CN1302847C - Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene - Google Patents

Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
oxide
ethylbenzene
catalyst
dehydrogenation
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CNB031507174A
Other languages
Chinese (zh)
Other versions
CN1589961A (en
Inventor
缪长喜
宋磊
徐永繁
杨诚
毛连生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CNB031507174A priority Critical patent/CN1302847C/en
Publication of CN1589961A publication Critical patent/CN1589961A/en
Application granted granted Critical
Publication of CN1302847C publication Critical patent/CN1302847C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

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

The dehydrogenation that is used for preparing styrene from ethylbenzene
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:
Figure C0315071700051
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.
CNB031507174A 2003-09-03 2003-09-03 Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene Expired - Lifetime CN1302847C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB031507174A CN1302847C (en) 2003-09-03 2003-09-03 Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB031507174A CN1302847C (en) 2003-09-03 2003-09-03 Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene

Publications (2)

Publication Number Publication Date
CN1589961A CN1589961A (en) 2005-03-09
CN1302847C true CN1302847C (en) 2007-03-07

Family

ID=34597651

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB031507174A Expired - Lifetime CN1302847C (en) 2003-09-03 2003-09-03 Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene

Country Status (1)

Country Link
CN (1) CN1302847C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN1589961A (en) 2005-03-09

Similar Documents

Publication Publication Date Title
CN1883796A (en) Catalysts for ethyl benzene dehydrogenation preparation of styrene
CN1810370A (en) Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene
CN101993336B (en) Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition
CN1302847C (en) Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene
CN1810368A (en) Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene
CN100453174C (en) Low-water ratio alkyl aromatics dehydrogenation catalyst
CN100391603C (en) Catalyst for dehydrogenating alkyl arene
CN107790148B (en) Catalyst for preparing divinylbenzene by dehydrogenating diethylbenzene and preparation method and application thereof
CN1204098C (en) Oxide catalyst for ethylbenzene dehydrogenation to prepare styrene
CN106582684B (en) catalyst for dehydrogenation of alkyl aromatic hydrocarbon
CN1184176C (en) Method for preparing alkyl aromatics dehydrogenation catalyst
CN102040464B (en) Method for preparing styrene from crude ethylbenzene by dehydrogenation
CN1263541C (en) Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene
CN100391605C (en) Dehydrogenating catalyst for preparing alkyl alkenyl arene
CN1810365A (en) Alkyl arene dehydrogenating catalyst
CN112657503B (en) Iron-based catalyst and preparation method and application thereof
CN100460069C (en) Production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation
CA3116597C (en) Catalyst for dehydrogenation of alkyl aromatic hydrocarbon and preparation method therefor
CN1226091C (en) Deoxidizing catalyst for producing alkyl thiazolinyl aromatic hydrocarbon
CN1076633C (en) Low-temperature alkyl arene dehydrogenating catalyst
CN1268398A (en) Alkyl aromatics catalytic dehydrogenation catalyst
CN101279268B (en) Energy-saving alkyl aromatics dehydrogenation catalyst
CN1290615C (en) Alkyl aromatics dehydrogen catalyst
CN1927458A (en) Catalyst for ethylbenzene dehydrogenation-hydroxide reaction
CN100443171C (en) Oxide catalysts for ethyl benzene dehydrogenation preparation of styrene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20070307