CN106423187A - Styrene catalyst - Google Patents
Styrene catalyst Download PDFInfo
- Publication number
- CN106423187A CN106423187A CN201510493346.4A CN201510493346A CN106423187A CN 106423187 A CN106423187 A CN 106423187A CN 201510493346 A CN201510493346 A CN 201510493346A CN 106423187 A CN106423187 A CN 106423187A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- grams
- parts
- preparation
- iron oxide
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a styrene catalyst and a preparation method thereof. A purpose of the present invention is to mainly solve the problem of not enough high activity of the catalyst in the prior art. The styrene catalyst comprises the following active components by weight: a) 55-94 parts of Fe2O3, b) 5-30 parts of K2O, c) 3-15 parts of Ce2O3, d) 0.1-5 parts of MoO3 and/or WO3, e) 0.1-5 parts of a tungsten carbide, and f) 0.1-10 parts of at least the oxide of an alkaline earth metal selected from Mg, Ca, Sr and Ba. With the technical program of the present invention, the problem in the prior art is well solved. The styrene catalyst can be used in the industrial production of styrene.
Description
Technical field
The present invention relates to phenylethylene catalyst and preparation method thereof.
Background technology
Industrial at present cinnamic be mostly realized by ethylbenzene direct catalytic thermal dehydrogenation.The basic composition of used catalyst includes major catalyst, promoter and porogen, reinforcing agent etc..Report about catalyst generally can be divided into two big class, and a class is the Fe-K series catalysts containing Cr of early stage, United States Patent (USP) US4467046, US4684619 and European patent EP 0195252A2 etc. such as disclosed in oneself.Although the activity of such catalyst and stability are preferably, due to more or less there is the oxide of Cr in composition, thus certain environmental pollution in the preparation of catalyst, operation and dead catalyst processing procedure, can be caused, oneself is gradually eliminated.Another kind of is the Fe-K-Ce-Mo series that early eighties are succeeded in developing, United States Patent (USP) US5190906, US4804799, world patent W009839278A1 etc. such as disclosed in oneself.Such catalyst substitutes, with Ce, Mo binary auxiliary agent, the role originally being taken on by Cr, make catalyst on the basis of maintaining original stability, activity, selectivity there has also been certain raising compared with the former, adopted by countries in the world production of styrene producer, the subject matter that it exists is due to the volatility of Mo component, lead to the stability of catalyst low, some patent reports substitute the Mo of less stable although solving MoO with the very high W of heat stability3Sublimation problem, but catalysis activity is not high enough.For this reason, searching is a kind of produces cinnamic low temperature high activity, high stability catalyst always people's problem very interested.
Content of the invention
One of the technical problem to be solved is to overcome to have the shortcomings that in previous literature that catalyst activity is not high enough, stability is low, provides a kind of new phenylethylene catalyst.This catalyst has and can improve conversion of ethylbenzene, the good feature of catalyst stability simultaneously.
The two of the technical problem to be solved are the preparation methoies of above-mentioned catalyst.
The three of the technical problem to be solved are applications in ethylbenzene dehydrogenation ethylbenzene for the above-mentioned catalyst.
For solving one of above-mentioned technical problem, technical scheme is as follows：Phenylethylene catalyst, in parts by weight, including following active constituent：
A) 55～94 parts of Fe2O3；
B) 5～30 parts of K2O；
C) 3～15 parts of Ce2O3；
D) 0.1～5 part of MoO3And/or WO3；
E) carbide of 0.1～5 part of tungsten；
F) 0.1～10 part of oxide being selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
In technique scheme, MoO3And/or WO3It is preferably 0.1～3 part.
In technique scheme, the carbide of tungsten is preferably 0.1～3 part.
In technique scheme, the oxide consumption selected from least one of Mg, Ca, Sr, Ba is preferably 0.5～7 part.
In technique scheme, in described catalyst, preferably also the cement containing less than 10 parts is binding agent.
In above-mentioned technical side, further preferably contain Mo2C, still more preferably with weight ratio meter Mo2C：The carbide of tungsten=(0～100): 1.
In technique scheme, the carbide of tungsten can be WC and W2The carbide of at least one in C, more preferably tungsten includes WC and W simultaneously2C, WC and W2C has synergism in terms of improving styrene conversion rate.
For solving the two of above-mentioned technical problem, technical scheme is as follows：Any one of the technical scheme of one of above-mentioned technical problem, the preparation method of catalyst, comprises the following steps：Need the raw material of component, porogen to mix homogeneously with water by described, mediate, extrusion, be dried, pelletizing, roasting.
In technique scheme, the preferred autoxidisable substance of raw material of the oxide of described alkaline-earth metal, hydroxide or its salt, further described salt preferably nitrate, nitrite, carbonate or carboxylate.
In technique scheme, Fe2O3Raw material be preferably iron oxide red and/or iron oxide yellow, more preferably with weight ratio meter, iron oxide yellow:Iron oxide red is (0～0.5): 1, the most further preferred iron oxide yellow:Iron oxide red is (0～0.3): 1.
In technique scheme, K2The optional K of raw material of O2O, KOH are fired to generate K2The potassium salt of O, these potassium salt can be for example potassium nitrate, potassium nitrite, potassium carbonate, potassium bicarbonate or carboxylic acid potassium.
In technique scheme, Mo2The raw material of the carbide of C or tungsten can be with the form of its own.In the present invention, molybdenum carbide refers both to Mo2C.
In technique scheme, Ce2O3Raw material can be that the oxide of cerium, hydroxide or metallic salt form add, and metallic salts such as, but not limited to, nitrate.
In technique scheme, described porogen can be chosen from graphite, polystyrene microsphere, carboxymethyl cellulose etc.；Its consumption is preferably the 1～4% of catalyst weight.
The method for preparing catalyst of the such as present invention can be specially：
The described raw material needing component, binding agent, porogen are added appropriate deionized water, through mediating the paste made toughness, be suitable for extrusion, become a diameter of 3 millimeters, grow 5～10 millimeters of granule through extrusion, pelletizing, in 40～150 DEG C of dryings 1～10 hour, then roasting 1～8 hour at 400～1000 DEG C, you can obtain finished catalyst.
Catalyst of the present invention can carry out performance evaluation and use in isotherm formula fixed bed.For carrying out ethyl benzene dehydrogenation preparation of styrene activity rating in isotherm formula fixed bed, summary process is as follows：
By ethylbenzene and deionized water respectively through preheating in dosing pump input mixer, enter reactor in a gaseous form, reactor adopts electric-heating-wire-heating, makes up to predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interior load 100 milliliters, particle diameter be 3.0 millimeters of catalyst.The dehydrogenation product that flowed out by reactor water cooled solidifying after with chromatographic, it forms.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows：By 100 milliliters, particle diameter be that internal diameter 1 put into by 3 millimeters of catalyst " isothermal reactor, reaction pressure is normal pressure, ethylbenzene air speed 1.0 hours-1, 620 DEG C of reaction temperature, water ratio (water/ethylbenzene) (weight) 2.0.
Conversion of ethylbenzene and selectivity of styrene calculate as follows：
(%)=conversion of ethylbenzene (%) × selectivity of styrene (%) received by styrene list.
The main side reaction of ethylbenzene dehydrogenation is to generate toluene and benzene.Have shown that through research：The rate-determining step of reaction is the dehydrogenation step in catalyst surface for the ethylbenzene of absorption, and the carbide of tungsten ensures that catalyst has good low temperature active, increases the stability of catalyst, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
195 iron oxide reds, 80.5 grams of iron oxide yellows, 60.6 grams of potassium carbonate, 90.5 grams of nitric acid Fructus Kakis, 13.3 grams of ammonium molybdates, 1.1 grams of molybdenum carbides, 10.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 15 grams of cement and 10 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add 83 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.
【Embodiment 2】
130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 6.2 grams of molybdenum carbides, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, put into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 3】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 6.2 grams of W2C, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 4】
By 123.7 iron oxide reds, 167.5 grams of iron oxide yellows, 65.6 grams of potassium carbonate, 70.7 grams of nitric acid Fructus Kakis, 1.3 grams of ammonium molybdates, 9.2 grams of W2C, 10.1 grams of magnesium oxide, 8.5 grams of calcium oxide, 19 grams of cement and 12 grams of carboxymethyl celluloses stir 1 hour in kneader, add 73 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 5】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 3.1 grams of molybdenum carbides, 3.1 grams of W2C, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 6】
130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 3.1 grams of molybdenum carbides, 3.1 grams of WC, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, put into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 7】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 3.1 grams of molybdenum carbides, 1.6 grams of WC, 1.5 grams of W2C, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Comparative example 1】
In addition to being added without molybdenum carbide, remaining is all same as Example 2, specially for the preparation method of catalyst：
130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add 76 grams of deionized waters, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From comparative example 1 and embodiment 2 on year-on-year basis knowable to, include Mo due in catalyst2C is hence it is evident that improve the conversion of ethylbenzene of catalyst, and makes catalyst of the present invention have more preferable stability.
【Comparative example 2】
The preparation method of catalyst is except being added without W2Beyond C, remaining is all same as Example 4, specially：
123.7 iron oxide reds, 167.5 grams of iron oxide yellows, 65.6 grams of potassium carbonate, 70.7 grams of nitric acid Fructus Kakis, 1.3 grams of ammonium molybdates, 10.1 grams of magnesium oxide, 8.5 grams of calcium oxide, 19 grams of cement and 12 carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, it is extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, puts into baking oven, 80 DEG C are dried 4 hours, it is subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From comparative example 2 and embodiment 4 on year-on-year basis knowable to, due to including the carbide of tungsten in catalyst, improve the conversion of ethylbenzene of catalyst, and make the stability that catalyst of the present invention had.
Table 1
Table 2
*：Catalyst performance is the evaluation meansigma methodss of 200 hours.
Table 3
| 200 hours single receipts* | 1000 hours single receipts* | Single receipts reduction rate, % | |
| Comparative example 1 | 69.0 | 68.0 | 1.45 |
| Comparative example 2 | 69.1 | 68.1 | 1.45 |
| Embodiment 2 | 71.4 | 71.0 | 0.56 |
| Embodiment 4 | 71.0 | 70.7 | 0.42 |
| Embodiment 6 | 72.7 | 72.4 | 0.41 |
| Embodiment 7 | 73.1 | 72.9 | 0.27 |
*：Catalyst performance is the meansigma methodss in corresponding evaluation time.
Claims (10)
1. phenylethylene catalyst, in parts by weight, including following active constituent：
A) 55～94 parts of Fe2O3；
B) 5～30 parts of K2O；
C) 3～15 parts of Ce2O3；
D) 0.1～5 part of MoO3And/or WO3；
E) carbide of 0.1～5 part of tungsten；
F) 0.1～10 part of oxide being selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
2. phenylethylene catalyst according to claim 1 is it is characterised in that MoO3And/or WO3For 0.1～3 part.
3. phenylethylene catalyst according to claim 1 is it is characterised in that the carbide of tungsten is 0.1～3 part.
4. phenylethylene catalyst according to claim 1 is it is characterised in that be selected from Mg, Ca, Sr, Ba at least
A kind of oxide consumption is 0.5～7 part.
5. phenylethylene catalyst according to claim 1 is it is characterised in that the also water containing less than 10 parts in catalyst
Mud is binding agent.
6. the preparation method of the high stable catalyst described in any one of Claims 1 to 5, comprises the following steps：By institute
State and need the raw material of active component, porogen to mix homogeneously with water, mediate, extrusion, be dried, pelletizing, roasting.
7. preparation method according to claim 6 is it is characterised in that the raw material of the oxide of alkaline-earth metal is selected from oxidation
Thing, hydroxide or its salt.
8. preparation method according to claim 6 is it is characterised in that Fe2O3Raw material be iron oxide red and/or iron oxide yellow.
9. preparation method according to claim 8 is it is characterised in that with weight ratio meter, iron oxide yellow:Iron oxide red is (0～0.5):
1.
10. application in ethyl benzene dehydrogenation preparation of styrene for the catalyst any one of Claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493346.4A CN106423187B (en) | 2015-08-12 | 2015-08-12 | Phenylethylene catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493346.4A CN106423187B (en) | 2015-08-12 | 2015-08-12 | Phenylethylene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423187A true CN106423187A (en) | 2017-02-22 |
| CN106423187B CN106423187B (en) | 2019-02-19 |
Family
ID=58092731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510493346.4A Active CN106423187B (en) | 2015-08-12 | 2015-08-12 | Phenylethylene catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423187B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018593A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst having a bimodal pore size distribution |
| CN1207330A (en) * | 1997-08-01 | 1999-02-10 | 舒德化学公司 | Catalysts for dehydrogenating ethylbenzene to styrene |
| US6166280A (en) * | 1996-03-08 | 2000-12-26 | Montecatini Technologies S.R.L. | Catalyst for the dehydrogenation of ethylbenzene to styrene |
| CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 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 |
| CN102069002A (en) * | 2010-12-31 | 2011-05-25 | 浙江工业大学 | Preparation method of wolfram carbide-carbon (WC-C) composite material with large specific surface area |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
-
2015
- 2015-08-12 CN CN201510493346.4A patent/CN106423187B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018593A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst having a bimodal pore size distribution |
| US6166280A (en) * | 1996-03-08 | 2000-12-26 | Montecatini Technologies S.R.L. | Catalyst for the dehydrogenation of ethylbenzene to styrene |
| CN1207330A (en) * | 1997-08-01 | 1999-02-10 | 舒德化学公司 | Catalysts for dehydrogenating ethylbenzene to styrene |
| CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 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 |
| CN102069002A (en) * | 2010-12-31 | 2011-05-25 | 浙江工业大学 | Preparation method of wolfram carbide-carbon (WC-C) composite material with large specific surface area |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HENRY H. HWU ET AL.: ""Surface Chemistry of transition Metal Carbides"", 《CHEMICAL REVIEWS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423187B (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100531905C (en) | Catalysts for ethyl benzene dehydrogenation for preparation of styrene | |
| CN106582687B (en) | Catalyst of low-water ratio ethylbenzene dehydrogenation and preparation method thereof | |
| CN102039204B (en) | Method for preparing styrene catalyst by ethyl benzene dehydrogenation | |
| CN103537291B (en) | Catalyst of ethyl benzene dehydrogenation preparation of styrene and preparation method thereof | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN106582693B (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN101279263B (en) | Catalyst for preparation of styrene by ethylbenzene dehydrogenation | |
| CN101623642B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio | |
| CN109569638A (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN106582681B (en) | catalyst for low-water-ratio ethylbenzene dehydrogenation | |
| CN106582683A (en) | Low water ratio ethylbenzene dehydrogenation catalyst | |
| CN109569639A (en) | It is used to prepare the dehydrogenation and preparation method thereof of styrene | |
| CN106582689B (en) | It is used to prepare the dehydrogenation of styrene | |
| CN104959146A (en) | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio | |
| CN106582691B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof | |
| CN106582688B (en) | It is used to prepare the dehydrogenation and preparation method thereof of styrene | |
| CN106582827A (en) | High activity and low water ratio ethylbenzene dehydrogenation catalyst | |
| CN106582685B (en) | Low-temperature ethyl benzene dehydrogenation catalyst and preparation method thereof | |
| CN110681391A (en) | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN106423187A (en) | Styrene catalyst | |
| CN105478132B (en) | Catalyst for phenylethylene dehydrogenation of low-carbon type and its preparation method and application | |
| CN106423240A (en) | Styrene catalyst and preparation method thereof | |
| CN106423238A (en) | Styrene catalyst and preparation method thereof | |
| CN106423239A (en) | High-stability styrene catalyst | |
| CN103537295B (en) | The low temperature catalyst of 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |