CN1184176C - Method for preparing alkyl aromatics dehydrogenation catalyst - Google Patents
Method for preparing alkyl aromatics dehydrogenation catalyst Download PDFInfo
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- CN1184176C CN1184176C CNB021110077A CN02111007A CN1184176C CN 1184176 C CN1184176 C CN 1184176C CN B021110077 A CNB021110077 A CN B021110077A CN 02111007 A CN02111007 A CN 02111007A CN 1184176 C CN1184176 C CN 1184176C
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Abstract
The present invention relates to a method for preparing a dehydrogenation catalyst of alkyl aromatics, which mainly solves the problem that a catalyst can not simultaneously have good reaction property and good waterproof property in the prior art. The present invention has the technical scheme that high roasting temperature and long roasting time are adopted in a preparation process of the catalyst, and thus, the problem is favorably solved. The present invention can be used for the industrial preparation of the dehydrogenation catalyst of alkyl aromatics.
Description
Technical field
The present invention relates to a kind of method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst.
Background technology
Common industrial production alkyl alkenyl arene is to be made by alkyl aromatics catalytic dehydrogenation, and one of key of this method is to select the dehydrogenation catalyst of a kind of high reactivity, highly selective, high stability.At present, industrial what generally adopt is the Fe-K-Ce-Mo-Mg series catalysts, Fe
2O
3Be main active component, K
2O is wherein most important accelerative activator, and its interpolation can make the activity of Fe-series catalyst improve an order of magnitude.K
2O be introduced in effective raising catalyst reaction performance the time, also exist some problems such as catalyzer in preparation, transportation, filling process, particularly liquid water is very responsive to steam.In addition, in the certain embodiments, when misoperation or operating mode were undesired, catalyzer will contact with liquid water inevitably.Catalyzer is with after water contacts, expand probably, physicals degradation phenomena such as deliquescing, fracture even efflorescence, and then directly influence the physical strength of catalyzer, cause in the use bed pressure drop to increase, be unfavorable for increasing the load that feeds intake, realize quiet run and prolongation catalyzer work-ing life.For this reason, people also very pay close attention to and improve the research work of catalyzer to water resistance when making great efforts to improve catalyst activity.The general method that adopts is by introduce binding agent, toughener such as cement, gypsum, kaolin, silica gel etc. in the Fe-K-Ce-Mo-Mg system, in order to strengthen the interaction between catalyst component.As laid-open U.S. Patents US4804799, U.S. Pat 4975407, European patent EP 0296285A1, European patent EP 0482276A1 etc., but the interpolation of a large amount of binding agents, toughener, can cause that activity of such catalysts, selectivity descend, thereby be difficult to take into account the problem that catalyst activity, selectivity and water resistance improve simultaneously.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming that exists catalyst reaction performance and water resistance not to take into account simultaneously in the document in the past in order to overcome, and a kind of new method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst is provided.The Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst that this method makes has high catalytic activity, optionally has enhanced water resistance energy, the characteristics of high mechanical strength simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst, at first will be by active ingredient, tackiness agent and the pore-creating agent uniform mixing of catalyst proportion, add an amount of water and make the face dough of toughness and suitable extrusion, make the finished catalyst that comprises following component by weight percentage through extrusion, moulding, drying and roasting:
(a) Fe
2O
3: 65～90%, (b) K
2O:3～15%, (c) Ce
2O
3: 4～10%, (d) MoO
3: 0.3～5%, (e) MgO:2～6%, wherein Fe
2O
3By Fe
2O
3And Fe
2O
3H
2O forms, by weight Fe
2O
3: Fe
2O
3H
2O is 0.2～5: 1, and its roasting condition is for being under 800～980 ℃ of conditions at maturing temperature, and roasting time is 1～8 hour.
The preferable range of maturing temperature is 810～950 ℃ in the technique scheme, and more preferably scope is 820～890 ℃, and the preferable range of roasting time is 4～8 hours, and more preferably scope is 6～8 hours.Drying conditions is under 80～120 ℃ of conditions dry 1～10 hour, and preferred version be a drying 1～4 hour under 80～120 ℃ of conditions.
The used raw material of the catalyst component that the inventive method makes is as follows:
Potassium adds with the form of sylvite; Cerium adds with oxide compound, oxyhydroxide or cerium salt; Molybdenum adds with its salt or oxide compound; Magnesium adds with its oxide compound or salt, and iron is made up of red iron oxide and iron oxide yellow.Perforating agent in the catalyzer, its consumption are 1～4% of catalyst weight, can choose from graphite, polystyrene microsphere, carboxymethyl cellulose etc., and binding agent is generally used cement in addition.
The catalyzer that makes as stated above carries out activity rating in the isotherm formula fixed bed, for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through volume pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the nichrome wire heating, makes it to reach preset temperature.Reactor inside diameter is 1 " stainless steel tube, it is interior that to load 100 milliliters, particle diameter be 3.0 millimeters catalyzer.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer hour, 620 ℃ of temperature of reaction, water are than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result and stability data see Table 1,2.
Water resistance is the important criterion of catalyzer quality.The catalyzer water resistance is expressed with intensity before and after catalyzer soaking-resistant ability, the immersion and three kinds of modes of rate of wear variation respectively among the present invention.
The test of the soaking-resistant of catalyst sample is finished in two steps among the present invention, and the first step is got 20 samples, places beaker, and 200 milliliters of adding distil waters soaked 30 minutes.In second step, the heating beaker boiled 30 minutes.After each step is finished, check, write down the particle integrity degree, observe clarity of solution.Particle integrity and solution clarification are for qualified.
The crush strength of catalyzer is measured by the technical requirements of State Standard of the People's Republic of China GB/T 3635 regulations.Finished catalyst after the stochastic sampling roasting, get wherein 20 with quartering, use QCY-602 granule strength determinator to measure, the crush strength of single catalyzer calculates as follows: Pi=Fi/L, in the formula: the crush strength of single catalyzer of Pi-, Newton/millimeter; Single catalyzer anti-crushing power of Fi-, kilogram; Single catalyst length of L-, millimeter.The crush strength of catalyzer calculates with the arithmetical av of 20 measurement results.
The wear attrition of catalyst rate is determined on the CM-3B type particle wear test instrument carries out, and wearing time is 24 hours.Rate of wear calculates as follows; (W
1-W
2)/W
1, W
1Complete particle is heavy before the-wear attrition of catalyst, gram; W
2Complete particle is heavy behind the-wear attrition of catalyst, gram.
Crush strength and rate of wear measurement result also see Table 1 before and after catalyzer soaking-resistant ability, the water logging bubble.
The dehydrogenation catalyst that method of the present invention makes under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate vinylbenzene, divinylbenzene and alpha-methyl styrene.
The inventor is by discovering, catalyzer especially catalyst strength and its water resistance of low potassium content is closely related, and the many wustites amount that contains in water resistance and the catalyzer closely links to each other.Many wustites amount is big more, and then the water resistance of catalyzer, physical strength are good more.The present invention helps the generation of many wustites amount by the technical scheme that adopts under hot conditions roasting and prolong roasting time, thereby make catalyzer under same catalytic activity component condition, the one side activity of such catalysts, when the selectivity of purpose product alkyl alkenyl arene increases, catalyzer has kept high water resistance and physical strength, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
232.2 gram red iron oxides, 172.4 gram iron oxide yellow, 77.8 gram salt of wormwood, 82.1 gram cerous nitrates, 7.5 gram molybdenum oxides, 20.0 gram magnesium oxide and 25 gram cement, 10.0 gram carboxymethyl celluloses were stirred in kneading machine 1 hour, add deionized water, mixed and stirred again 0.5 hour, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8～10 millimeters of length, put into baking oven, dry certain hour under certain temperature, place muffle furnace then, the roasting certain hour makes catalyzer under certain temperature.The preparation method of embodiment 2,3, charging capacity are that drying temperature, time and maturing temperature, roasting time are different with embodiment 1.
The Preparation of Catalyst charging capacity is:
The raw material charging capacity, gram
Fe
2O
3 232.2
Fe
2O
3·H
2O 172.4
K
2CO
3 77.8
Ce(NO
3)
3·6H
2O 82.1
MoO
3 7.5
MgO 20.0
Cement 25.0
Carboxymethyl cellulose 10.0
The catalyzer roasting condition is:
The sample drying temperature, ℃ time of drying hour maturing temperature, ℃ roasting time, hour
Embodiment 1 80 10 810 8
Embodiment 2 90 8 850 6
Embodiment 3 120 4 890 4
Gained catalyzer composed as follows:
Form oxide content
Fe
2O
3 77.4
K
2O 10.6
CeO
2 6.5
MoO
3 1.5
MgO 4.0
[comparative example 1～3]
The method for preparing catalyst of comparative example has just changed drying conditions and roasting condition with embodiment 1, and actual conditions is:
The sample drying temperature, ℃ time of drying, hour maturing temperature, ℃ roasting time, hour
Comparative example 1 120 4 620 6
Comparative example 2 100 4 650 4
Comparative example 3 120 2 600 8
[embodiment 4]
The catalyzer that the foregoing description 1～3 and comparative example 1～3 obtain is measured crush strength with the GB/T3635 method with QCY-602 granule strength determinator, measure rate of wear with CM-3B type particle abrasion test instrument, it the results are shown in table 1.At internal diameter is 1, and " examination catalyzer in the stainless steel tube isotherm formula fixed-bed reactor; the examination condition is that reaction pressure is a normal pressure, liquid air speed are 1.0 liters of ethylbenzene/rise catalyzer hour, and temperature of reaction is 620 ℃; water is than (water/ethylbenzene) 2.0 (weight ratio), and evaluation result sees Table 1.The catalyzer that embodiment 3 is made is under above-mentioned examination condition, and the activity data under the examination differential responses time sees Table 2.
The contrast of table 1 catalyst performance
The test of water logging bubble
*Intensity, Newton/millimeter rate of wear % transformation efficiency selectivity
Catalyzer
Soak before the cold water hot-water soak and soak back % % before soak the back
Embodiment 1 P F 20.4-2.17-76.4 95.2
Embodiment 2 P P 23.2 20.1 0.94 1.32 77.8 95.1
Embodiment 3 P P 25.0 24.1 0.31 0.64 78.3 95.4
Comparative example 1 P F 20.8-1.16-75.7 94.3
Comparative example 2 P P 20.7 18.3 1.64 1.87 72.3 94.1
Comparative example 3 P P 19.3 17.4 1.76 1.99 70.6 93.2
*P-passes through; The F-failure
Table 2 embodiment 3 catalyzer differential responses time activity datas
Reaction times
50 hours 100 hours 200 hours 300 hours 400 hours 500 hours
Con Sel Con Sel Con Sel Con Sel Con Sel Con Sel
(％) (％) (％) (％) (％) (％) (％) (％) (％) (％) (％) (％)
78.3 95.4 78.1 95.3 77.7 95.2 77.8 95.4 77.9 95.6 77.7 95.4
Annotate: Con is a transformation efficiency, and Sel is a selectivity.
From the embodiment data, catalyzer of the present invention is on the basis of Fe-K-Ce-Mo-Mg essentially consist, promptly improve the catalyzer maturing temperature by improving heat-treat condition, prolong roasting time, and need not solve the problem that catalyzer dehydrogenation and water resistance improve synchronously preferably by adding too much binding agent.It can be soaking-resistant ability, crush strength height and the low characteristics of rate of wear that made dehydrogenation catalyst not only has excellent water tolerance, but also have high activity and selectivity, thereby improving the load that feeds intake, realize that quiet run and long-term operation provide reliable assurance for production of styrene producer, is that a kind of effective enhanced water resistance can dehydrogenation catalyst.
Claims (7)
1, a kind of method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst, at first will be by active ingredient, tackiness agent and the pore-creating agent uniform mixing of catalyst proportion, add an amount of water and make the face dough of toughness and suitable extrusion, make the finished catalyst that comprises following component by weight percentage through extrusion, moulding, drying and roasting:
(a) Fe
2O
3: 65～90%, (b) K
2O:3～15%, (c) Ce
2O
3: 4～10%, (d) MoO
3: 0.3～5%, (e) MgO:2～6%, wherein Fe
2O
3By Fe
2O
3And Fe
2O
3H
2O forms, by weight Fe
2O
3: Fe
2O
3H
2O is 0.2～5: 1, it is characterized in that roasting condition is is under 800～980 ℃ of conditions at maturing temperature, and roasting time is 1～8 hour.
2,, it is characterized in that maturing temperature is 810～950 ℃ according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 1.
3,, it is characterized in that maturing temperature is 820～890 ℃ according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 2.
4,, it is characterized in that roasting time is 4～8 hours according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 1.
5,, it is characterized in that roasting time is 6～8 hours according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 4.
6,, it is characterized in that drying conditions is under 80～120 ℃ of conditions dry 1～10 hour according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 1.
7,, it is characterized in that drying conditions is under 80～120 ℃ of conditions dry 1～4 hour according to the described method for preparing Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021110077A CN1184176C (en) | 2002-03-13 | 2002-03-13 | Method for preparing alkyl aromatics dehydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021110077A CN1184176C (en) | 2002-03-13 | 2002-03-13 | Method for preparing alkyl aromatics dehydrogenation catalyst |
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|---|---|
| CN1443735A CN1443735A (en) | 2003-09-24 |
| CN1184176C true CN1184176C (en) | 2005-01-12 |
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ID=27811171
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021110077A Expired - Lifetime CN1184176C (en) | 2002-03-13 | 2002-03-13 | Method for preparing alkyl aromatics dehydrogenation catalyst |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368083C (en) * | 2004-10-29 | 2008-02-13 | 中国石油化工股份有限公司 | Catalyst for preparing cinnamene by dehydrogenation of ethylbenzene |
| CN100408175C (en) * | 2005-08-15 | 2008-08-06 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing alkyl alkenyl arene |
| CN100408174C (en) * | 2005-08-15 | 2008-08-06 | 中国石油化工股份有限公司 | Catalyst for ethyl benzene dehydrogenation |
| CN101091915B (en) * | 2006-06-21 | 2010-05-12 | 中国石油化工股份有限公司 | Catalyst of ethyl benzene dehydrogenation |
| CN101279263B (en) * | 2007-04-04 | 2010-07-21 | 中国石油化工股份有限公司 | Catalyst for preparation of styrene by ethylbenzene dehydrogenation |
| CN101658790B (en) * | 2008-08-28 | 2013-06-12 | 北京三聚环保新材料股份有限公司 | Method for preparing dehydrogenation catalyst |
| CN101992095B (en) * | 2009-08-31 | 2012-10-10 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof |
| CN102040464B (en) * | 2009-10-13 | 2013-01-23 | 中国石油化工股份有限公司 | Method for preparing styrene from crude ethylbenzene by dehydrogenation |
-
2002
- 2002-03-13 CN CNB021110077A patent/CN1184176C/en not_active Expired - Lifetime
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