzer, also can contain the oxide compound of active constituent magnesium, count 0.01～5% with MgO.By weight percentage, preferred version is for also to contain at least a oxide compound that is selected from copper, calcium, tin, lead, scandium, titanium, vanadium, manganese, zirconium or niobium in the catalyzer, and its consumption is 0.001～5%.
Method for preparing catalyst of the present invention is as follows:
Press compound, binding agent cement, the pore-creating agent carboxymethyl cellulose of other metal of proportioning weighing Fe, K, Ce, Li, W and selection, dry powder blend adds an amount of deionized water, and wet feed is mediated to the face dough that is fit to extrusion.It is 3 millimeters that extrusion, pelletizing become diameter, and bar length is the particle of 5 millimeter.In aged at room temperature 2～10 hours, 80～120 ℃ of dryings 4 hours, 600～1000 ℃ of roastings 2 hours can obtain the catalyzer finished product.
Activity rating of catalyst carries out in the isothermal fixed-bed reactor among the present invention, and reactor is that internal diameter is 25 millimeters a stainless steel tube, loads 100 milliliters of catalyzer.The activity rating process is as follows: reactor cleaned out, and the 100 milliliters of catalyzer of packing into, the affirmation system does not have the back of leakage and connects water coolant, connects power supply again to the reactor heat temperature raising.When temperature of reactor is raised to 300 ℃, open the water feed valve, feed water to system.When temperature of reactor is raised to 540 ℃, open the ethylbenzene feed valve, feed ethylbenzene to system.After the heating that heats up after a while, temperature is done suitably to adjust, make it be stabilized in required temperature.Throw ethylbenzene and begin sampling after 5 hours, be 30 minutes each sample time, and sample is carried out oily water separation, gets dehydrogenation liquid and water layer, and dehydrogenation liquid records ethylbenzene and styrene content for stratographic analysis by GB12688.1-1998.Throw ethylbenzene after 36 hours, it is stable that data reach.From then on can obtain valid data and test, every sampling in 2 hours once, serial sampling is finished test five times.Calculating formula is as follows:
The vinylbenzene list is received (%)=conversion of ethylbenzene (%) * selectivity of styrene (%)
The anti-crushing power of catalyzer is measured by the technical requirements of standard HG/T 2782-1996 regulation among the present invention, uses DL-II type intelligence granule strength instrument.5 millimeters of specimen lengths are one group with 40 and test that the arithmetical av of getting its measurement result is final anti-crushing power value, is the resistance to crusing unit of force with newton (N).
The wear attrition of catalyst rate is measured by the technical requirements of standard GB10505.2-89 regulation among the present invention, uses CM-3B type particle wear test instrument.
Fe in the catalyzer of the present invention
2O
3Be main active constituent, K
2O is main promotor, Ce
2O
3It is structural stabilizing agent.At low potassium catalyst activity and the lower problem of selectivity, the present invention has introduced WO
3, improved the selectivity of styrene of low potassium catalyzer effectively.Li
2The introducing of O makes activity of such catalysts shortening inductive phase, has higher initial activity.Multiple metal oxide be added with the raising that is beneficial to the catalyzer over-all properties.Fe
2O
3Form with red iron oxide and/or iron oxide yellow adds K
2O adds Ce with the form of oxide compound, oxyhydroxide or the salt of potassium
2O
3Form with oxide compound, oxyhydroxide or the salt of cerium adds Li
2O adds WO with the oxyhydroxide of lithium or the form of salt
3Add with the oxide compound of tungsten or the form of salt.
The present invention has added W, Li and other multiple metal oxide in the Fe-K-Ce catalyst system, thereby makes low potassium content (K
2O≤13%) catalyzer still keeps higher activity, particularly under cold condition, higher vinylbenzene yield is arranged, and catalyzer has the broken power of higher compression simultaneously.Catalyzer of the present invention is under 610 ℃ of conditions, and conversion of ethylbenzene is 75.1%, and the vinylbenzene list receives 71.5%, selectivity of styrene 95.2%, the catalyzer anti-crushing power has reached 121 newton, and cerium content is lower in the catalyzer, make the Preparation of Catalyst cost lower, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
300 gram red iron oxides, 53 gram salt of wormwood, 35 gram cerium oxide, 15 gram Quilonum Retards, 11 gram magnesium oxide, 5 gram aluminum oxide, 12 gram cement, 8 gram carboxymethyl celluloses are mixed, add an amount of deionized water, wet feed is mediated to the face dough that is fit to extrusion.It is 3 millimeters that extrusion, pelletizing become diameter, and bar length is the particle of 5 millimeter.In aged at room temperature 8 hours, put into baking oven, in 80 ℃ of dryings 4 hours, place stoving oven, made the catalyzer finished product in 2 hours in 800 ℃ of roastings.With 100 milliliters of catalyzer assessing reactor of packing into, 610 ℃ of temperature of reaction, water is than carrying out catalytically active assessment under 2.0 conditions, and measures anti-crushing power, the rate of wear of catalyzer.Test result: conversion of ethylbenzene 75.1%, selectivity of styrene 94.3%, the vinylbenzene list receives 70.8%, anti-crushing power 100 newton, rate of wear 2%.
[embodiment 2]
210 gram red iron oxides, 120 gram iron oxide yellow, 56 gram salt of wormwood, 35 gram cerium oxide, 15 gram Quilonum Retards, 6 gram Tungsten oxide 99.999s, 11 gram magnesium oxide, 20 gram cement, 8 gram carboxymethyl celluloses are mixed, add an amount of deionized water, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 74.5%, selectivity of styrene 95.1%, the vinylbenzene list receives 70.8%, anti-crushing power 100 newton, rate of wear 1%.
[embodiment 3]
210 gram red iron oxides, 120 gram iron oxide yellow, 61 gram salt of wormwood, 35 gram cerium oxide, 15 gram Quilonum Retards, 6 gram Tungsten oxide 99.999s, 11 gram magnesium oxide, 2 gram molybdenum oxides, 4 gram cupric oxide, 2 gram plumbous oxide, 2 gram stannic oxide, 20 gram cement, 8 gram carboxymethyl celluloses are mixed, add an amount of deionized water, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 75.1%, selectivity of styrene 95.2%, the vinylbenzene list receives 71.5%, anti-crushing power 121 newton, rate of wear 0.2%.
[comparative example 1]
210 gram red iron oxides, 120 gram iron oxide yellow, 56 gram salt of wormwood, 35 gram cerium oxide, 11 gram magnesium oxide, 5 gram aluminum oxide, 12 gram cement, 8 gram carboxymethyl celluloses are mixed, add an amount of deionized water, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 64.9%, selectivity of styrene 94.0%, the vinylbenzene list receives 61.0%, anti-crushing power 50 newton, rate of wear 8%.
More than each embodiment explanation, catalyzer of the present invention has added W, Li and other multiple metal oxide in the Fe-K-Ce catalyst system, make catalyzer have catalytic activity preferably, but also has crushing resistance and wear resistance preferably.
Table 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Weight percentage % | Weight percentage % | Weight percentage % | Weight percentage % | |
| Ferric oxide | 76 | 74 | 72 | 77 |
| Potassium oxide | 9 | 8.5 | 9 | 8.8 |
| Cerium oxide | 8.8 | 7.9 | 7.7 | 8.1 |
| Lithium Oxide 98min | 1.1 | 1.3 | ||
| Tungsten oxide 99.999 | 1.3 | 1.3 | ||
| Magnesium oxide | 2.8 | 2.5 | 2.4 | 2.6 |
| Aluminum oxide | 1.3 | 1.2 | ||
| Molybdenum oxide | 0.4 | |||
| Cupric oxide | 0.9 | |||
| Plumbous oxide | 0.4 | |||
| Stannic oxide | 0.4 | |||
| Cement | 3 | 4.5 | 4.4 | 2.8 |
| Transformation efficiency, % | 75.1 | 74.5 | 75.1 | 64.9 |
| Selectivity, % | 94.3 | 95.1 | 95.2 | 94.0 |
| Single receipts, % | 70.8 | 70.8 | 71.5 | 61.0 |
| Anti-crushing power, newton | 100 | 100 | 121 | 50 |
| Rate of wear, % | 2 | 1 | 0.2 | 8 |
[embodiment 4～6]
Press each step and the examination condition of embodiment 3, just change the content of Lithium Oxide 98min in the catalyzer, Tungsten oxide 99.999, it the results are shown in table 2.
Table 2
| Component | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Weight percentage % | Weight percentage % | Weight percentage % | |
| Ferric oxide | 73 | 72.5 | 71.9 |
| Potassium oxide | 9 | 9 | 9.2 |
| Cerium oxide | 7.7 | 7.7 | 7.7 |
| Lithium Oxide 98min | 1.0 | 0.5 | 0.3 |
| Tungsten oxide 99.999 | 0.3 | 1.3 | 1.8 |
| Magnesium oxide | 2.4 | 2.5 | 2.4 |
| Molybdenum oxide | 0.5 | 0.5 | 0.5 |
| Cupric oxide | 0.9 | 0.9 | 0.9 |
| Plumbous oxide | 0.4 | 0.4 | 0.4 |
| Stannic oxide | 0.4 | 0.4 | 0.4 |
| Cement | 4.4 | 4.3 | 4.5 |
| Transformation efficiency, % | 75.0 | 74.7 | 75.3 |
| Selectivity, % | 94.8 | 95.0 | 95.1 |
| Single receipts, % | 71.1 | 71.0 | 71.6 |
| Anti-crushing power, newton | 119 | 117 | 114 |
| Rate of wear, % | 0.3 | 0.4 | 0.6 |
Claims (9)
1, a kind of catalyzer that is used for alkyl aromatics dehydrogenation, contain following active constituent by weight percentage:
A) oxide compound of iron is with Fe
2O
3Count 60～90%;
B) oxide compound of potassium is with K
2O counts 5～13%;
C) oxide compound of cerium is with Ce
2O
3Count 3～13%;
D) oxide compound of tungsten is with WO
3Count 0.005～5%;
E) oxide compound of lithium is with Li
2O counts 0.005～5%;
All the other are binding agent, and the amount of binding agent is 0.1～10% of a catalyst weight.
2, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1, it is characterized in that the oxide compound of tungsten by weight percentage, with WO
3Count 0.01～2%.
3, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 2, it is characterized in that the oxide compound of tungsten by weight percentage, with WO
3Count 0.1～1.0%.
4, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1, it is characterized in that the oxide compound of lithium by weight percentage, with Li
2O counts 0.01～2.5%.
5, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 4, it is characterized in that the oxide compound of lithium by weight percentage, with Li
2O counts 0.1～1.0%.
6,, it is characterized in that binding agent is a cement according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1.
7, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1, it is characterized in that by weight percentage, also contain the oxide compound of active constituent molybdenum in the catalyzer, with MoO
3Count 0.1～5%.
8, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1, it is characterized in that by weight percentage, also contain the oxide compound of active constituent magnesium in the catalyzer, count 0.01～5% with MgO.
9, according to the described catalyzer that is used for alkyl aromatics dehydrogenation of claim 1, it is characterized in that by weight percentage, also contain at least a oxide compound that is selected from copper, calcium, tin, lead, scandium, titanium, vanadium, manganese, zirconium or niobium in the catalyzer, its consumption is 0.001～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021374473A CN1181918C (en) | 2002-10-16 | 2002-10-16 | Catalyst for alkyl aromatics dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021374473A CN1181918C (en) | 2002-10-16 | 2002-10-16 | Catalyst for alkyl aromatics dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1490084A CN1490084A (en) | 2004-04-21 |
| CN1181918C true CN1181918C (en) | 2004-12-29 |
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ID=34147026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021374473A Expired - Lifetime CN1181918C (en) | 2002-10-16 | 2002-10-16 | Catalyst for alkyl aromatics dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1181918C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279268B (en) * | 2007-04-04 | 2011-05-18 | 中国石油化工股份有限公司 | Energy-saving alkyl aromatics dehydrogenation catalyst |
| CN103028421B (en) * | 2011-09-30 | 2014-11-26 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst |
| CN106582686A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with high activity and low steam-to-oil ratio and preparing method thereof |
| CN109569640B (en) * | 2017-09-29 | 2020-06-09 | 中国石油化工股份有限公司 | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CA3116597C (en) * | 2018-10-16 | 2024-06-11 | China Petroleum & Chemical Corporation | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon and preparation method therefor |
-
2002
- 2002-10-16 CN CNB021374473A patent/CN1181918C/en not_active Expired - Lifetime
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|---|---|
| CN1490084A (en) | 2004-04-21 |
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Granted publication date: 20041229 |