CN105268444B - The production method of phenylethylene catalyst and styrene - Google Patents
The production method of phenylethylene catalyst and styrene Download PDFInfo
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Abstract
The present invention relates to the production method of the catalyst of ethyl benzene dehydrogenation preparation of styrene and styrene, mainly solving the Cerium in Catalysts content height used in conventional production of styrene causes phenylethylene catalyst production cost high, and reduce the problem of cerium content causes catalyst activity reduction, the present invention is by using phenylethylene catalyst, including following component in terms of parts by weight：Fe2O3, 60~90 parts；K2O, 5~10 parts；Ce2O3, 2~8 parts；MgO, 0.1~10 part；CaO, 0.1~10 part；Nb2O5, 0.01~4 part；ZrO2, 0.01~4 part；The catalyst is free of the technical scheme of molybdenum element, preferably solves the technical problem, available in the industrial production of ethyl benzene dehydrogenation preparation of styrene.
Description
Technical field
The present invention relates to the production method of the catalyst of ethyl benzene dehydrogenation preparation of styrene and styrene.
Background technology
At present, industrially preparing styrene is made by ethylbenzene dehydrogenation, and one of key of the production method is that selection is a kind of
Efficient dehydrogenation, catalyst for phenylethylene dehydrogenation are mostly Fe-K-Ce-Mo series catalysts, the Ce in such catalyst system
It is indispensable auxiliary agent, catalytic activity is played an important role, therefore its usage amount is improved constantly to increase catalyst work
Property, but Ce price is also improved constantly in recent years, and very big pressure is brought to Catalyst Production cost.Chinese patent 96116541.3
(dehydrogenating technology that CN1180687A is used to produce styrene) has invented a kind of dehydrogenating technology for being used to produce styrene, the dehydrogenation
Catalyst used in technique has high activity and product yield, there is stronger from power of regeneration, but its rare earth element again
The use of content is 2~15%, because rare earth element increasingly appreciates, catalyst cost constantly rises, and also gives production of styrene cost
Bring pressure.
The content of the invention
One of technical problems to be solved by the invention are that the Cerium in Catalysts content height used in conventional production of styrene is led
Cause phenylethylene catalyst production cost high, and reduce the problem of cerium content causes catalyst activity reduction, there is provided it is a kind of newly
Phenylethylene catalyst；The catalyst has still keep higher catalytic activity in the case of reducing cerium content the advantages of.
The two of the technical problems to be solved by the invention are the styrene using the catalyst of one of above-mentioned technical problem
Production method.
To solve one of above-mentioned technical problem, technical scheme is as follows：Phenylethylene catalyst, in terms of parts by weight
Including following component：
Fe2O3, 60~90 parts；
K2O, 5~10 parts；
Ce2O3, 2~8 parts；
MgO, 0.1~10 part；
CaO, 0.1~10 part；
Nb2O5, 0.01~4 part；
ZrO2, 0.01~4 part；
The catalyst is free of molybdenum element.
In above-mentioned technical proposal, described catalyst Ce in terms of parts by weight2O3Dosage be preferably 3~6 parts.
In above-mentioned technical proposal, described catalyst Nb in terms of parts by weight2O5Dosage be preferably 0.1~3 part；It is more excellent
Elect 0.5~2 part as.
In above-mentioned technical proposal, described catalyst ZrO in terms of parts by weight2Dosage be preferably 0.1~3 part；It is more excellent
Elect 0.5~2 part as.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The production method of styrene, is included in water
With the technical scheme of one of above-mentioned technical problem any one of in the presence of catalyst ethylbenzene carry out dehydrogenation reaction and obtain benzene second
Alkene.
In above-mentioned technical proposal, reaction pressure is preferably normal pressure~-0.07MPa.
In above-mentioned technical proposal, reaction temperature is preferably 550~650 DEG C.
In above-mentioned technical proposal, water/ethylbenzene mass ratio is preferably 0.6~2.5.
In above-mentioned technical proposal, ethylbenzene liquid volume air speed is preferably 0.3~1.0h-1。
The preparation method of catalyst of the present invention is as follows：
Fe, K, Ce, Mg, Ca, Nb and Zr compound are weighed by proportioning, dry powder blend, adds appropriate deionized water, wet feed
It is kneaded into the dough thing of suitable extrusion.Extrusion, pelletizing are into a diameter of 3mm, a length of 5mm of bar particle.In aged at room temperature 2~10
Hour, 80~120 DEG C of drying 4~10 hours, 600~1000 DEG C are calcined 2~4 hours, you can acquisition finished catalyst.Wherein,
Raw material Fe2O3Added in the form of iron oxide red, K2O is added in the form of potassium carbonate, Ce2O3With cerous nitrate and/or cerium oxalate
Form is added, and MgO is added in the form of magnesia and/or magnesium carbonate, and CaO is added in the form of calcium oxide and/or calcium carbonate,
Nb2O5Add in the form of the oxide, ZrO2Add in the form of the oxide.
The activity rating of catalyst is carried out in isothermal fixed bed reactors in the present invention, and reactor is that internal diameter is 25mm
Stainless steel tube, loads 100ml catalyst, and dehydrogenation liquid supplies chromatography, measures ethylbenzene and styrene-content.Calculating formula is as follows：
Styrene list receives (%)=conversion of ethylbenzene (%) × selectivity of styrene (%)
The boiling test method of testing of catalyst is as follows in the present invention：By 100 catalyst samples with 10 for one group, point
Tested for 10 groups.In the water that 10 catalyst samples inputs are boiled, continue after boiling 30 minutes, cool down 30 minutes.See
The integrity degree of catalyst granules in water is examined, records the granule number of rupture.Retest 10 times, crack-free are qualified.
The cold water test method of testing of catalyst is as follows in the present invention：By 100 catalyst samples with 10 for one group, point
Tested for 10 groups.10 catalyst samples are put into cold water, stand 30 minutes.Catalyst granules is complete in observation water
Degree, record the granule number of rupture.Retest 10 times, crack-free are qualified.
The anti-crushing power of catalyst technical requirements as defined in standard HG/T 2782-1996 are measured in the present invention, are made
With DL-II type intelligence granule strength instrument.Specimen length 5mm, it is one group with 40 and is tested, take the arithmetic of its measurement result to put down
Average is final resistance to crusing force value, with the unit that newton (N) is anti-crushing power.
Due to present invention employs in Fe-K-Ce catalyst systems, with the addition of Nb and Zr technical scheme, inventor shies
Very find that low cerium content catalyst still keeps higher catalytic activity, achieve preferable technique effect.
Below by embodiment and comparative example, the invention will be further elaborated.
Specific embodiment
In a specific embodiment, Ce2O3Added in the form of cerous nitrate, MgO is added in the form of magnesia；CaO is with oxygen
The form for changing calcium adds.
【Embodiment 1】
1st, catalyst preparation
By 88 parts of iron oxide reds, 6 parts of potassium oxides, 7 parts of cerium oxide, 6 parts of magnesia, 4 parts of calcium oxide, 0.5 part of niobium oxide, 2
Part zirconium oxide, 4 parts of carboxymethyl celluloses, are well mixed, and add 40 parts of deionized waters, and wet feed is mediated to the dough of suitable extrusion
Thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in 800 DEG C of roastings
Burn 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 74.2%, selectivity of styrene 95.3%, resistance to crusing
Power 121N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 2】
1st, catalyst preparation
By 70 parts of iron oxide reds, 5.4 parts of potassium oxides, 2 parts of cerium oxide, 0.5 part of magnesia, 2 parts of calcium oxide, 0.02 part of oxidation
Niobium, 2.3 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in
800 DEG C of roastings, 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 0.5h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 75.3%, selectivity of styrene 95.2%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 3】
1st, catalyst preparation
By 61 parts of iron oxide reds, 9.6 parts of potassium oxides, 7.9 parts of cerium oxide, 2 parts of magnesia, 0.5 part of calcium oxide, 3.5 parts of oxygen
Change niobium, 4 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, be well mixed, add 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in
800 DEG C of roastings, 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 74.2%, selectivity of styrene 95.1%, resistance to crusing
Power 121N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 4】
1st, catalyst preparation
By 81 parts of iron oxide reds, 7 parts of potassium oxides, 5 parts of cerium oxide, 5 parts of magnesia, 5 parts of calcium oxide, 2.2 parts of niobium oxide,
0.05 part of zirconium oxide, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the face of suitable extrusion
Dough, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster, in 800 in 80 DEG C
DEG C roasting 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 0.5h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 75.1%, selectivity of styrene 95.2%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 5】
1st, catalyst preparation
By 86 parts of iron oxide reds, 10 parts of potassium oxides, 3 parts of cerium oxide, 4.2 parts of magnesia, 3 parts of calcium oxide, 4 parts of niobium oxide, 3
Part zirconium oxide, 4 parts of carboxymethyl celluloses, are well mixed, and add 40 parts of deionized waters, and wet feed is mediated to the dough of suitable extrusion
Thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in 800 DEG C of roastings
Burn 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 74.1%, selectivity of styrene 95.1%, resistance to crusing
Power 122N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 6】
1st, catalyst preparation
By 77 parts of iron oxide reds, 9 parts of potassium oxides, 6 parts of cerium oxide, 3 parts of magnesia, 7 parts of calcium oxide, 0.05 part of niobium oxide, 1
Part zirconium oxide, 4 parts of carboxymethyl celluloses, are well mixed, and add 40 parts of deionized waters, and wet feed is mediated to the dough of suitable extrusion
Thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in 800 DEG C of roastings
Burn 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 0.5h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 76.1%, selectivity of styrene 94.8%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 7】
1st, catalyst preparation
By 78 parts of iron oxide reds, 8 parts of potassium oxides, 4 parts of cerium oxide, 1 part of magnesia, 8 parts of calcium oxide, 1 part of niobium oxide, 0.02
Part zirconium oxide, 4 parts of carboxymethyl celluloses, are well mixed, and add 40 parts of deionized waters, and wet feed is mediated to the dough of suitable extrusion
Thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in 800 DEG C of roastings
Burn 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 74.2%, selectivity of styrene 95.2%, resistance to crusing
Power 122N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 8】
1st, catalyst preparation
By 63 parts of iron oxide reds, 5 parts of potassium oxides, 3.5 parts of cerium oxide, 8 parts of magnesia, 9.5 parts of calcium oxide, 1.5 parts of oxidations
Niobium, 1.4 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in
800 DEG C of roastings, 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 0.5h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 75.1%, selectivity of styrene 95.1%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 9】
1st, catalyst preparation
By 66 parts of iron oxide reds, 10 parts of potassium oxides, 5 parts of cerium oxide, 1.3 parts of magnesia, 1.2 parts of calcium oxide, 0.5 part of oxidation
Niobium, 2.3 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in
800 DEG C of roastings, 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 610 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 72.6%, selectivity of styrene 96.2%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 10】
1st, catalyst preparation
By 68 parts of iron oxide reds, 9 parts of potassium oxides, 4.5 parts of cerium oxide, 8.8 parts of magnesia, 1.4 parts of calcium oxide, 1.6 parts of oxygen
Change niobium, 3.2 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, be well mixed, add 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, be put into baking oven, dry 6 hours, be placed in roaster in 80 DEG C,
2 hours obtained finished catalysts are calcined in 800 DEG C.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 1.8, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 72.1%, selectivity of styrene 95.8%, resistance to crusing
Power 121N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Embodiment 11】
1st, catalyst preparation
By 72 parts of iron oxide reds, 8 parts of potassium oxides, 2.6 parts of cerium oxide, 9.8 parts of magnesia, 10 parts of calcium oxide, 2.2 parts of oxidations
Niobium, 2.2 parts of zirconium oxides, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to suitable extrusion
Dough thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, in
800 DEG C of roastings, 2 hours obtained finished catalysts.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 640 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 75.6%, selectivity of styrene 94.5%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Comparative example 1】
1st, catalyst preparation
By 88 parts of iron oxide reds, 6 parts of potassium oxides, 14 parts of cerium oxide, 6 parts of magnesia, 4 parts of calcium oxide, 3.2 parts of molybdenum oxides, 4
Part carboxymethyl cellulose, is well mixed, and adds 40 parts of deionized waters, and wet feed is mediated to the dough thing of suitable extrusion, extrusion, cut
Grain, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, made within 2 hours in 800 DEG C of roastings
Obtain finished catalyst.For ease of comparing, the composition of catalyst is listed in table 1.2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 74.1%, selectivity of styrene 95.1%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Comparative example 2】
1st, catalyst preparation
By 88 parts of iron oxide reds, 6 parts of potassium oxides, 7 parts of cerium oxide, 6 parts of magnesia, 4 parts of calcium oxide, 4 parts of carboxymethyl celluloses
Element, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated old in room temperature to the dough thing of suitable extrusion, extrusion, pelletizing
Change 10 hours, be put into baking oven, in 80 DEG C dry 6 hours, be placed in roaster, in 800 DEG C be calcined 2 hours obtained catalyst into
Product.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 72.5%, selectivity of styrene 95.5%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Comparative example 3】
1st, catalyst preparation
By 88 parts of iron oxide reds, 6 parts of potassium oxides, 7 parts of cerium oxide, 6 parts of magnesia, 4 parts of calcium oxide, 2.5 parts of niobium oxide, 4
Part carboxymethyl cellulose, is well mixed, and adds 40 parts of deionized waters, and wet feed is mediated to the dough thing of suitable extrusion, extrusion, cut
Grain, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, made within 2 hours in 800 DEG C of roastings
Obtain finished catalyst.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 71.3%, selectivity of styrene 95.8%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
【Comparative example 4】
1st, catalyst preparation
By 88 parts of iron oxide reds, 6 parts of potassium oxides, 7 parts of cerium oxide, 6 parts of magnesia, 4 parts of calcium oxide, 2.5 parts of zirconium oxides, 4
Part carboxymethyl cellulose, is well mixed, and adds 40 parts of deionized waters, and wet feed is mediated to the dough thing of suitable extrusion, extrusion, cut
Grain, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, made within 2 hours in 800 DEG C of roastings
Obtain finished catalyst.For ease of comparing, the composition of catalyst is listed in table 1.
2nd, evaluating catalyst
100ml catalyst is loaded into assessing reactor, reaction pressure is normal pressure, 620 DEG C of reaction temperature, water/ethylbenzene quality
Than 2.0, ethylbenzene liquid volume air speed 1.0h-1Under the conditions of carry out catalytically active assessment, and determine the anti-crushing power of catalyst, boiling water
Pass the test rate, cold water test qualification rate.Test result：Styrene list receipts 70.6%, selectivity of styrene 96.6%, resistance to crusing
Power 120N, boiling test is qualified, cold water test is qualified.For ease of comparing, catalyst performance is listed in table 2.
Various embodiments above illustrates, in the present invention, in Fe-K-Ce catalyst systems, after reducing cerium content, using addition
Other substitute Nb and Zr method, so that low cerium content catalyst keeps reducing catalyst while higher catalytic activity
Production cost.
Table 1
| Parts by weight | Fe2O3 | K2O | Ce2O3 | MgO | CaO | Nb2O5 | ZrO2 | MoO3 |
| Embodiment 1 | 88 | 6 | 7 | 6 | 4 | 0.5 | 2 | |
| Embodiment 2 | 70 | 5.4 | 2 | 0.5 | 2 | 0.02 | 2.3 | |
| Embodiment 3 | 61 | 9.6 | 7.9 | 2 | 0.5 | 3.5 | 4 | |
| Embodiment 4 | 81 | 7 | 5 | 5 | 5 | 2.2 | 0.05 | |
| Embodiment 5 | 86 | 10 | 3 | 4.2 | 3 | 4 | 3 | |
| Embodiment 6 | 77 | 9 | 6 | 3 | 7 | 0.05 | 1 | |
| Embodiment 7 | 78 | 8 | 4 | 1 | 8 | 1 | 0.02 | |
| Embodiment 8 | 63 | 5 | 3.5 | 8 | 9.5 | 1.5 | 1.4 | |
| Embodiment 9 | 66 | 10 | 5 | 1.3 | 1.2 | 0.5 | 2.3 | |
| Embodiment 10 | 68 | 9 | 4.5 | 8.8 | 1.4 | 1.6 | 3.2 | |
| Embodiment 11 | 72 | 8 | 2.6 | 9.8 | 10 | 2.2 | 2.2 | |
| Comparative example 1 | 88 | 6 | 14 | 6 | 4 | 3.2 | ||
| Comparative example 2 | 88 | 6 | 7 | 6 | 4 | |||
| Comparative example 3 | 88 | 6 | 7 | 6 | 4 | 2.5 | ||
| Comparative example 4 | 88 | 6 | 7 | 6 | 4 | 2.5 |
Table 2
Claims (9)
1. phenylethylene catalyst, including following component in terms of parts by weight：
Fe2O3, 60~90 parts；
K2O, 5~10 parts；
Ce2O3, 2~8 parts；
MgO, 0.1~10 part；
CaO, 0.1~10 part；
Nb2O5, 0.01~4 part；
ZrO2, 0.01~4 part；
The catalyst is free of molybdenum element.
2. catalyst according to claim 1, it is characterized in that described catalyst Ce in terms of parts by weight2O3Dosage be 3
~6 parts.
3. catalyst according to claim 1, it is characterized in that described catalyst Nb in terms of parts by weight2O5Dosage be
0.1~3 part.
4. catalyst according to claim 1, it is characterized in that described catalyst ZrO in terms of parts by weight2Dosage be
0.1~3 part.
5. the production method of styrene, ethylbenzene is carried out in the presence of being included in catalyst any one of water and Claims 1-4
Dehydrogenation reaction obtains styrene.
6. production method according to claim 5, it is characterized in that reaction pressure is normal pressure~-0.07MPa.
7. production method according to claim 5, it is characterized in that reaction temperature is 550~650 DEG C.
8. production method according to claim 5, it is characterized in that water/ethylbenzene mass ratio is 0.6~2.5.
9. production method according to claim 5, it is characterized in that ethylbenzene liquid volume air speed is 0.3~1.0h-1。
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| CN201410355522.3A CN105268444B (en) | 2014-07-24 | 2014-07-24 | The production method of phenylethylene catalyst and styrene |
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| CN105268444B true CN105268444B (en) | 2017-12-15 |
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| CN103539627A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method of preparing styrene |
| CN103769142A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing phenethylene through ethylbenzene dehydrogenation |
| CN103772135A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method |
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| CN101279263A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for preparation of styrene by ethylbenzene dehydrogenation |
| CN103539627A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method of preparing styrene |
| CN103769142A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing phenethylene through ethylbenzene dehydrogenation |
| CN103772135A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method |
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