CN1136047C - Alkyl aromatics catalytic dehydrogenation catalyst - Google Patents
Alkyl aromatics catalytic dehydrogenation catalyst Download PDFInfo
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- CN1136047C CN1136047C CNB991135725A CN99113572A CN1136047C CN 1136047 C CN1136047 C CN 1136047C CN B991135725 A CNB991135725 A CN B991135725A CN 99113572 A CN99113572 A CN 99113572A CN 1136047 C CN1136047 C CN 1136047C
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- catalyst
- oxide
- catalytic dehydrogenation
- dehydrogenation catalyst
- 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 an alkyl aromatic catalytic dehydrogenation catalyst. The present invention mainly aims to solve the problems that the characteristics of high single-pass yield of styrene, high crushing strength, low abrasion rate and good water resistance can not simultaneous exist in the existing catalyst. The present invention is mainly prepared in such a manner that calcium oxide, sodium oxide and a plurality of metallic oxides in a Fe-K-Ce-Mo-Zr system with a low kalium content (5 to 15 wt%). The prepared catalyst has high activity, high selectivity, good crushing strength and good water immersion resistance, and is suitable for the long-term stable operation and application in industrial equipment.
Description
The present invention relates to a kind of alkyl aromatics catalytic dehydrogenation catalyst.This catalyst can be used for ethyl benzene dehydrogenation preparation of styrene, diethylbenzene dehydrogenation system divinylbenzene, also can be used for methyl-ethyl benzene dehydrogenation system methyl styrene.
As everyone knows, industrial alkenyl arene is to be made by alkyl aromatics catalytic dehydrogenation.One of key of this method is to select a kind of dehydrogenation efficiently.The catalyst of patent report divides two classes: a class is a Fe-K-Cr series, as laid-open U.S. Patents US4134858, US4152300, US4144197, BP GB1405796, WO8300687 or Chinese patent CN87100517A etc.Though such activity of such catalysts and stability are better, because catalyst itself contains the chromated oxide that environment is easily polluted, commercial Application is very limited, and is eliminated gradually.Another kind of is Fe-K-Ce-Mo series, as laid-open U.S. Patents US4804799, European patent EP 0502510A
1This type of catalyst has substituted Cr with Ce, Mo, and activity of such catalysts and stability improves, but the potassium content of such catalyst is too high, makes the reaction temperature of catalyst higher, has limited the further raising of product styrene yield.In the U.S. Pat 4804799, adopt the Fe-K-Ce-Mo-Cu system, wherein potash content is 30～50% (weight), and its product styrene yield is up to 48.5%.European patent EP 0502510A
1In reported that titanium is to Fe-K-Ce-Mo-Mg system catalytic activity and facilitation optionally.Even in catalyst system, add a spot of titanium, just can significantly improve activity of such catalysts and selectivity of product, potassium oxide content is when 20～25% (weight) left and right sides in the catalyst system and catalyzing, preferably catalyst is investigated under 620 ℃ of conditions, conversion of ethylbenzene is 76.8%, selectivity of styrene is 94%, and its styrene yield is 72.19% on the low side relatively; During in 10% (weight) left and right sides, better catalyst is investigated under 620 ℃ of conditions at potassium oxide content, and conversion of ethylbenzene is 75.4%, and selectivity of styrene is 91.2%, and its styrene yield is 68.76% lower.Because the reduction of potassium content can reduce the crush strength of catalyst, reduce the water-resistant capacity of catalyst in addition, promptly can increase the rate of wear of catalyst.Like this in Preparation of catalysts, transportation or filling process, especially in certain embodiments, when unexpected generation parking accident or aqueous water pour in down a chimney, catalyst will contact with aqueous water inevitably, make that catalyst expands, deliquescing, even rupture, cause bed pressure drop increase in the use, be unfavorable for reaching the purpose that increases the load that feeds intake, realizes quiet run and prolongation catalyst life.
The objective of the invention is need reaction temperature higher, but the styrene yield to be lower in order to overcome in the past catalyst when potassium content was higher; When potassium content was low, the catalyst crush strength was low, and water-resistant capacity is low, and the shortcoming that wear rate is high provides a kind of new alkyl aromatics catalytic dehydrogenation catalyst.This catalyst has the crush strength height, the water-resistant capacity height, and wear rate is low, can keep simultaneously high activity and advantage optionally again.
The objective of the invention is to realize by following technical scheme: a kind of alkyl aromatics catalytic dehydrogenation catalyst, by weight percentage, active constituent is made up of following component:
A) 50～90% ferriferous oxides are with Fe
2O
3Meter;
B) 5～15% potassium oxides are with K
2The O meter;
C) 3～10% cerium oxides are with Ce
2O
3Meter;
D) 0.5～5% molybdenum oxide is with MoO
3Meter;
E) 0.01～1.5% Zirconium oxide is with ZrO
2Meter;
F) 0.001～10% at least a be selected from Mg, Cu, Zn, Sc, Ti, W, Mn, Co, Ni, V, Al, Ge,
The oxide of Se, Bi, P, B, Sn, Pb or Si;
G) 0.001～8% calcium oxide is in CaO;
H) 0.1～2% na oxide is with Na
2The O meter;
All the other are binding agent, and the percentage that binder amount accounts for catalyst weight is＞0～20%.
In the technique scheme by weight percentage, na oxide Na
2The preferred span of O is 0.1～0.4%, and the raw material sources of na oxide are sodium carbonate or NaOH.The raw material sources of calcium oxide are calcium hydroxide, calcium nitrate, calcium oxide or calcium carbonate.By weight percentage, being selected from amount at least a in Mg, Cu, Zn, Sc, Ti, W, Mn, Ni, Co or the V oxide during catalyst is formed is 0.001～2%.Ferriferous oxide was by Fe during catalyst was formed
2O
3And Fe
2O
3H
2O provides for raw material, and its weight proportion is Fe
2O
3: Fe
2O
3H
2O=0.2～5: 1, preferred span is 0.4～4.5: 1.Alkylaromatic hydrocarbon is ethylbenzene, diethylbenzene or Alpha-Methyl ethylbenzene in the technical scheme.Except that above-mentioned active constituent, also contain perforating agent 1～2% (weight) in the Preparation of Catalyst, be selected from graphite, polystyrene microsphere or carboxymethyl cellulose, all the other are binding agent, and the percentage that accounts for catalyst weight is＞0～20%, can use cement.
Ferriferous oxide Fe in the technique scheme
2O
3Form with iron oxide red and iron oxide yellow form; The potassium oxide adds with potassium oxide, potassium nitrate or potash form; Cerium oxide adds with cerium oxide, cerium oxalate, cerium hydroxide, cerous carbonate or cerous nitrate form; Molybdenum oxide adds with molybdenum oxide or molybdate form, and Zirconium oxide adds with zirconia or nitrate form; The oxide that is selected from Mg, Cu, Zn, Sc, Ti, W, Mn, Co, Ni, V, Al, Ge, Se, Bi, P, B, Sn, Pb or Si generally also adds with oxide, nitrate, carbonate or respective salt.
Method for preparing catalyst of the present invention is as follows:
After metal oxide, binding agent and the perforating agent that will add by Fe, K, Ce, Mo, Zr, Ca, Na and the selectivity of proportioning weighing evenly mixes, add an amount of deionized water, make the face dough of toughness, suitable extrusion.Becoming diameter through extrusion, pelletizing is 3 millimeters, and long 8～10 millimeters particle in 80～120 ℃ of dryings 4 hours, 500～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, methyl-ethyl benzene dehydrogenation generate styrene, divinylbenzene and methyl styrene.
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.Reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 25.4 millimeters a stainless steel tube, interiorly loads 100 milliliters of catalyst.The reactant that reactor flows out is analyzed its composition with gas chromatograph behind water condensation.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The crush strength of catalyst is measured by the specification requirement of State Standard of the People's Republic of China GB/T3635 regulation among the present invention.Finished catalyst after the random sampling roasting is got wherein 20 with quartering, uses QCY-602 granule strength analyzer to measure, and the crush strength of single catalyst calculates as follows:
Pi＝Fi/L
In the formula: the crush strength of single catalyst of Pi-, kilogram/millimeter;
The anti-crushing power of single catalyst of Fi-, kilogram;
Single catalyst length of L-, millimeter.
The crush strength of catalyst calculates with the arithmetic mean of instantaneous value of 20 measurement results.
The 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
In the formula: W
1Complete particle is heavy before the-attrition of catalyst, gram;
W
2Complete particle is heavy behind the-attrition of catalyst, gram.
Catalyst soaking-resistant ability was soaked in cold water 24 hours with catalyst, and the crush strength and the rate of wear that record after particle integrity degree and the oven dry are represented.
Owing to adopting i.e. 5～15% (weight) of low potassium, given catalyst and under cryogenic conditions, still can keep better activity and optionally performance among the present invention.Because in catalyst, potassium forms the strong basicity center of catalyst, after adding has weakly acidic zirconium, make catalyst inside form the soda acid centre bit, help catalyst and keep catalytic activity preferably.Add multiple metal oxide and perforating agent and binding agent in iron-potassium-cerium-molybdenum system, made dehydrogenation has had activity and optionally function preferably.Add calcium oxide and na oxide in the catalyst, make the anti-mechanical strength of catalyst and anti-wear performance and water resistance obtained-step improves.Among the present invention, by in iron-potassium-cerium-molybdenum-zirconium system, adding other metal oxide and structure reinforcing agent calcium oxide and na oxide, make the catalyst potassium content when 11% (weight) left and right sides, in 620 ℃ of reaction temperatures, reaction pressure is normal pressure, the liquid air speed is 1.0 liters of ethylbenzene/rise catalyst hour, water is to react under 2.0 (weight ratio) condition than (water/ethylbenzene), its styrene yield reaches 74.3%, catalyst strength reaches 2.5 kilograms/millimeter, rate of wear only 0.4%, have very strong soaking-resistant ability simultaneously, obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
233 gram iron oxide reds, 130.9 gram iron oxide yellows, 75.3 gram potash, 28.8 gram cerous nitrates, 6.3 gram molybdenum oxides, 8.2 gram magnesia, 2.5 gram zirconias and 25.0 gram cement, 18.0 gram graphite, 67.6 gram calcium nitrate and 10.0 gram sodium carbonate were stirred in kneading machine 1 hour, add deionized water, mixed and stirred again 2 hours, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8～10 millimeters of length, put into baking oven, in 80 ℃ of bakings 2 hours, 120 ℃ were dried by the fire 2 hours, place roaster then, made catalyst in 4 hours in 550 ℃ of roastings.The evaluating catalyst condition is as follows: with 100 milliliters, particle diameter is the isothermal reactor that 3 millimeters catalyst is put into 25.4 millimeters of internal diameters, and reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 2.0 (weight ratio).Crush strength uses QCY-602 granule strength analyzer to measure, and rate of wear is determined on the CM-3B type particle wear test instrument and carries out, and wearing time is 24 hours.The results are shown in Table 1, table 2 and table 5.[embodiment 2～4]
Each step according to embodiment 1 prepares catalyst, just changes the content of catalyst component, uses the same method evaluation of embodiment 1 then, and it the results are shown in Table 1, table 2 and table 5.
The concrete inventory of table 1
| Raw material | Inventory, gram | |||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Fe 2O 3 | 223.0 | 223.0 | 223.0 | 223.0 |
| Fe 2O 3·H 2O | 130.9 | 130.9 | 130.9 | 130.9 |
| K 2CO 3 | 75.3 | 75.3 | 75.3 | 75.3 |
| Ce 2(CO 3) 3 | 40.5 | 40.5 | 40.5 | 40.5 |
| MoO 3 | 6.3 | 6.3 | 6.3 | 6.3 |
| MgO | 8.2 | 8.2 | 8.2 | 8.2 |
| ZrO 2 | 2.5 | 2.5 | 2.5 | 2.5 |
| Cement | 25.0 | 25.0 | 25.0 | 25.0 |
| Graphite | 18.0 | 18.0 | 18.0 | 18.0 |
| Ca(NO 3) 2·4H 2O | 67.6 | 67.6 | 67.6 | 67.6 |
| Na 2CO 3 | 10.0 | 5.0 | 2.5 | 1.0 |
The composition of table 2 gained catalyst
[comparative example 1～3]
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Fe 2O 3 | 73.7 | 74.4 | 74.5 | 74.6 |
| K 2O | 11.0 | 11.2 | 11.3 | 11.3 |
| Ce 2O 3 | 6.2 | 6.3 | 6.3 | 6.3 |
| MoO 3 | 1.4 | 1.4 | 1.4 | 1.4 |
| MgO | 1.8 | 1.8 | 1.8 | 1.8 |
| ZrO 2 | 0.5 | 0.5 | 0.5 | 0.5 |
| CaO | 3.9 | 4.0 | 4.0 | 4.0 |
| Na 2O | 1.5 | 0.4 | 0.2 | 0.1 |
Each step according to embodiment 1 prepares catalyst, just changes the content of catalyst component, uses the same method evaluation of embodiment 1 then, and it the results are shown in Table 3, table 4 and table 5.
The concrete inventory of table 3
| Raw material | Inventory, gram | ||
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Fe 2O 3 | 223.0 | 223.0 | 223.0 |
| Fe 2O 3·H 2O | 130.9 | 130.9 | 130.9 |
| K 2CO 3 | 75.3 | 75.3 | 75.3 |
| Ce 2(CO 3) 3 | 40.5 | 40.5 | 40.5 |
| MoO 3 | 6.3 | 6.3 | 6.3 |
| MgO | 8.2 | 8.2 | 8.2 |
| ZrO 2 | 2.5 | 2.5 | 2.5 |
| Cement | 25.0 | 25.0 | 25.0 |
| Graphite | 18.0 | 18.0 | 18.0 |
| Ca(NO 3) 2·4H 2O | - | 67.6 | - |
| Na 2CO 3 | - | - | 2.5 |
The composition of table 4 gained catalyst
Catalyst activity evaluation result and crush strength, rate of wear see Table 5.
| Form | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Fe 2O 3 | 77.8 | 74.7 | 77.3 |
| K 2O | 11.7 | 11.2 | 11.6 |
| Ce 2O 3 | 6.6 | 6.3 | 6.5 |
| MoO 3 | 1.4 | 1.4 | 1.4 |
| MgO | 1.9 | 1.8 | 1.9 |
| ZrO 2 | 0.6 | 0.5 | 0.5 |
| CaO | - | 4.1 | - |
| Na 2O | - | - | 0.8 |
The contrast of table 5 catalyst performance
[embodiment 5]
| Catalyst | Conversion of ethylbenzene % | Selectivity of styrene % | The styrene list is received % | Intensity kilogram/millimeter | Rate of wear % |
| Embodiment 1 | 75.6 | 94.3 | 71.3 | 2.6 | 0.3 |
| Embodiment 2 | 76.1 | 94.7 | 72.1 | 2.5 | 0.4 |
| Embodiment 3 | 78.2 | 95.0 | 74.3 | 2.5 | 0.4 |
| Embodiment 4 | 77.6 | 94.8 | 73.6 | 2.1 | 1.1 |
| Comparative example 1 | 74.2 | 94.0 | 69.8 | 1.1 | 4.3 |
| Comparative example 2 | 76.1 | 94.6 | 72.3 | 2.0 | 1.3 |
| Comparative example 3 | 77.0 | 94.2 | 72.6 | 2.1 | 1.1 |
The catalyst that embodiment 3 is made carries out the water resistance contrast, and it the results are shown in Table 6.
The contrast of table 6 embodiment 3 catalyst water resistances
| Particle integrity degree % | Intensity kilogram/millimeter | Rate of wear % | The styrene list is received % | ||||
| Before soaked | After soaked | Before soaked | After soaked | Before soaked | After soaked | Before soaked | After soaked |
| 100 | 100 | 2.5 | 2.4 | 0.4 | 0.4 | 74.3 | 74.2 |
From the embodiment data, catalyst of the present invention in the Fe-K-Ce-Mo-Zr system, adds calcium oxide and na oxide and multiple metal oxide auxiliary agent, adds perforating agent, binding agent.Made dehydrogenation had both had good crush strength, lower rate of wear and very high soaking-resistant ability, and high activity, selectivity are arranged again, was a kind of efficient dehydrogenation.
Claims (7)
1, a kind of alkyl aromatics catalytic dehydrogenation catalyst, active constituent is made up of following component by weight percentage:
A) 50～90% ferriferous oxides are with Fe
2O
3Meter;
B) 5～15% potassium oxides are with K
2The O meter;
C) 3～10% cerium oxides are with Ce
2O
3Meter;
D) 0.5～5% molybdenum oxide is with MoO
3Meter;
E) 0.01～1.5% Zirconium oxide is with ZrO
2Meter;
F) 0.001～10% at least a be selected from Mg, Cu, Zn, Sc, Ti, W, Mn, Co, Ni, V, Al, Ge,
The oxide of Se, Bi, P, B, Sn, Pb or Si;
G) 0.001～8% calcium oxide is in CaO;
H) 0.1～2% na oxide is with Na
2The O meter;
All the other are binding agent, and the percentage that binder amount accounts for catalyst weight is＞0～20%.
2,, it is characterized in that by weight percentage, na oxide is with Na according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 1
2O counts 0.1～0.4%.
3,, it is characterized in that calcium oxide derives from calcium hydroxide, calcium nitrate, calcium oxide or calcium carbonate according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 1.
4,, it is characterized in that na oxide derives from sodium carbonate or NaOH according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 1.
5, according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 1, it is characterized in that being selected from by weight percentage amount at least a in Mg, Cu, Zn, Sc, Ti, W, Mn, Ni, Co or the V oxide is 0.001～2%.
6,, it is characterized in that ferriferous oxide is by Fe according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 1
2O
3And Fe
2O
3H
2O provides for raw material, and its weight proportion is Fe
2O
3: Fe
2O
3H
2O=0.2～5: 1.
7, according to the described alkyl aromatics catalytic dehydrogenation catalyst of claim 6, it is characterized in that Fe
2O
3: Fe
2O
3H
2O=0.4～4.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991135725A CN1136047C (en) | 1999-03-30 | 1999-03-30 | Alkyl aromatics catalytic dehydrogenation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991135725A CN1136047C (en) | 1999-03-30 | 1999-03-30 | Alkyl aromatics catalytic dehydrogenation catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1268398A CN1268398A (en) | 2000-10-04 |
| CN1136047C true CN1136047C (en) | 2004-01-28 |
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ID=5276747
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991135725A Expired - Lifetime CN1136047C (en) | 1999-03-30 | 1999-03-30 | Alkyl aromatics catalytic dehydrogenation catalyst |
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| CN (1) | CN1136047C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391605C (en) * | 2005-01-26 | 2008-06-04 | 中国石油化工股份有限公司 | Dehydrogenating catalyst for preparing alkyl alkenyl arene |
| CN101279267B (en) * | 2007-04-04 | 2011-07-13 | 中国石油化工股份有限公司 | Energy-saving catalyst for phenylethylene dehydrogenation |
| CN104959146A (en) * | 2015-05-27 | 2015-10-07 | 廖仕杰 | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio |
| 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 |
| JP6648157B2 (en) * | 2015-12-11 | 2020-02-14 | クラリアント触媒株式会社 | Alkyl aromatic compound dehydrogenation catalyst, method for producing the same, and dehydrogenation method using the same |
| CN106890647B (en) * | 2015-12-17 | 2020-02-14 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof |
| CN113877596B (en) * | 2020-07-02 | 2023-09-29 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
-
1999
- 1999-03-30 CN CNB991135725A patent/CN1136047C/en not_active Expired - Lifetime
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