CN1302847C - Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene - Google Patents
Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene Download PDFInfo
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- CN1302847C CN1302847C CNB031507174A CN03150717A CN1302847C CN 1302847 C CN1302847 C CN 1302847C CN B031507174 A CNB031507174 A CN B031507174A CN 03150717 A CN03150717 A CN 03150717A CN 1302847 C CN1302847 C CN 1302847C
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- oxide
- ethylbenzene
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to dehydrogenation catalysts for preparing styrene from ethylbenzene, which mainly the problems of the relatively high cost of catalysts, the relatively low activity of catalysts, the low yields of styrene and the low selectivity of B/T (mol) in a former technology. The dehydrogenation catalysts better solve the problems by a technical scheme that noble metal element rhodium with ppm level and at least one kind of metal or oxide which is chosen from Pd, Pt, Ir, Re, Os or Ru are simultaneously introduced into an iron-potassium-cerium-molybdenum catalytic system, and the dehydrogenation catalysts can be used in industrial production for preparing styrene from ethylbenzene.
Description
Technical field
The present invention relates to be used for the dehydrogenation of preparing styrene from ethylbenzene.
Background technology
As everyone knows, normally make alkenyl arene by alkyl aromatics catalytic dehydrogenation on the industrial production, selecting a kind of dehydrogenation efficiently is one of key technology of this method.The catalyst of patent report divides two classes.One class is to contain Cr series, as laid-open U.S. Patents US5376613, US4717781, European patent EP 0794004A1 and German patent DE 2815874A1.Though such activity of such catalysts and stability are better, because catalyst itself contains environmentally harmful chromated oxide, are very limited on the commercial Application, are eliminated gradually.Another kind of is Fe-K-Ce-Mo series, and this type of catalyst has substituted Cr with Ce, Mo, and activity of such catalysts and stability have by a relatively large margin raising than the former, but the catalyst selectivity aspect still remains to be improved.In addition, the benzene/methylbenzene in the dehydrogenation product, can be delivered to ethylbenzene workshop section to recycle after accessory substances such as benzene separate in the later separation step than an important indicator that also is the decision catalyst efficiency; And toluene can not enter circulation fluid after separating again, needs to enter Sales Channel as product, and its economic worth is lower.Therefore, when other index was identical, the higher catalyst of B/T ratio was the product that production of styrene producer welcomes.For this reason, people have carried out some in this regard and have explored, and studied as laid-open U.S. Patents US6177602 and add the method that Pt, Pd improve catalyst selectivity and reduce the toluene growing amount in the Fe-K-Ce-Mo-Mg system.Because Pt in the document, Pd consumption are higher, about 300ppm, have increased catalyst production cost greatly.A kind of dehydrogenation that comprises iron, alkali metal and noble metal is at least disclosed among document Chinese patent CN1298323A and the US6191065.This catalyst adds precious metal element, contains the compound of noble metal and the noble metal source of combination thereof in iron compound and alkali metal oxide system.Noble metal is selected from platinum, palladium, iridium, rhodium and ruthenium, and its objective is provides a kind of high activity and catalyst optionally, makes the B/T selectivity better simultaneously.See at first the example that openly rhodium and other precious metal element are used in combination from the disclosed content of the document, only disclose the embodiment of independent use rhodium or palladium.The consumption of palladium is minimum in an embodiment is 100ppm, and catalyst this moment conversion of ethylbenzene under 600 ℃ of temperature only is 47.7%, and selectivity of styrene is 97.3%, and promptly the styrene yield only is 46.4%, and this moment, B/T was about 0.30; The minimum dosage of rhodium is 10ppm in an embodiment, and this moment, the conversion of ethylbenzene under 600 ℃ of temperature was 40.48%, and cinnamic selectivity is 98.28%, and the styrene yield only is 39.78%, and the data of B/T are not open.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst cost is higher in the conventional art, and activity of such catalysts is lower, and the styrene yield is low, and the low problem of B/T (mole) selectivity provides a kind of new dehydrogenation that is used for preparing styrene from ethylbenzene.It is low that this catalyst has a production cost, active high, styrene yield height, the characteristics that the B/T selectivity is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of dehydrogenation that is used for preparing styrene from ethylbenzene comprises following component by weight percentage:
A) oxide of 59.3~75.7% iron is with Fe
2O
3Meter;
B) oxide of 12.4~23.6% potassium is with K
2The O meter;
C) oxide of 3~10% ceriums is with Ce
2O
3Meter;
D) oxide of 0.5~5% molybdenum is with MoO
3Meter;
E) metal of 1~20ppm rhodium or oxide;
F) metal of 1~100ppm Pd or oxide;
G) 0.5~10% at least a binding agent that is selected from kaolin, diatomite or the cement.
In the technique scheme, preferred version is also to contain alkaline earth oxide in the catalyst, and its consumption is 0.05~8%, and the alkaline earth oxide preferred version is a magnesia.The oxide preferred version of iron is by Fe
2O
3And Fe
2O
3H
2O forms, and its weight ratio is Fe
2O
3: Fe
2O
3H
2O=0.2~5: 1.The metal of rhodium or oxide consumption preferable range are 1.5~9.5ppm by weight percentage, and more preferably scope is 4~8ppm.The metal of Pd or the consumption of oxide preferable range by weight percentage are 1~20ppm, and more preferably scope is 10~20ppm.The binding agent preferred version is a cement.
In the dehydrogenation of the present invention, Fe is with Fe
2O
3Form add Fe
2O
3Formed by iron oxide red, iron oxide yellow and nanometer ferro oxide; Used potassium adds with potassium salt form; Used cerium adds with the form of oxide, nitrate, carbonate; Mo adds with its salt or oxide; Alkaline earth oxide adds with oxide form.The metal of Rh or Pd or oxide are with the form adding of nitrate or acylate.
Perforating agent 1~2% can be selected from graphite, polystyrene microsphere, carboxymethyl cellulose; All the other are binding agent, available cement.
Preparation of catalysts method of the present invention:
After will evenly mixing by Fe, the K of proportioning weighing, Ce, Mo, noble metal nitrate, adhesive, perforating agent and the metal that needs or oxide composition, add proper amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8~10 millimeters particle, in 60~120 ℃ of dryings 4 hours, 400~1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
The catalyst 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 measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyst.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 catalyst hour, reaction temperature are respectively 620 ℃, 600 ℃, and water is than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result sees Table 1.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate styrene, divinylbenzene and AMS.
Among the present invention, owing to introduced metal or the oxide of alkaline-earth metal and precious metal element rhodium and Pd in iron-potassium-cerium-molybdenum catalyst system and catalyzing respectively, and their rational amount ranges have been chosen, as rhodium consumption most preferred range only is 4~8ppm, the metal of Pd or the consumption preferable range of oxide are 10~20ppm only simultaneously, greatly reduce catalyst production cost.The inventor not only has higher activity by the catalyst that adopts such technical scheme to be surprised to find that to make in addition, conversion of ethylbenzene can be up to 69.8% at 600 ℃, the styrene yield can reach 67.5%, and B/T (mole) selectivity can reach 0.55, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1~3]
With 302.1 gram iron oxide reds, 60.5 gram iron oxide yellows, 85.8 gram potash, 76.6 gram cerous nitrates, 11.9 gram ammonium molybdates, 17.6 gram magnesia, 3.57 ml concns is 10
-3Rh (the NO of mol
3)
2Solution, 10.86 ml concns are 10
-3Pd (the NO of mol
3)
2Solution and 15 gram cement, 10 gram carboxymethyl celluloses stirred in kneading machine 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8~10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, placed muffle furnace then, made catalyst in 5 hours in 800 ℃ of roastings.The preparation method of embodiment 2,3 is Rh (NO with embodiment 1
3)
2The addition of solution is respectively 7.16 milliliters and 8.04 milliliters, Pd (NO
3)
2The addition of solution is respectively 16.29 milliliters and 21.71 milliliters.
Preparation of Catalyst inventory gram is:
Raw material | Inventory, gram | ||
Embodiment 1 | Embodiment 2 | Embodiment 3 | |
Fe 2O 3 Fe 2O 3·H 2O K 2CO 3 Ce(NO 3) 3·6H 2O (NH 4) 6Mo 7O 24·4H 2O MgO cement carboxymethyl cellulose Rh (NO 3) 2Solution (milliliter) Pd (NO 3) 2Solution (milliliter) | 302.1 60.5 85.8 76.6 11.9 17.6 15.0 10.0 3.57 10.86 | 203.6 152.4 200.3 126.3 25.6 30.0 40.0 20.0 7.16 16.29 | 129.3 237.1 99.5 80.7 10.2 19.8 24.8 9.9 8.04 21.71 |
The percentage by weight of gained catalyst is composed as follows:
Form | Embodiment 1 | Embodiment 2 | Embodiment 3 |
Fe 2O 3 K 2O Ce 2O 3 MoO 3 MgO Rh Pd | 71.2 14.3 6.5 1.8 6.2 0.0004 0.0010 | 59.3 23.6 8.3 3.6 5.2 0.0008 0.0015 | 75.7 12.4 6.1 2.0 3.8 0.0009 0.0020 |
[comparative example 1~3]
The method for preparing catalyst of comparative example is with embodiment 1.Comparative example 1 does not add noble metal, comparative example 2Rh (NO
3)
2The addition of solution is 30 milliliters, 3 of comparative examples be that 380 ml concns are 10
-3Pd (the NO of mol
3)
2Solution.
Concrete inventory is:
Raw material | Inventory, gram | ||
Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Fe 2O 3 Fe 2O 3·H 2O K 2CO 3 Ce(NO 3) 3·6H 2O (NH 4) 6Mo 7O 24·4H 2O MgO cement carboxymethyl cellulose Rh (NO 3) 2Solution (milliliter) Pd (NO 3) 2Solution (milliliter) | 163.4 231.4 99.5 88.4 15.6 30.0 35.0 15.0 - - | 264.4 106.8 152.0 126.7 8.1 25.3 20.0 10.0 30.00 - | 324.7 62.9 89.3 79.9 12.3 18.4 25.0 20.0 - 380 |
The percentage by weight of gained catalyst is composed as follows:
Form | Comparative example 1 | Comparative example 2 | Comparative example 3 |
Fe 2O 3 K 2O Ce 2O 3 MoO 3 MgO Rh Pd | 73.5 13.4 6.6 2.5 4.0 - - | 66.4 18.9 8.8 1.2 4.7 0.0033 - | 76.2 12.1 6.0 2.0 3.7 - 0.035 |
The contrast of table 1 catalyst dehydrogenation
Catalyst | 620℃ | 600℃ | ||||
Conversion ratio % | Selectivity % | B/T (mole) | Conversion ratio % | Selectivity % | B/T (mole) | |
Embodiment 1 embodiment 2 embodiment 3 comparative examples 1 comparative example 2 comparative examples 3 | 72.3 74.5 77.6 70.3 74.7 75.2 | 93.6 94.7 95.4 93.1 94.3 94.9 | 0.17 0.20 0.30 0.15 0.18 0.22 | 64.2 66.6 69.8 62.0 66.8 67.1 | 94.7 95.4 96.8 94.3 95.2 95.5 | 0.37 0.39 0.55 0.34 0.39 0.42 |
From implementation, catalyst of the present invention, on the basis of Fe-K-Ce-Mo basic composition, introduce the oxide of alkaline-earth metal magnesium and noble metal Rh, the Pd of ppm level, made dehydrogenation had both had high activity, selectivity, higher B/T (mole) ratio is arranged again, is a kind of high performance catalyst for phenylethylene dehydrogenation.
Claims (9)
1, a kind of dehydrogenation that is used for preparing styrene from ethylbenzene comprises following component by weight percentage:
A) oxide of 59.3~75.7% iron is with Fe
2O
3Meter;
B) oxide of 12.4~23.6% potassium is with K
2The O meter;
C) oxide of 3~10% ceriums is with Ce
2O
3Meter;
D) oxide of 0.5~5% molybdenum is with MoO
3Meter;
E) metal of 1~20ppm rhodium or oxide;
F) metal of 1~100ppm Pd or oxide;
G) 0.5~10% at least a binding agent that is selected from kaolin, diatomite or the cement.
2, according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 1, it is characterized in that also containing in the catalyst alkaline earth oxide, its consumption is 0.05~8%.
3,, it is characterized in that alkaline earth oxide is a magnesia according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 2.
4, according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 1, the oxide that it is characterized in that iron is by Fe
2O
3And Fe
2O
3H
2O forms, and its weight ratio is Fe
2O
3: Fe
2O
3H
2O=0.2~5: 1.
5,, it is characterized in that the metal or the oxide consumption of rhodium are 1.5~9.5ppm by weight percentage according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 1.
6,, it is characterized in that the metal or the oxide consumption of rhodium are 4~8ppm by weight percentage according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 5.
7,, it is characterized in that the metal of Pd or the consumption of oxide are 1~20ppm by weight percentage according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 1.
8,, it is characterized in that the metal of Pd or the consumption of oxide are 10~20ppm by weight percentage according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 7.
9,, it is characterized in that binding agent is a cement according to the described dehydrogenation that is used for preparing styrene from ethylbenzene of claim 1.
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CNB031507174A CN1302847C (en) | 2003-09-03 | 2003-09-03 | Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene |
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CNB031507174A CN1302847C (en) | 2003-09-03 | 2003-09-03 | Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene |
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CN1589961A CN1589961A (en) | 2005-03-09 |
CN1302847C true CN1302847C (en) | 2007-03-07 |
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CNB031507174A Expired - Lifetime CN1302847C (en) | 2003-09-03 | 2003-09-03 | Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101279269B (en) * | 2007-04-04 | 2010-10-27 | 中国石油化工股份有限公司 | Low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane |
CN101602003B (en) * | 2008-06-12 | 2011-07-20 | 中国石油化工股份有限公司 | Oxide catalyst for preparing styrene by ethylbenzene dehydrogenation |
WO2020106447A1 (en) * | 2018-11-19 | 2020-05-28 | Clariant International Ltd | Dehydrogenation catalysts for converting alkyl aromatic compounds such as ethylbenzene |
CN115475628B (en) * | 2021-06-16 | 2024-01-30 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804799A (en) * | 1987-08-28 | 1989-02-14 | The Dow Chemical Company | Dehydrogenation catalyst |
US5190906A (en) * | 1991-03-05 | 1993-03-02 | Nissan Girdler Catalyst Co., Ltd. | Alkyl aromatic hydrocarbon dehydrogenation catalyst and method for producing the catalyst |
US6037305A (en) * | 1997-03-03 | 2000-03-14 | Rhodia Chimie | Use of Ce/Zr mixed oxide phase for the manufacture of styrene by dehydrogenation of ethylbenzene |
US6177602B1 (en) * | 1998-04-01 | 2001-01-23 | United Catalysts, Inc. | Process for dehydrogenation of alkylaromatic hydrocarbons using a dehydrogenation catalyst |
CN1298323A (en) * | 1998-04-01 | 2001-06-06 | 苏德一化学公司 | Dehydrogenation catalysts comprising at least iron, alkali metal and a noble metal |
-
2003
- 2003-09-03 CN CNB031507174A patent/CN1302847C/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804799A (en) * | 1987-08-28 | 1989-02-14 | The Dow Chemical Company | Dehydrogenation catalyst |
US5190906A (en) * | 1991-03-05 | 1993-03-02 | Nissan Girdler Catalyst Co., Ltd. | Alkyl aromatic hydrocarbon dehydrogenation catalyst and method for producing the catalyst |
US6037305A (en) * | 1997-03-03 | 2000-03-14 | Rhodia Chimie | Use of Ce/Zr mixed oxide phase for the manufacture of styrene by dehydrogenation of ethylbenzene |
US6177602B1 (en) * | 1998-04-01 | 2001-01-23 | United Catalysts, Inc. | Process for dehydrogenation of alkylaromatic hydrocarbons using a dehydrogenation catalyst |
CN1298323A (en) * | 1998-04-01 | 2001-06-06 | 苏德一化学公司 | Dehydrogenation catalysts comprising at least iron, alkali metal and a noble metal |
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