CN106423240B - Phenylethylene catalyst and preparation method - Google Patents
Phenylethylene catalyst and preparation method Download PDFInfo
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Abstract
The present invention relates to the present invention relates to phenylethylene catalysts and preparation method thereof, it is not high enough mainly to solve the problems, such as in conventional art that there are catalyst activities.The present invention is by using phenylethylene catalyst, in parts by weight, including following active constituent: a) 55~95 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 molybdenum；F) 0.1~10 part of technical solution selected from least one of Mg, Ca, Sr and Ba oxide of alkaline-earth metal, preferably solves the problems, such as this, can be used in the industrial production of styrene.
Description
Technical field
The present invention relates to phenylethylene catalysts and preparation method thereof.
Background technique
Industrial styrene is mostly to be realized by the direct catalytic thermal dehydrogenation of ethylbenzene at present.Used catalyst
Basic composition includes major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc..It is big that report in relation to catalyst generally can be divided into two
Class, one kind are the Fe-K series catalysts containing Cr of early stage, United States Patent (USP) US4467046, US4684619 and Europe as disclosed in oneself
Patent EP0195252A2 etc..Although the activity and stability of such catalyst are preferable, due to more or less there is Cr in composition
Oxide, thus will cause certain environmental pollution in the preparation of catalyst, operation and dead catalyst treatment process, oneself by by
Gradually eliminate.Another kind of is the Fe-K-Ce-Mo series that early eighties are succeeded in developing, the United States Patent (USP) as disclosed in oneself
US5190906, US4804799, world patent W009839278A1 etc..Such catalyst Ce, Mo binary auxiliary agent substitutes original
The role taken on by Cr, so that catalyst, on the basis of maintaining original stability, activity, there has also been certain compared with the former for selectivity
Raising, used by countries in the world production of styrene producer, its existing main problem is led due to the volatility of Mo component
Cause the stability of catalyst relatively low, the Mo of some patent reports very high W substitution less stable of thermal stability, although solving
MoO3Sublimation problem, but catalytic activity is not high enough.For this purpose, finding a kind of low temperature high activity for producing styrene, high stable
Property catalyst is always the very interested project of people.
Summary of the invention
The first technical problem to be solved by the present invention is that overcome in previous literature that there are catalyst activities not high enough, stablizes
Property relatively low disadvantage, a kind of new phenylethylene catalyst is provided.The catalyst have can improve conversion of ethylbenzene, while catalyst
The good feature of stability.
The second technical problem to be solved by the present invention is the preparation method of above-mentioned catalyst.
The third technical problem to be solved by the present invention is application of the above-mentioned catalyst in ethylbenzene dehydrogenation ethylbenzene.
One of to solve above-mentioned technical problem, technical scheme is as follows: phenylethylene catalyst, in parts by weight,
Including following active constituent:
A) 55~95 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 molybdenum；
F) 0.1~10 part of oxide selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
In above-mentioned technical proposal, MoO3And/or WO3Preferably 0.1~3 part.
In above-mentioned technical proposal, the carbide of molybdenum is preferably 0.1~3 part.
In above-mentioned technical proposal, the oxide dosage selected from least one of Mg, Ca, Sr, Ba is preferably 0.5~7 part.
Preferably also containing 10 parts of cement below in above-mentioned technical proposal, in the catalyst is binder.
In above-mentioned technical side, further preferably contain W2C, the still more preferably carbide with weight ratio meter molybdenum: W2C=(0~
100): 1, and the carbide of molybdenum: W2C is not 0.
In above-mentioned technical proposal, the carbide of molybdenum can be MoC and Mo2At least one of C, the carbide of more preferable molybdenum
It simultaneously include MoC and Mo2C, MoC and Mo2C has synergistic effect in terms of improving styrene conversion rate.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The preparation method of catalyst described in any one of case, comprising the following steps: mix the raw material for needing component, pore-foaming agent with water
Uniformly, it mediates, extrusion, dry, pelletizing, roasting.
In above-mentioned technical proposal, the preferred autoxidisable substance of the raw material of the oxide of the alkaline-earth metal, hydroxide or its salt,
Further salt preferably nitrate, nitrite, carbonate or the carboxylate.
In above-mentioned technical proposal, Fe2O3Raw material be preferably iron oxide red and/or iron oxide yellow, more preferably with weight ratio meter, iron oxide yellow: iron
Red is (0~0.5): 1, most further preferred iron oxide yellow: iron oxide red is (0~0.3): 1.
In above-mentioned technical proposal, K2The optional K of the raw material of O2O, KOH is fired producible K2The sylvite of O, these sylvite are for example
It can be potassium nitrate, potassium nitrite, potassium carbonate, saleratus or carboxylic acid potassium.
In above-mentioned technical proposal, the carbide or W of molybdenum2The raw material of C can use the form of its own.It is carbonized in the present invention
Tungsten is W2C。
In above-mentioned technical proposal, Ce2O3Raw material can be cerium oxide, hydroxide or metallic salt form be added, and
Metallic salts such as, but not limited to, nitrate.
In above-mentioned technical proposal, the pore-foaming agent can be chosen from graphite, polystyrene microsphere, carboxymethyl cellulose etc.；
Its dosage is preferably the 1~4% of catalyst weight.
Such as method for preparing catalyst of the invention can be with specifically:
Suitable deionized water is added in the raw material for needing component, adhesive, pore-foaming agent, mediated be made toughness,
It is suitble to the paste of extrusion, through extrusion, pelletizing at diameter is 3 millimeters, long 5~10 millimeters of particle, in 40~150 DEG C dry 1
It~10 hours, is then roasted 1~8 hour at 400~1000 DEG C, can be obtained finished catalyst.
Catalyst of the present invention can carry out performance evaluation and use in isotherm formula fixed bed.It is carried out in isotherm formula fixed bed
For ethyl benzene dehydrogenation preparation of styrene activity rating, summary process is as follows:
By ethylbenzene and deionized water respectively through preheating in metering pump input mixer, enter reactor in a gaseous form, instead
It answers device using electric-heating-wire-heating, makes up to predetermined temperature.Reactor inside diameter be 1 " stainless steel tube, it is interior load 100 milliliters,
The catalyst that partial size is 3.0 millimeters.With chromatographic, it is formed after being coagulated by the dehydrogenation product of reactor outflow is water cooled.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors: by 100 milliliters, the catalyst that partial size is 3 millimeters
Be put into internal diameter 1 " isothermal reactor, reaction pressure be 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:
Styrene list receives (%)=conversion of ethylbenzene (%) × selectivity of styrene (%).
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 second of absorption
Benzene is in the dehydrogenation step of catalyst surface, and the carbide of molybdenum guarantees that catalyst has good low temperature active, increases catalyst
The service life is reacted, preferable technical effect is achieved.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
By 195 iron oxide reds, 80.5 grams of iron oxide yellows, 60.6 grams of potassium carbonate, 90.5 grams of nitric acid persimmons, 13.3 grams of ammonium molybdates,
1.1 grams of Mo2C, 10.4 grams of magnesia, 19.5 grams of calcium oxide and 15 grams of cement and 10 grams of carboxymethyl celluloses stir in kneader
1 hour, 83 grams of deionized waters are added, then mix and stir half an hour, take out extrusion, be extruded into of 3 millimeters of diameter, 5~10 millimeters of length
Grain is put into baking oven, and 80 DEG C are dried 4 hours, is subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It is listed in table 2.
[embodiment 2]
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 persimmons, 10.6 grams of molybdic acids
Ammonium, 6.2 grams of Mo2C, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir in kneader
It mixes 1 hour, 76 grams of deionized waters is added, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, 5~10 millimeters of length
Particle is put into baking oven, and 80 DEG C are dried 4 hours, is subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It 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 persimmons, 10.6 grams of molybdic acids
Ammonium, 6.2 grams of tungsten carbides, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses are in kneader
Stirring 1 hour, is added 76 grams of deionized waters, then mix and stir half an hour, takes out extrusion, is extruded into 3 millimeters of diameter, 5~10 millimeters of length
Particle, be put into baking oven, 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It 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 persimmons, 1.3 grams of molybdic acids
Ammonium, 9.2 grams of tungsten carbides, 10.1 grams of magnesia, 8.5 grams of calcium oxide, 19 grams of cement and 12 grams of carboxymethyl celluloses are in kneader
Stirring 1 hour, is added 73 grams of deionized waters, then mix and stir half an hour, takes out extrusion, is extruded into 3 millimeters of diameter, 5~10 millimeters of length
Particle, be put into baking oven, 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It 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 persimmons, 10.6 grams of molybdic acids
Ammonium, 3.1 grams of Mo2C, 3.1 grams of tungsten carbides, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses
It is stirred 1 hour in kneader, 76 grams of deionized waters is added, then mix and stir half an hour, taken out extrusion, be extruded into 3 millimeters of diameter, length
5~10 millimeters of particle is put into baking oven, and 80 DEG C are dried 4 hours, is subsequently placed in muffle furnace, roasts to be made for 6 hours in 780 DEG C and urge
Agent.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
[embodiment 6]
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 persimmons, 10.6 grams of molybdic acids
Ammonium, 3.1 grams of MoC, 3.1 grams of tungsten carbides, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses exist
It is stirred 1 hour in kneader, 76 grams of deionized waters is added, then mix and stir half an hour, taken out extrusion, be extruded into 3 millimeters of diameter, length 5
~10 millimeters of particle is put into baking oven, and 80 DEG C are dried 4 hours, is subsequently placed in muffle furnace, roasts 6 hours in 780 DEG C and catalysis is made
Agent.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It 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 persimmons, 10.6 grams of molybdic acids
Ammonium, 1.5 grams of Mo2C, 1.6 grams of MoC, 3.1 grams of tungsten carbides, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxylic first
Base cellulose stirs 1 hour in kneader, 76 grams of deionized waters is added, then mix and stir half an hour, takes out extrusion, is extruded into diameter 3
Millimeter, 5~10 millimeters of length of particle are put into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, small in 780 DEG C of roastings 6
When be made catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
[comparative example 1]
The preparation method of catalyst is in addition to being added without Mo2Other than C, remaining is same as Example 2, specifically:
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 persimmons, 10.6 grams of molybdic acids
Ammonium, 8.4 grams of magnesia, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 hour in kneader, add
Enter 76 grams of deionized waters, then mix and stir half an hour, takes out extrusion, be extruded into the particle of 3 millimeters of diameter, 5~10 millimeters of length, be put into baking
Case, 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From the year-on-year of comparative example 1 and embodiment 2 it is found that due to include in catalyst molybdenum carbide, hence it is evident that improve
The conversion of ethylbenzene of catalyst, and make catalyst of the present invention that there is better stability.
[comparative example 2]
For the preparation method of catalyst other than being added without tungsten carbide, remaining is same as Example 4, specifically:
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 persimmons, 1.3 grams of molybdic acids
Ammonium, 10.1 grams of magnesia, 8.5 grams of calcium oxide, 19 grams of cement and 12 carboxymethyl celluloses stir 1 hour in kneader, are added
Deionized water, then mix and stir half an hour takes out extrusion, is extruded into the particle of 3 millimeters of diameter, 5~10 millimeters of length, is put into baking oven, and 80
DEG C dry 4 hours, be subsequently placed in muffle furnace, in 780 DEG C of roastings, 6 hours obtained catalyst.
For convenient for comparing, the inventory in catalyst preparation is listed in Table 1 below, by 200 hours results of evaluating catalyst
It is listed in table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From the year-on-year it is found that due to including W in catalyst of comparative example 2 and embodiment 42C improves the ethylbenzene of catalyst
Conversion ratio, and the stability that catalyst of the present invention has been had.
Table 1
Table 2
*: catalyst performance is the average value for evaluating 200 hours.
Table 3
| 200 hours single receipts* | 1000 hours single receipts* | It is single to receive reduced 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 | 72.8 | 72.5 | 0.41 |
| Embodiment 7 | 73.2 | 73.0 | 0.27 |
*: catalyst performance is the average value in corresponding evaluation time.
Claims (10)
1. phenylethylene catalyst, in parts by weight, including following active constituent:
A) 55~95 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 molybdenum；
F) 0.1~10 part of oxide selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
2. phenylethylene catalyst according to claim 1, it is characterised in that MoO3And/or WO3It is 0.1~3 part.
3. phenylethylene catalyst according to claim 1, it is characterised in that the carbide of molybdenum is 0.1~3 part.
4. phenylethylene catalyst according to claim 1, it is characterised in that the oxygen selected from least one of Mg, Ca, Sr, Ba
Compound dosage is 0.5~7 part.
5. phenylethylene catalyst according to claim 1, it is characterised in that also contain 10 parts of cement below in catalyst
For binder.
6. the preparation method of catalyst described in any one of Claims 1 to 5, comprising the following steps: by required active component
Raw material, pore-foaming agent are uniformly mixed with water, are mediated, extrusion, dry, pelletizing, roasting.
7. preparation method according to claim 6, it is characterised in that the raw material of the oxide of alkaline-earth metal be selected from oxide,
Hydroxide or its salt.
8. preparation method according to claim 6, it is characterised in that Fe2O3Raw material be iron oxide red and/or iron oxide yellow.
9. preparation method according to claim 8, which is characterized in that with weight ratio meter, iron oxide yellow: iron oxide red is (0~0.5):
1。
10. application of the catalyst described in any one of Claims 1 to 5 in ethyl benzene dehydrogenation preparation of styrene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045671B2 (en) * | 2002-12-10 | 2006-05-16 | Haldor Topsoe A/S | Process for catalytic dehydrogenation and catalyst therefor |
| CN100413830C (en) * | 2005-08-15 | 2008-08-27 | 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 |
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- 2015-08-12 CN CN201510493349.8A patent/CN106423240B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045671B2 (en) * | 2002-12-10 | 2006-05-16 | Haldor Topsoe A/S | Process for catalytic dehydrogenation and catalyst therefor |
| CN100413830C (en) * | 2005-08-15 | 2008-08-27 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 碳化钼催化剂的研究进展;张新等;《中国钼业》;20101231;第34卷(第6期);第25-29页 |
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