CN105312059B - The catalyst of dehydrogenation of ethylbenzene to styrene - Google Patents
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Abstract
The present invention relates to the production method of the catalyst of dehydrogenation of ethylbenzene to styrene and styrene, to be solved by this invention is that 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, by using the catalyst of dehydrogenation of ethylbenzene to styrene, including following component in terms of parts by weight：65~95 parts of Fe2O3, 5~10 parts of K2O, 2~8 parts of Ce2O3, 0.1~8 part of MgO, 0.1~8 part of CaO, 0.01~4 part of ZnO, 0.01~4 part of Ni2O3；Technical scheme without molybdenum or its oxide in catalyst, available in the industrial production of dehydrogenation of ethylbenzene to styrene.
Description
Technical field
The present invention relates to the production method of the catalyst of dehydrogenation of ethylbenzene to styrene and styrene.
Background technology
At present, industrially production 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
A kind of dehydrogenating technology for being used to produce styrene is invented, catalyst used in the dehydrogenating technology has high activity and product
Yield, have again it is stronger from power of regeneration, but the use content of its rare earth element be 2~15%, because rare earth element increasingly rises
Valency, catalyst cost constantly rise, and also bring pressure to production of styrene cost.
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
The catalyst of dehydrogenation of ethylbenzene to styrene；The catalyst has still keeps higher catalytic activity in the case where 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：The catalysis of dehydrogenation of ethylbenzene to styrene
Agent, including following component in terms of parts by weight：
65~95 parts of Fe2O3,
5~10 parts of K2O,
2~8 parts of Ce2O3,
0.1~8 part of MgO,
0.1~8 part of CaO,
0.01~4 part of ZnO,
0.01~4 part of Ni2O3；
Molybdenum or its oxide are free of in catalyst.
In above-mentioned technical proposal, the Ce in terms of parts by weight2O3Dosage be preferably 3~6 parts.
In above-mentioned technical proposal, the dosage of the ZnO in terms of parts by weight is preferably 0.1~3 part.
In above-mentioned technical proposal, the dosage of the ZnO in terms of parts by weight is preferably 0.5~2 part.
In above-mentioned technical proposal, the Ni in terms of parts by weight2O3Dosage be preferably 0.1~3 part；More preferably 0.5~2 part.
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。
Method for preparing catalyst of the present invention is as follows：
Fe, K, Ce, Mg, Ca, Zn and Ni 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 into a diameter of 3mm, a length of 5mm of bar or so particle.In aged at room temperature 2
~10 hours, 80~120 DEG C of dryings 4~10 hours, 600~1000 DEG C were calcined 2~4 hours, you can obtain finished catalyst.Its
In, 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 add, MgO added in the form of magnesia and/or magnesium carbonate, and CaO is added in the form of calcium oxide and/or calcium carbonate,
ZnO is added in the form of the oxide, Ni2O3Add 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 Zn and Ni 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.
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 65 parts of iron oxide reds, 6 parts of potassium oxides, 2 parts of cerium oxide, 7 parts of magnesia, 0.3 part of calcium oxide, 0.5 part of zinc oxide,
2 parts of nickel oxide, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the dough of suitable extrusion
Shape thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster, in 800 DEG C in 80 DEG C
2 hours obtained finished catalysts are calcined, 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 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 94 parts of iron oxide reds, 9.5 parts of potassium oxides, 3 parts of cerium oxide, 8 parts of magnesia, 7 parts of calcium oxide, 1.2 parts of zinc oxide,
0.2 part of nickel 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 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 73.8%, selectivity of styrene 95.2%, 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 3】
1st, catalyst preparation
By 66 parts of iron oxide reds, 9 parts of potassium oxides, 5 parts of cerium oxide, 0.8 part of magnesia, 8 parts of calcium oxide, 0.1 part of zinc oxide,
4 parts of nickel oxide, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the dough of suitable extrusion
Shape thing, extrusion, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster, in 800 DEG C in 80 DEG C
2 hours obtained finished catalysts are calcined, 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 95.2%, 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 4】
1st, catalyst preparation
By 82 parts of iron oxide reds, 10 parts of potassium oxides, 7 parts of cerium oxide, 0.1 part of magnesia, 4 parts of calcium oxide, 3.2 parts of oxidations
Zinc, 3 parts of nickel 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 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 73.9%, 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 5】
1st, catalyst preparation
By 73 parts of iron oxide reds, 5 parts of potassium oxides, 6 parts of cerium oxide, 5 parts of magnesia, 3.6 parts of calcium oxide, 2.5 parts of zinc oxide,
0.02 part of nickel 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 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 6】
1st, catalyst preparation
By 75 parts of iron oxide reds, 7 parts of potassium oxides, 8 parts of cerium oxide, 3 parts of magnesia, 3 parts of calcium oxide, 0.01 part of zinc oxide,
2.5 parts of nickel 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 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 73.9%, 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 7】
1st, catalyst preparation
By 86 parts of iron oxide reds, 8 parts of potassium oxides, 4 parts of cerium oxide, 0.4 part of magnesia, 6 parts of calcium oxide, 0.05 part of oxidation
Zinc, 2.4 parts of nickel oxide, 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, table 1 is listed in by the composition of catalyst.
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 94.7%, 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 68 parts of iron oxide reds, 8.6 parts of potassium oxides, 5 parts of cerium oxide, 6 parts of magnesia, 0.5 part of calcium oxide, 4 parts of zinc oxide,
0.01 part of nickel 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 74.9%, 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 9】
1st, catalyst preparation
By 70 parts of iron oxide reds, 6 parts of potassium oxides, 4 parts of cerium oxide, 4 parts of magnesia, 1.8 parts of calcium oxide, 1.8 parts of zinc oxide,
3.5 parts of nickel 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, 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 72.3%, selectivity of styrene 96.7%, 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 10】
1st, catalyst preparation
By 88 parts of iron oxide reds, 8.8 parts of potassium oxides, 4.5 parts of cerium oxide, 2.2 parts of magnesia, 1.4 parts of calcium oxide, 2.2 parts
Zinc oxide, 1 part of nickel oxide, 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, 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 72.8%, selectivity of styrene 95.8%, 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 11】
1st, catalyst preparation
By 90 parts of iron oxide reds, 8.2 parts of potassium oxides, 6 parts of cerium oxide, 1.5 parts of magnesia, 5 parts of calcium oxide, 0.5 part of oxidation
Zinc, 3.2 parts of nickel oxide, 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, table 1 is listed in by the composition of catalyst.
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 75.9%, selectivity of styrene 94.5%, 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.
【Comparative example 1】
1st, catalyst preparation
By 65 parts of iron oxide reds, 6 parts of potassium oxides, 14 parts of cerium oxide, 0.3 part of magnesia, 0.3 part of calcium oxide, 3 parts of MoO3、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
Finished catalyst is obtained, 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 65 parts of iron oxide reds, 6 parts of potassium oxides, 2 parts of cerium oxide, 0.3 part of magnesia, 0.3 part of calcium oxide, 4 parts of carboxymethyls
Cellulose, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the dough thing of suitable extrusion, extrusion, pelletizing, in room
Warm aging 10 hours, is put into baking oven, dries 6 hours, is placed in roaster in 80 DEG C, and 2 hours obtained catalyst are calcined in 800 DEG C
Finished 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 70.5%, 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.
【Comparative example 3】
1st, catalyst preparation
By 65 parts of iron oxide reds, 6 parts of potassium oxides, 2 parts of cerium oxide, 0.3 part of magnesia, 0.3 part of calcium oxide, 2.5 parts of oxidations
Zinc, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the dough thing of suitable extrusion, is squeezed
Bar, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, it is small in 800 DEG C of roastings 2
When be made 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 70.3%, 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 4】
1st, catalyst preparation
By 65 parts of iron oxide reds, 6 parts of potassium oxides, 2 parts of cerium oxide, 0.3 part of magnesia, 0.3 part of calcium oxide, 2.5 parts of oxidations
Nickel, 4 parts of carboxymethyl celluloses, it is well mixed, adds 40 parts of deionized waters, wet feed is mediated to the dough thing of suitable extrusion, is squeezed
Bar, pelletizing, in aged at room temperature 10 hours, baking oven is put into, dries 6 hours, be placed in roaster in 80 DEG C, it is small in 800 DEG C of roastings 2
When be made 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 66.2%, selectivity of styrene 97.2%, 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.
Various embodiments above illustrates, in the present invention, in Fe-K-Ce catalyst systems, after reducing cerium content, using addition
Other substitute Zn and Ni 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 | ZnO | Ni2O3 | MoO3 |
| Embodiment 1 | 65 | 6 | 2 | 0.3 | 0.3 | 0.5 | 2 | |
| Embodiment 2 | 94 | 9.5 | 3 | 8 | 7 | 1.2 | 0.2 | |
| Embodiment 3 | 66 | 9 | 5 | 0.8 | 8 | 0.1 | 4 | |
| Embodiment 4 | 82 | 10 | 7 | 0.1 | 4 | 3.2 | 3 | |
| Embodiment 5 | 73 | 5 | 6 | 5 | 3.6 | 2.5 | 0.02 | |
| Embodiment 6 | 75 | 7 | 8 | 3 | 3 | 0.01 | 2.5 | |
| Embodiment 7 | 86 | 8 | 4 | 0.4 | 6 | 0.05 | 2.4 | |
| Embodiment 8 | 68 | 8.6 | 5 | 6 | 0.5 | 4 | 0.01 | |
| Embodiment 9 | 70 | 6 | 4 | 4 | 1.8 | 1.8 | 3.5 | |
| Embodiment 10 | 88 | 8.8 | 4.5 | 2.2 | 1.4 | 2.2 | 1 | |
| Embodiment 11 | 90 | 8.2 | 6 | 1.5 | 5 | 0.5 | 3.2 | |
| Comparative example 1 | 65 | 6 | 14 | 0.3 | 0.3 | 3 | ||
| Comparative example 2 | 65 | 6 | 2 | 0.3 | 0.3 | |||
| Comparative example 3 | 65 | 6 | 2 | 0.3 | 0.3 | 2.5 | ||
| Comparative example 4 | 65 | 6 | 2 | 0.3 | 0.3 | 2.5 |
Table 2
Claims (10)
1. the catalyst of dehydrogenation of ethylbenzene to styrene, counted with parts by weight and be made up of following component：
65~95 parts of Fe2O3,
5~10 parts of K2O,
2~8 parts of Ce2O3,
0.1~8 part of MgO,
0.1~8 part of CaO,
0.01~4 part of ZnO,
0.01~4 part of Ni2O3；
Molybdenum or its oxide are free of in catalyst.
2. the catalyst of dehydrogenation of ethylbenzene to styrene according to claim 1, it is characterized in that the Ce in terms of parts by weight2O3
Dosage be 3~6 parts.
3. the catalyst of dehydrogenation of ethylbenzene to styrene according to claim 1, it is characterized in that the ZnO in terms of parts by weight
Dosage is 0.1~3 part.
4. the catalyst of dehydrogenation of ethylbenzene to styrene according to claim 3, it is characterized in that the ZnO in terms of parts by weight
Dosage is 0.5~2 part.
5. the catalyst of dehydrogenation of ethylbenzene to styrene according to claim 1, it is characterized in that the Ni in terms of parts by weight2O3
Dosage be 0.1~3 part.
6. the production method of styrene, ethylbenzene is carried out in the presence of being included in catalyst any one of water and claim 1 to 5
Dehydrogenation reaction obtains styrene.
7. production method according to claim 6, it is characterized in that reaction pressure is normal pressure~-0.07MPa.
8. production method according to claim 6, it is characterized in that reaction temperature is 550~650 DEG C.
9. production method according to claim 6, it is characterized in that water/ethylbenzene mass ratio is 0.6~2.5.
10. production method according to claim 6, it is characterized in that ethylbenzene liquid volume air speed is 0.3~1.0h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410355433.9A CN105312059B (en) | 2014-07-24 | 2014-07-24 | The catalyst of dehydrogenation of ethylbenzene to styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410355433.9A CN105312059B (en) | 2014-07-24 | 2014-07-24 | The catalyst of dehydrogenation of ethylbenzene to styrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105312059A CN105312059A (en) | 2016-02-10 |
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