CN101422735B - Effective styrene preparation catalyst by dehydrogenation of ethyl benzene and preparation method thereof - Google Patents

Effective styrene preparation catalyst by dehydrogenation of ethyl benzene and preparation method thereof Download PDF

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CN101422735B
CN101422735B CN2007101766817A CN200710176681A CN101422735B CN 101422735 B CN101422735 B CN 101422735B CN 2007101766817 A CN2007101766817 A CN 2007101766817A CN 200710176681 A CN200710176681 A CN 200710176681A CN 101422735 B CN101422735 B CN 101422735B
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CN101422735A (en
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王涛
王继龙
辛国萍
梁玉龙
颉伟
李晓艳
陈跟平
陈红
曾令志
曹风霞
李慧文
张茵
龚光碧
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China Petroleum and Natural Gas Co Ltd
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Abstract

The invention relates to a high-efficiency ethylbenzene dehydrogenation catalyst for producing ethylene and a preparation method thereof. The invention adds a Cu-Zn-Pb oxide compound into the catalyst with the main system of Fe-K-Ce-Mo-Mg (or Ca, Mg-Ca), prepares at least one oxide of titanium, zirconium or hafnium and at least one oxide of manganese, stannum, cobalt or lanthanum, to produce the catalyst by dry mixing, molding and activating. Under the condition of the temperature of 620 DEG C, the speed space velocity of 1.0 per hour and the water and oil weight ratio of 2.0, the catalyst can reach the transformation rate of over 80.20 percent and the selectivity of over 95.30 percent, is characterized by high selectivity and high stability when keeping the catalyst activity simultaneously, and better solves current industrial application problem.

Description

A kind of Catalysts and its preparation method of ethyl benzene dehydrogenation preparation of styrene
Technical field
The present invention relates to a kind of Catalysts and its preparation method of efficient ethyl benzene dehydrogenation preparation of styrene, this catalyst also can be used for cumene, p-Methylisopropylbenzene dehydrogenation system isopropenylbenzene and to the methyl isopropyl alkenyl benzene.
Background technology
The most devices of the styrene in the whole world all adopt the catalytic dehydrogenation method to produce at present, in several generations, gone through in the development of dehydrogenation, developed into general Fe-series catalyst at present by former zinc system catalyst, the Fe-series catalyst that contains chromium is eliminated owing to chromium easily pollutes environment, the substitute is iron-potassium-cerium-molybdenum series.Ethyl benzene dehydrogenation preparation of styrene belongs to heat absorption, increases molecular reaction, commercial plant generally adopts high-temperature heat insulation negative reaction device, in 580～640 ℃ temperature range, activity of such catalysts increases substantially with the rising of temperature, be subjected to the influence of energy consumption and material, the temperature of reactor generally is controlled at 620～640 ℃, but high temperature is accompanied by the generation of more side reaction, make ethylbenzene conversion generate cinnamic selectivity and reduce greatly, also generally maintain about 15～20 months the service life of catalyst.For this reason, when improving catalyst activity, improve developing direction and the research focus that selection of catalysts, stability and life-span become this catalyst.
Reported vanadium in the United States Patent (USP) 4098723,4052338, cobalt optionally improves iron-potassium-chromium System Catalyst, pointed out in catalyst, to add the compound of a spot of vanadium and cobalt, not only can improve the stability of catalyst, and improve cinnamic yield.After United States Patent (USP) 4144197 had been reported vanadium, cobalt adding dehydrogenation, its conversion ratio was under 70% situation, and selection of catalysts is about 94%.After European patent EP 5,025 10 is reported in and adds titanium dioxide in iron-potassium-cerium-molybdenum-calcium system, under the situation that keeps high conversion, selectivity increases, under 620 ℃ of temperature, 2.0 water-oil factors, 1.0 air speed conditions, conversion of ethylbenzene reaches 78.37%, the high selectivity 95.19% of styrene.
Chinese patent CN1443738 report adds the nanometer ferro oxide component solution problem that catalyst activity is not high, selectivity is on the low side by adopting in iron-potassium-cerium-molybdenum System Catalyst.Chinese patent CN1470325 has reported and added vanadium, cobalt, manganese, titanium oxide combination in iron-potassium-cerium-molybdenum-calcium system, and these four kinds of oxides have significantly increased selection of catalysts when keeping catalyst activity in optimum addition scope.Chinese patent CN1810367 reported in iron-potassium-cerium-molybdenum-calcium-calcium system adopt potassium oxide in the oxide that adds an amount of niobium, the control catalyst content in the technical scheme below 11%, solved not high, the low problem of selectivity especially of low potassium catalyst activity preferably.Chinese patent CN1810368 has reported to adopt in iron-potassium-cerium-molybdenum system and has added zirconium, tin and at least a technical scheme that is selected from the combination of oxides of calcium, manganese, tungsten, has solved the problem that accessory substance is many, selectivity is low preferably.Chinese patent CN1883796 has reported and has adopted interpolation 0.1～5% to be selected from the technical scheme of oxide at least a among Y, Eu, Gd, Tb, Dy, the Yb in iron-potassium-cerium-molybdenum system, solved catalyst activity preferably, selectivity of styrene is not high enough, the problem that the styrene yield is on the low side.
Summary of the invention
Shortcomings such as it is not high to the objective of the invention is to overcome in the commercial Application catalyst activity, and the styrene yield is not high, selectivity is not high and the life-span is long are at 620 ℃, liquid air speed 1.0h -1, the water weight of oil is than making ethylbenzene dehydrogenation generate cinnamic conversion ratio 〉=80.20%, selectivity 〉=95.30% under 2.0 the process conditions, obtained performance stable oxide catalyst.
For solving the problems of the technologies described above, the present invention adopts following technical scheme, and a kind of catalyst of efficient ethyl benzene dehydrogenation preparation of styrene is 100 parts in catalyst weight, comprises following component:
A) 35～88 parts ferriferous oxide is with Fe 2O 3Meter;
B) 5～35 parts potassium oxide is with K 2The O meter;
C) 3～20 parts cerium oxide is with Ce 2O 3Meter;
D) 1～10 part molybdenum oxide is with MoO 3Meter;
E) 1～10 part calcium and/or magnesium oxide are respectively in CaO, MgO;
F) 0.1～10 part Cu oxide is in CuO;
G) 0.01～5 part zinc oxide is in ZnO;
H) 0.001～5 part lead oxides is with PbO 2Meter;
I) oxide of 0.001～0.5 part of titanium, zirconium, hafnium, can be wherein one or more, respectively with TiO 2, ZrO 2, H fO 2Meter;
J) oxide of 0.001～0.5 part of manganese, tin, cobalt, lanthanum, can be wherein one or more, respectively with MnO 2, SnO 2, Co 2O 3, La 2O 3Meter.
Do not get rid of in the catalyst of the present invention and add other catalyst usual auxiliaries.As also adding 1～10 part reinforcing agent in the catalyst, as cement etc.
In above-mentioned each constituent content, iron can iron oxide red and the form of iron oxide yellow add, wherein the weight content ratio of iron oxide red and iron oxide yellow is 0.5～2.5, and optimal proportion is 0.8～1.8, and the total content of iron oxide red and iron oxide yellow is with 50～75 parts of the bests;
Potassium adds K with the form of sylvite 2The content of O is with 8～20 parts of the bests, K 2O content is low excessively, and activity of such catalysts is on the low side, the too high performance that then influences catalyst etc.;
Cerium adds Ce with the form of oxide or salt 2O 3Content with 5～15 parts of the bests, content is low excessively, it is not obvious that catalyst activity improves, too high levels is little to the catalyst performance effect;
Molybdenum adds MoO with the form of oxide or salt 3Content with 3～8 parts of the bests, content is low excessively, it is not obvious that catalyst selectivity improves, too high levels is little to the catalyst performance effect;
Calcium and/or magnesium add with the form of oxide or salt, and the content of CaO and/or MgO can catalytic water gas shift react the knot carbon that reduces catalyst with 1～7 part of the best, makes catalyst obtain higher activity and selectivity;
Copper adds with the form of oxide or salt, and the content of CuO is with 0.1～3 part of the best, and the oxidisability of its metal cation is in Fe 2+With Fe 3+Between, improve the stability of catalyst, thereby improve life of catalyst;
Zinc adds with the form of oxide or salt, and the content of ZnO is that activity of such catalysts promotes auxiliary agent with 0.1～3 part of the best, can improve activity of such catalysts and stability;
Plumbous form with oxide or salt adds PbO 2Content with 0.01～1 part of the best, be the auxiliary agent that promotes the activated centre, content is too low, activity of such catalysts is promoted not obvious, content is too high, cost up;
Copper, zinc and lead all are to add component, in the catalyst of Fe-K-Ce-Mo-Mg (Ca or Mg-Ca) for main body system, synergy between the Cu-Zn-Pb combination of oxides can improve the stability of catalyst significantly, promote the formation of activated centre crystalline phase, be the auxiliary agent that improves catalyst activity and stability, indispensable.
Titanium, zirconium, hafnium add with the form of oxide or salt, are structural promoters, and content is in corresponding oxide, and total addition is with 0.005～0.1 part of the best.Manganese, tin, cobalt, lanthanum add with the form of oxide or salt, are structural promoters, and content is in corresponding oxide, and total addition is with 0.005～0.1 part of the best.
It is the preparation method of dehydrogenation that Preparation of catalysts method of the present invention can adopt conventional iron, as: with catalyst component elder generation dry mixed 0.5～4 hour, adding deionized water mediated 0.5～4 hour, after the moulding, through 60～150 ℃ of dryings, 250～900 ℃ of activation burnings promptly became catalyst of the present invention in 6～18 hours.The drying of catalyst, activation condition adopt method in common, the present invention is not particularly limited, same the present invention is the shape of special defined catalyst not also, recommends catalyst to be preferably extrusion pelletizing moulding, as being the cylindrical catalyst of Φ (2.8～3.3) mm * (5～7) mm.
Catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of the present invention under certain process conditions, also can be used for cumene, p-Methylisopropylbenzene dehydrogenation system isopropenylbenzene and to the methyl isopropyl alkenyl benzene.
The present invention is by adding the Cu-Zn-Pb combination of oxides in the catalyst that for main body is at Fe-K-Ce-Mo-Mg (Ca or Mg-Ca), the oxide of the oxide of at least a titanium of assembly, zirconium, hafnium and at least a manganese, tin, cobalt, lanthanum again, make catalyst by dry mixed, moulding, activation, at 620 ℃, liquid air speed 1.0h -1, the water weight of oil is than under 2.0 the condition, conversion ratio can reach more than 80.20%, selectivity can reach more than 95.30%, when keeping catalyst activity, has characteristics such as selectivity height, stable height, has solved the problem in the present commercial Application preferably.
Below by embodiment and Comparative Examples the present invention is further set forth.
The specific embodiment
Catalyst carries out activity rating at the isotherm formula fixed bed, and it is as follows to estimate process description:
By the requirement of process conditions, ethylbenzene and water are pumped into blender with metering respectively, enter beds after preheating, vaporization.Product after the dehydrogenation enters cooler through quencher, carries out gas-liquid separation through gas-liquid separator, liquid product through oil water separator with oil and moisture from, with the composition of liquid-phase chromatographic analysis oil phase.Wherein reaction tube is a stainless steel tube, but loading catalyst 100ml.Conversion of ethylbenzene and selectivity of styrene are calculated as follows:
Figure S2007101766817D00052
Embodiment 1
With 199.0 gram iron oxide reds, 151.0 gram iron oxide yellow, 88.0 gram potash, 18.0 gram ammonium molybdate, 15.0 gram magnesia, 5.0 gram calcium oxide, 5.0 gram cupric oxide, 2.5 gram zinc oxide, 0.5 gram brown lead oxide, 0.05 gram hafnium oxide, mix after 2 hours 35.0 gram cement adds to do in the kneader, 106.0 gram cerous nitrates and 0.05 gram cobalt nitrate are added wherein after with deionized water dissolving, mediated 2 hours, take out after making material be kneaded into squeezable paste, through extruded moulding, disconnected bar operation, make the cylindrical catalyst of Φ (2.8～3.3) mm * (5～7) mm, drying is 4 hours under 90～120 ℃, place muffle furnace, 300～700 ℃ of calcinings 10 hours, after calcining 4 hours under 770 ℃, naturally cooling obtains finished catalyst and carries out activity rating.The 100ml catalyst is packed in the isothermal boiler tube, at 620 ℃, liquid air speed 1.0h -1, the water weight of oil is than continuously estimating 1000 hours under 2.0 the condition, initial activity and lifetime results see Table 2 and table 3 respectively.
Embodiment 2
Method by embodiment 1 prepares catalyst, the amount of magnesia, cupric oxide, zinc oxide, brown lead oxide is constant, different is, iron oxide red 184.0 grams, iron oxide yellow 140.0 grams, potash 110.0 grams, cerous nitrate 132.0 grams, ammonium molybdate 24.5 grams, calcium oxide 20.0 grams, titanium dioxide 0.05 gram, manganese dioxide 0.05 gram, cement 20.0 grams, drying is 3 hours under 70～120 ℃, places muffle furnace, 340～800 ℃ of calcinings 7 hours, calcining is after 2 hours down at 800 ℃, and cooling obtains finished catalyst and carries out activity rating naturally.Evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, performance is very stable.
Embodiment 3
Method by embodiment 1 prepares catalyst, different is iron oxide red 178.6 grams, iron oxide yellow 203.5 grams, potash 73.4 grams, cerous nitrate 79.4 grams, ammonium molybdate 36.0 grams, magnesium hydroxide 21.8 grams, cupric oxide 2.5 grams, zinc oxide 5.0 grams, brown lead oxide 2.5 grams, zirconium dioxide 0.1, tin ash 0.1 gram, cement 15.0 grams, evaluation method is with embodiment 1, the initial activity evaluation result of catalyst sees Table 2, life test showed in 1000 hours, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 4
Method by embodiment 1 prepares catalyst, and different is iron oxide red 148.0 grams, iron oxide yellow 168.6, potash 132.0 grams, ammonium molybdate 18.0 grams, calcium carbonate 35.7 grams, cupric oxide 2.5 grams, zinc oxide 2.5 grams, brown lead oxide 2.0 grams, titanium dioxide 0.1 gram, manganese dioxide 0.1 gram, tin ash 0.1 gram, lanthanum nitrate 0.1 gram (same cobalt nitrate, water-soluble then add again), cement 10.0 grams, in kneader, mediated 3 hours, evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 5
Method by embodiment 1 prepares catalyst, different is iron oxide red 189.8 grams, iron oxide yellow 144.2 grams, potash 88.0 grams, cerium oxalate 107.6 grams, ammonium molybdate 30.6 grams, calcium oxide 15.0 grams, magnesium carbonate 3 1.5 grams, cupric oxide 4.0 grams, zinc oxide 4.0 grams, brown lead oxide 4.0 grams, titanium dioxide 0.05 gram, hafnium oxide 0.05 gram, zirconium dioxide 0.05 gram, manganese dioxide 0.05 gram, tin ash 0.05 gram, cobalt nitrate 0.05 gram (water-soluble back adds), lanthanum nitrate 0.05 gram (water-soluble back adds), cement 10.0 grams, evaluation method is with embodiment 1, and the initial activity evaluation result of catalyst sees Table 2,1000 hours life tests and shows, as embodiment 1 catalyst, catalyst performance stabilised.
Embodiment 6
Press the formulation catalyst of embodiment 1, different is that material was done in kneader mixed 2.5 hours, back kneading 1.5 hours is dissolved in water, cylindrical catalyst behind extrusion, disconnected bar is following dry 4 hours at 80～120 ℃, after placing muffle furnace to calcine 4 hours down respectively at 4 hours, 820 ℃ of 580 ℃ of following calcinings, naturally cooling obtains finished catalyst and carries out activity rating.Evaluation method the results are shown in Table 2 with embodiment 1.
The percentage composition of each component tabulation among table 1 embodiment
Form % Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Fe 2O 3 65.00? 60.00? 70.00? 58.00? 62.00?
K 2O 12.00? 15.00? 10.00? 18.00? 12.00?
Ce 2O 3 8.00? 10.00? 6.00? 12.00? 10.00?
MoO 3 3.00? 4.00? 6.00? 3.00? 5.00?
CaO? 1.00? 4.00? -? 4.00? 3.00?
MgO? 3.00? 3.00? 3.00? -? 3.00?
CuO? 1.00? 1.00? 0.50? 0.50? 0.80?
ZnO? 0.50? 0.50? 1.00? 0.50? 0.80?
PbO 2 0.10? 0.10? 0.50? 0.40? 0.80?
TiO 2 -? 0.01? -? 0.02? 0.01?
H fO 2 0.01? -? -? -? 0.01?
ZrO 2 -? -? 0.02? -? 0.01?
MnO 2 -? 0.01? -? 0.02? 0.01?
Co 2O 3 0.01? -? -? -? 0.01?
SnO 2 -? -? 0.02? 0.02? 0.01?
La 2O 3 -? -? -? 0.02? 0.01?
Comparative example 1
Method according to embodiment 1 prepares catalyst, and different is not add zinc oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 2
Method according to embodiment 2 prepares catalyst, the different cupric oxide that do not add, evaluation method is with embodiment 1, evaluation result sees Table 2.
Comparative example 3
Method according to embodiment 3 prepares catalyst, and different is not add brown lead oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 4
Method according to embodiment 4 prepares catalyst, and different is not add cupric oxide, zinc oxide and brown lead oxide, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
Comparative example 5
Method according to embodiment 5 prepares catalyst, and different is not add ammonium molybdate and cerium oxalate, and evaluation method is with embodiment 1, and evaluation result sees Table 2.
The evaluation result of table 2 embodiment, comparative example gained catalyst
Example Reaction temperature (℃) Liquid air speed (h -1) Water-oil factor (mass ratio) Conversion of ethylbenzene % Selectivity of styrene % Styrene yield %
Embodiment 1 620? 1.0? 2.0? 80.65? 95.32? 76.88?
Embodiment 2 620? 1.0? 2.0? 80.36? 95.51? 76.75?
Embodiment 3 620? 1.0? 2.0? 80.41? 95.78? 77.02?
Embodiment 4 620? 1.0? 2.0? 80.28? 95.62? 76.76?
Embodiment 5 620? 1.0? 2.0? 80.92? 95.37? 77.17?
Embodiment 6 620? 1.0? 2.0? 80.82? 95.34? 77.05?
Comparative example 1 620? 1.0? 2.0? 78.49? 94.82? 74.42?
Comparative example 2 620? 1.0? 2.0? 78.26? 94.77? 74.17?
Comparative example 3 620? 1.0? 2.0? 78.08? 94.32? 73.65?
Comparative example 4 620? 1.0? 2.0? 75.29? 93.63? 70.49?
Comparative example 5 620? 1.0? 2.0? 71.28? 93.59? 66.71?
Life of catalyst test data among table 3 embodiment 1
Evaluation time (hour) Reaction temperature (℃) Liquid air speed (h -1)? Water-oil factor (mass ratio) Conversion of ethylbenzene % Selectivity of styrene % Styrene yield %
100? 620? 1.0? 2.0? 81.34? 94.91? 77.20?
200? 620? 1.0? 2.0? 81.09? 95.69? 77.59?
300? 620? 1.0? 2.0? 80.49? 95.88? 77.17?
400? 620? 1.0? 2.0? 80.46? 95.92? 77.18?
500? 620? 1.0? 2.0? 80.35? 95.69? 76.60?
600? 620? 1.0? 2.0? 80.78? 95.50? 77.14?
700? 620? 1.0? 2.0? 80.74? 95.52? 77.12?
800? 620? 1.0? 2.0? 81.05? 95.48? 77.39?
900? 620? 1.0? 2.0? 80.98? 95.51? 77.34?
1000? 620? 1.0? 2.0? 80.76? 95.56? 77.17?

Claims (15)

1. the catalyst of an ethyl benzene dehydrogenation preparation of styrene is characterized in that in catalyst weight be 100 parts, is made up of following component:
A) 35～88 parts ferriferous oxide is with Fe 2O 3Meter;
B) 5～35 parts potassium oxide is with K 2The O meter;
C) 3～20 parts cerium oxide is with Ce 2O 3Meter;
D) 1～10 part molybdenum oxide is with MoO 3Meter;
E) 1～10 part calcium and/or magnesium oxide are respectively in CaO, MgO;
F) 0.1～10 part Cu oxide is in CuO;
G) 0.01～5 part zinc oxide is in ZnO;
H) 0.001～5 part lead oxides is with PbO 2Meter;
I) one or more in the oxide of 0.001～0.5 part of titanium, zirconium, hafnium are respectively with TiO 2, ZrO 2, H fO 2Meter;
J) one or more in the oxide of 0.001～0.5 part of manganese, tin, cobalt, lanthanum are respectively with MnO 2, SnO 2, Co 2O 3, La 2O 3Meter;
K) 1～10 part reinforcing agent.
2. catalyst according to claim 1 is characterized in that ferriferous oxide adds with the form of iron oxide red and iron oxide yellow.
3. catalyst according to claim 2, the weight content ratio that it is characterized in that iron oxide red and iron oxide yellow is 0.5～2.5.
4. catalyst according to claim 2, the weight content ratio that it is characterized in that iron oxide red and iron oxide yellow is 0.8～1.8.
5. catalyst according to claim 2, the total content that it is characterized in that iron oxide red and iron oxide yellow is 50～75 parts.
6. catalyst according to claim 1 is characterized in that K in the catalyst 2The content of O is 8～20 parts.
7. catalyst according to claim 1 is characterized in that Ce in the catalyst 2O 3Content be 5～15 parts.
8. catalyst according to claim 1 is characterized in that MoO in the catalyst 3Content be 3～8 parts.
9. catalyst according to claim 1 is characterized in that the content of CaO in the catalyst and/or MgO is 1～7 part.
10. catalyst according to claim 1, the content that it is characterized in that CuO in the catalyst is 0.1～3 part.
11. catalyst according to claim 1, the content that it is characterized in that ZnO in the catalyst is 0.1～3 part.
12. catalyst according to claim 1 is characterized in that PbO in the catalyst 2Content be 0.01～1 part.
13. catalyst according to claim 1, the total content that it is characterized in that titanium in the catalyst, zirconium, hafnium in corresponding oxide, are 0.005～0.1 part.
14. catalyst according to claim 1, the total content that it is characterized in that manganese in the catalyst, tin, cobalt, lanthanum in corresponding oxide, are 0.005～0.1 part.
15. described Preparation of catalysts method of claim 1, it is characterized in that catalyst component elder generation dry mixed 0.5～4 hour is added deionized water and mediated 0.5～4 hour, after the moulding, through 60～150 ℃ of dryings, 250～900 ℃ of activation burnings promptly became catalyst in 6～18 hours.
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