CN1431047A - Catalyst for preparing ethenylbenzene as well as its preparing method and application - Google Patents
Catalyst for preparing ethenylbenzene as well as its preparing method and application Download PDFInfo
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- CN1431047A CN1431047A CN 01130480 CN01130480A CN1431047A CN 1431047 A CN1431047 A CN 1431047A CN 01130480 CN01130480 CN 01130480 CN 01130480 A CN01130480 A CN 01130480A CN 1431047 A CN1431047 A CN 1431047A
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Abstract
A catalyst for preparing styrene is prepared from carrier, active component, and assistant through preparing the mixed solution of active component's precursor and assistant precursor, immersing carrier in it, drying and calcining. Its advantage is high ethylbenzene transform rate (30%) and styrene selectivity (90%).
Description
Technical field:
The invention belongs to the cinnamic catalyst of preparation, relate in particular to a series of load type platinums, iron, vanadium catalyst and and the application in ethyl benzene dehydrogenation preparation of styrene and hydrogenation of chloronitrobenzene coupled reaction.
Background technology:
Ethylbenzene catalytic dehydrogenation is the main method of producing chemical industry benzene feedstock ethene, and the catalyst of use is the ferriferous oxide that a kind of carrier-free contains co-catalyst K.Because the strong endothermic reaction that this reaction is a molecular number to increase, conversion ratio is subjected to the restriction of thermodynamical equilibrium, and high temperature, low pressure are favourable.Therefore industrial operation (conversion ratio about 70%) under near normal pressure and 600～650 ℃ of high temperature, and (mol ratio: water/ethylbenzene=10～15), its effect is: (1) provides energy for the dehydrogenation reaction of heat absorption will to feed a large amount of water vapours; (2) the diluting reaction system is to increase equilibrium conversion; (3) prevent coking.The shortcoming of technology is that reaction temperature and operating cost height, energy consumption are big, and economic benefit is low.
F.Bautista etc. are " catalysis communication " 1999,60 volumes, in " oxidative dehydrogenation of ethylbenzene in the presence of nitrobenzene by hydrogen transfer reaction production styrene and aniline " literary composition of 229～235 pages reported first at amorphous AlPO
4, SiO
2, Al
2O
3, a kind of natural spinelle, and the reaction result on nickel catalyst carried (20wt%).Reaction condition is: 360～460 ℃ of temperature, and catalyst amount 0.3g, the mixing sample size of ethylbenzene and nitrobenzene is 6ml/h, dilution is 30ml/min with the flow velocity of nitrogen.Wherein at amorphous AlPO
4On the catalyst, obtaining the styrene yield in the time of 420 ℃ is 5.83%, and cinnamic selectivity is 59%～82% in the time of nickel catalyst carried last 420 ℃.Also mention metallic copper as the second nickel catalyst carried metal component.Shortcoming is: catalyst and reaction do not match, and the conversion ratio of reaction and cinnamic selectivity are all relatively poor.
Summary of the invention:
Purpose of the present invention promptly is to provide a series of conversion of ethylbenzene height, and the catalyst that selectivity of styrene is high is used for ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene coupling reactions.
Catalyst of the present invention respectively consists of: carrier: active component: auxiliary agent=1g: 0.002～6.0mmol: 0～0.6mmol.
Aforesaid carrier is active carbon, γ-Al
2O
3Or silica gel.
Aforesaid active component is platinum, palladium, iron or vanadium.
Aforesaid auxiliary agent is one or more among Li, Na, K, Cs, Mg, Ca, Ba, Co, Mo, Ni, Ti, Mn, Zn, Zr, W, La, the Ce.But add the Acidity of Aikalinity on auxiliary agent regulating catalyst surface, make and suppress the easier absorption of reactant ethylbenzene and carry out dehydrogenation reaction the cracking reaction of ethylbenzene simultaneously, thereby help improving the reactivity and the cinnamic selectivity of catalyst.
The specific area of aforesaid active carbon is 900～1500m
2/ gram, specific pore volume are 0.3～2.0 milliliter/gram, and average pore size is 0.4～3nm.
Aforesaid γ-Al
2O
3Specific area be 150～300m
2/ gram, specific pore volume are 0.3～1.2 milliliter/gram, average pore size 0.45～10nm.
Aforesaid silica gel specific area is 200～600m
2/ gram, specific pore volume are 0.3～0.6 milliliter/gram, and average pore size is 1.5～10nm.
It is as follows that the present invention does not have auxiliary agent Preparation of catalysts method:
(1) presoma with active component is made into the solution that concentration is 0.0001～6mol/l;
(2) by above-mentioned each component ratio, carrier impregnation in active component solution, was left standstill 18～36 hours;
(3) 110～120 ℃ of dryings 4～6 hours;
(4) under nitrogen protection,, go into drier and make no auxiliary agent catalyst in 450～650 ℃ of roastings 4～5 hours.
The present invention has the auxiliary agent method for preparing catalyst as follows:
(1) presoma with active component and auxiliary agent is made into the solution that concentration is 0.0001～6mol/l;
(2) by above-mentioned each component ratio, carrier impregnation is gone in the mixed solution of active component and auxiliary agent, left standstill 18～36 hours;
(3) 110～120 ℃ of dryings 4～6 hours;
(4) under nitrogen protection,, go into drier and made the auxiliary agent catalyst in 450～650 ℃ of roastings 4～5 hours.
The presoma of described platinum is a chloroplatinic acid; The presoma of described palladium is a palladium bichloride; The presoma of described vanadium is an ammonium metavanadate; The presoma of the presoma of the presoma of the presoma of the presoma of the presoma of the presoma of described iron, the presoma of lithium, sodium, the presoma of potassium, caesium, the presoma of magnesium, calcium, the presoma of barium, cobalt, the presoma of nickel, titanium, the presoma of manganese, zinc, the presoma of zirconium, the presoma of tungsten, the presoma of lanthanum, the presoma of cerium are nitrate, sulfate, acetate; The presoma of described molybdenum is an ammonium molybdate.
Catalyst of the present invention is used for ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene and produces cinnamic method and comprise the steps:
1. the preliminary treatment of catalyst has three kinds of methods
A. catalyst is put into reactor middle part, under inert atmosphere 350～450 ℃, closed inert gas valve from room temperature heat-activated catalyst to reaction temperature;
B. catalyst is put into reactor middle part, under inert atmosphere 350～450 ℃,, and then, closed inert gas valve with inert gas high-speed purging 0.5 hour with pure hydrogen reduction 2 hours from room temperature heat-activated catalyst to reaction temperature;
C. catalyst is put into the reactor middle part, under inert atmosphere 350～450 ℃ from room temperature heat-activated catalyst to reaction temperature, with pure hydrogen reduction after 2 hours, purged 0.5 hour with the inert gas high-speed again, used air oxidation then 0.5 hour, purged 0.5 hour with the inert gas high-speed again, close inert gas valve.
2. ethylbenzene and nitrobenzene are pressed ethylbenzene: nitrobenzene=1～5: 1 mol ratio feeds in the reactor, is 1.17～12h in the liquid air speed
-1, reaction temperature is 350～450 ℃, reacts under the condition of normal pressure, makes styrene.
Analytical method of the present invention is: product is after cold-trap is collected, by chromatogram fid detector Analysis and Identification on the OV-101 packed column.
Advantage of the present invention:
Catalyst provided by the present invention can be complementary with ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene coupling reactions well, realizes high conversion, high selectivity.According to calculation of thermodynamic equilibrium, ethylbenzene dehydrogenation reaction has only 3.5% 400 ℃ equilibrium conversion, and at the catalyst that is used for ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene coupling reactions provided by the present invention, conversion of ethylbenzene can reach more than 30%, and selectivity of styrene is all more than 90%.
The specific embodiment:
It is 942m that embodiment 1 accurately takes by weighing 120 ℃ of oven dry, specific areas
2Active carbon (20～40 order) 2.0000g of/gram is accurately measured the Fe (NO of 1.50mol/L with pipette
3)
3Solution 4.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain the catalyst that Fe content is the 3.0mmol/g active carbon, note is made catalyst A.It is a) that catalyst gives treatment conditions, is that 3: 1 ethylbenzene and nitrobenzene is raw material with mol ratio, and reaction temperature is 400 ℃, and the air speed of reactant is 2.35h
-1Analytical method: product is after cold-trap is collected, by chromatogram fid detector Analysis and Identification on the OV-101 packed column.The results are shown in Table 1.
It is 150m that embodiment 2 accurately takes by weighing 120 ℃ of oven dry, specific areas
2γ-the Al of/gram
2O
3(20～40 order) 2.0000g is accurately measured the Fe (NO of 1.50mol/L with pipette
3)
3Solution 4.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven; Measure the Fe (NO of 1.50mol/L again
3)
3Solution 4.00ml, the double-steeping carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 650 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtaining Fe content is 6.0mmol/g γ-Al
2O
3Catalyst, note is made catalyst B.Other condition is with embodiment 1.
It is 1200m that embodiment 3 accurately takes by weighing 120 ℃ of oven dry, specific areas
2Active carbon (20～40 order) 2.0000g of/gram is accurately measured the Fe (NO of 1.50mol/L with pipette
3)
3The NaNO of solution 3.60ml and 1.50mol/L
3Solution 0.40ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain Fe content 2.7mmol/g active carbon, sodium content is the FeNa/AC catalyst of 0.3mmol/g active carbon, and note is made catalyst C.The air speed of reactant is 1.17h
-1Other condition is with embodiment 1.
It is 300m that embodiment 4 accurately takes by weighing 120 ℃ of oven dry, specific areas
2γ-the Al of/gram
2O
3(20～40 order) 2.0000g is accurately measured the Fe (NO of 1.50mol/L with pipette
3)
3Ni (the NO of solution 2.40ml and 0.010mol/L
3)
2Solution 0.24ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 650 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain Fe content 1.8mmol/g active carbon, nickel content is 0.012mmol/g γ-Al
2O
3FeNi/ γ-Al
2O
3Catalyst, note is made catalyst D.Other condition is with embodiment 1.
It is 600m that embodiment 5 accurately takes by weighing 120 ℃ of oven dry, specific areas
2Silica gel (20～40 order) 2.0000g of/gram is accurately measured the NH of 0.579mol/L with pipette
4VO
3Solution 3.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain the V/ silica-gel catalyst, V content is 0.87mmol/g silica gel, and note is made catalyst E.Other condition is with embodiment 1.
It is 942m that embodiment 6 accurately takes by weighing 120 ℃ of oven dry, specific areas
2The active carbon 2.0000g of/gram is accurately measured the NH of 0.579mol/L with pipette
4VO
3La (the NO of solution 3.00ml and 0.503mol/L
3)
3Solution 0.20ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtaining V content is the 0.87mmol/g active carbon, and lanthanum content is the VLa/AC catalyst of 0.05mmol/g active carbon, and note is made catalyst F.The mol ratio of ethylbenzene and nitrobenzene is 5: 1, and the air speed of reactant is 4.7h
-1Other condition is with embodiment 1.
It is 1500m that embodiment 7 accurately takes by weighing 120 ℃ of oven dry, specific areas
2The active carbon 2.0000g of/gram is accurately measured the NH of 0.579mol/L with pipette
4VO
3Ce (the NO of solution 3.00ml and 0.899mol/L
3)
3Solution 0.20ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtaining V content is the 0.87mmol/g active carbon, and cerium content is the VCe/AC catalyst of 0.09mmol/g active carbon, and note is made catalyst G.The mol ratio of ethylbenzene and nitrobenzene is 1: 1, and the air speed of reactant is 11.75h
-1Other condition is with embodiment 1.
It is 942m that embodiment 8 accurately takes by weighing 120 ℃ of oven dry, specific areas
2(20～40 order) active carbon 2.0000g of/gram, note is made catalyst H.Other condition is with embodiment 1.
It is 942m that embodiment 9 accurately takes by weighing 120 ℃ of oven dry, specific areas
2/ restrain (20～40 order) active carbon 2.0000g, accurately measure the H of 0.000738mol/L with pipette
2PtCl
6Solution 3.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain the Pt/AC catalyst, Pt content 0.00110mmol/g active carbon, note is made catalyst I.Other condition is with embodiment 1.
Embodiment 10 is as catalyst I as described in the embodiment 9, and the preparation method is with embodiment 9.It is b that catalyst gives treatment conditions), other condition is with embodiment 1.
Embodiment 11 is as catalyst I as described in the embodiment 9, and the preparation method is with embodiment 9.It is c that catalyst gives treatment conditions), other condition is with embodiment 1.
It is 942m that embodiment 12 accurately takes by weighing 120 ℃ of oven dry, specific areas
2Active carbon (20～40 order) 2.0000g of/gram is accurately measured the H of 0.000137mol/L with pipette
2PtCl
6Solution 3.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain the catalyst of Pt content 0.000205mmol/g active carbon, note is made catalyst J.It is c that catalyst gives treatment conditions), other condition is with embodiment 1.
It is 400m that embodiment 13 accurately takes by weighing 120 ℃ of oven dry, specific areas
2(20～40 order) silica gel 2.0000g of/gram is accurately measured the H of 0.0137mol/L with pipette
2PtCl
6Solution 3.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain the Pt/ silica-gel catalyst, Pt content 0.0205mmol/g silica gel, note is made catalyst K.It is c that catalyst gives treatment conditions), other condition is with embodiment 1.
It is 942m that embodiment 14 accurately takes by weighing 120 ℃ of oven dry, specific areas
2Active carbon (20～40 order) 2.0000g of/gram is accurately measured the H of 0.000738mol/L with pipette
2PtCl
6Ca (the NO of solution 3.00ml and 3.00mol/L
3)
2Solution 0.20ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～6 hours in the baking oven; Measure the Ca (NO of 3.00mol/L again
3)
2Solution 0.20ml, the double-steeping carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtaining Pt content is the 0.00110mmol/g active carbon, and calcium content is the PtCa/AC catalyst of 0.60mmol/g active carbon, and note is made catalyst L.Other condition is with embodiment 1.
It is 942m that embodiment 15 accurately takes by weighing 120 ℃ of oven dry, specific areas
2(20～40 order) active carbon 2.0000g of/gram is accurately measured the H of 0.000738mol/L with pipette
2PtCl
6La (the NO of solution 3.00ml and 0.503mol/L
3)
3Solution 0.20ml evenly mixes, and impregnated carrier left standstill 24 hours altogether, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Following 500 ℃ of atmosphere, drier is gone in roasting 5 hours.Obtain Pt content 0.00110mmol/g active carbon, lanthanum content is the PtLa/AC catalyst of 0.05mmol/g active carbon, and note is made catalyst M.It is c that catalyst gives treatment conditions), other condition is with embodiment 1.
It is 230m that embodiment 16 accurately takes by weighing 120 ℃ of oven dry, specific areas
2(20～40 the order)-Al of/gram
2O
32.0000g, accurately measure the H of 0.00148mol/L with pipette
2PtCl
6Solution 2.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Drier is gone in the following 550 ℃ of roastings of atmosphere 4 hours.Obtain the Pt/Al catalyst, Pt content 0.00148mmol/g-Al
2O
3, note is made catalyst n.It is c that catalyst gives treatment conditions), other condition is with embodiment 1.
It is 200m that embodiment 17 accurately takes by weighing 120 ℃ of oven dry, specific areas
2/ restrain (20～40 order) silica gel 2.0000g, accurately measure the Fe (NO of 1.50mol/L with pipette
3)
3Solution 2.00ml impregnated carrier left standstill 24 hours, and 120 ℃ of dryings are 4～5 hours in the baking oven, N
2The following 650 ℃ of roastings of atmosphere 5 hours; Measure the Fe (NO of 1.50mol/L again
3)
3Solution 2.00ml, the double-steeping carrier left standstill 24 hours, and 120 ℃ of dryings are 4～6 hours in the baking oven, and drier is gone in 650 ℃ of roastings 5 hours.Obtain the Fe/ silica-gel catalyst, Fe content 3.0mmol/g silica gel, note is made catalyst O.Other condition is with embodiment 1.
Embodiment 18 accurately takes by weighing 500 ℃ of certain particle size scopes (20～40 order) after Muffle furnace activates 2 hours-aluminium oxide 2.0000g, and note is made catalyst P.Catalyst gives treatment conditions and reaction condition with embodiment 1.
Embodiment 19 is as catalyst I as described in the embodiment 9, and the preparation method is with embodiment 9.It is b that catalyst gives treatment conditions), reaction temperature is 450 ℃, other condition is with embodiment 1.
Embodiment 20 accurately takes by weighing the ultra-fine-Al of supercritical drying preparation
2O
32.0000g, accurately measure the palladium chloride solution 2.00ml impregnated carrier of 10mg/L with pipette, left standstill 24 hours, 120 ℃ of dryings are 4～5 hours in the baking oven, N
2Drier is gone in the following 500 ℃ of roastings of atmosphere 5 hours.Obtain ultra-fine Pd/Al catalyst, 1% of Pd content catalyst gross weight, note is made catalyst Q.Reaction temperature is 350 ℃, and catalyst gives treatment conditions and other condition with embodiment 1.
Catalyst A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q are that 3: 1 ethylbenzene and nitrobenzene is raw material with mol ratio, carry out ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene coupled reaction in the normal pressure continuous fixed bed reactor, the reaction result of embodiment 1 to embodiment 20 sees Table 1.Ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene coupled reaction have been realized higher conversion of ethylbenzene (can reach more than 30%) and higher selectivity of styrene (88.0%～99.9%) on above-mentioned catalyst.Table 1
Ethylbenzene conversion styrene is selected nitrobenzene to transform aniline and is selected the embodiment catalyst
Rate; %; % leads; %, %1 A 20.0 92.0 54.2 99.92 B 15.1 94.2 30.0 1003 C 24.5 93.1 60.4 1004 D 21.5 92.6 55.3 99.95 E 14.1 89.4 62.8 1006 F 15.8 94.0 97.2 99.97 G 10.4 95.3 45.7 99.98 H 30.9 98.0 45.2 99.99 I 27.5 98.6 55.3 10010 I 27.0 99.0 32.0 10011 I 33.8 99.2 72.3 99.912 J 31.9 98.9 50.3 10013 K 16.0 88.7 45.9 10014 L 23.2 98.6 45.2 99.915 M 32.9 99.0 49.8 99.916 N 20.9 98.9 75.9 99.917 O 12.4 87.4 76.2 10018 P 19.1 99.2 30.0 10019 I 36.7 95.7 79.2 10020 Q 12.3 99.4 25.3 99.9
Claims (12)
1. one kind is used to prepare cinnamic catalyst, it is characterized in that catalyst respectively consists of: carrier: active component: auxiliary agent=1g: 0.002～6.0mmol: 0～0.6mmol.
2. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 1 is characterized in that described carrier is active carbon, γ-Al
2O
3Or silica gel.
3. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 1, its feature is platinum, palladium, iron or vanadium in described active component.
4. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 1, its feature is among Li, Na, K, Cs, Mg, Ca, Ba, Co, Mo, Ni, Ti, Mn, Zn, Zr, W, La, the Ce one or more at described auxiliary agent.
5. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 2, its feature is 900～1500m in the specific area of described active carbon
2/ gram, specific pore volume are 0.3～2.0 milliliter/gram, and average pore size is 0.4～3nm.
6. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 2, its feature is at described γ-Al
2O
3Specific area be 150～300m
2/ gram, specific pore volume are 0.3～1.2 milliliter/gram, average pore size 4.5～10nm.
7. described a kind of cinnamic catalyst that is used to prepare as claimed in claim 2, its feature is 200～600m in described silica gel specific area
2/ gram, specific pore volume are 0.3～0.6 milliliter/gram, and average pore size is 1.5～10nm.
8. no auxiliary agent Preparation of catalysts method, it is as follows to it is characterized in that not having auxiliary agent Preparation of catalysts method:
(1) presoma with active component is made into the solution that concentration is 0.0001～6mol/l;
(2) in carrier: the ratio of active component=1g: 0.002～6.0mmol, in active component solution, leave standstill carrier impregnation 18～36 hours;
(3) 110～120 ℃ of dryings 4～6 hours;
(4) under nitrogen protection,, go into drier and make no auxiliary agent catalyst in 450～650 ℃ of roastings 4～5 hours.
9. one kind has auxiliary agent Preparation of catalysts method, it is characterized in that having auxiliary agent Preparation of catalysts method as follows:
(1) presoma with active component and auxiliary agent is made into the solution that concentration is 0.0001～6mol/l;
(2) in carrier: the ratio of active component: auxiliary agent=1g: 0.002～6.0mmol: 0～0.6mmol, change the mixed solution of carrier impregnation being gone into active component and auxiliary agent, left standstill 10～36 hours;
(3) 110～120 ℃ of dryings 4～6 hours;
(4) under nitrogen protection,, go into drier and made the auxiliary agent catalyst in 450～650 ℃ of roastings 4～5 hours.
10. Preparation of catalysts method as claimed in claim 8 or 9, the presoma that it is characterized in that described active constituent is that the presoma of platinum is a chloroplatinic acid; The presoma of palladium is a palladium bichloride; The presoma of vanadium is an ammonium metavanadate; The presoma of iron is nitrate, sulfate or acetate;
11. Preparation of catalysts method as claimed in claim 9, the presoma that it is characterized in that described auxiliary agent are the presoma of lithium, the presoma of sodium, the presoma of potassium, the presoma of caesium, the presoma of magnesium, the presoma of calcium, the presoma of barium, the presoma of cobalt, the presoma of nickel, the presoma of titanium, the presoma of manganese, the presoma of zinc, the presoma of zirconium, the presoma of tungsten, the presoma of lanthanum, the presoma of cerium is nitrate, sulfate or acetate; The presoma of molybdenum is an ammonium molybdate.
12. as claimed in claim 1ly describedly a kind ofly be used to prepare that cinnamic catalyst is used for ethylbenzene dehydrogenation and hydrogenation of chloronitrobenzene is produced cinnamic method, it is characterized in that comprising the steps:
(1) processing of giving of catalyst has three kinds of methods
A. catalyst is under inert atmosphere from the room temperature heat-activated to reaction temperature 350～450 ℃, closes inert gas valve;
B. catalyst is under inert atmosphere from the room temperature heat-activated to reaction temperature 350～450 ℃, with pure hydrogen reduction 2 hours, and then purges 0.5 hour with the inert gas high-speed, closes inert gas valve;
C. catalyst is under inert atmosphere from the room temperature heat-activated to reaction temperature 350～450 ℃,, purged 0.5 hour with the inert gas high-speed again after 2 hours with pure hydrogen reduction, used air oxidation then 0.5 hour, purged 0.5 hour with the inert gas high-speed again, close inert gas valve.
(2) with ethylbenzene and nitroaniline ethylbenzene: nitrobenzene=1～5: 1 mol ratio feeds in the reactor, is 1.17～12h in the liquid air speed
-1, reaction temperature is 350～450 ℃, reacts under the condition of normal pressure, makes styrene.
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| CN 01130480 CN1275688C (en) | 2001-11-23 | 2001-11-23 | Catalyst for preparing ethenylbenzene as well as its preparing method and application |
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2001
- 2001-11-23 CN CN 01130480 patent/CN1275688C/en not_active Expired - Fee Related
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| CN102441384A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas |
| CN102441384B (en) * | 2010-10-12 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin catalyst by high-activity-stability carrier-type iron-based synthetic gas |
| CN103537317A (en) * | 2013-10-15 | 2014-01-29 | 太原理工大学 | Ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN103537317B (en) * | 2013-10-15 | 2016-05-11 | 太原理工大学 | A kind of catalyst for phenylethylene dehydrogenation and preparation method thereof |
| CN104130129A (en) * | 2014-08-12 | 2014-11-05 | 西安凯立化工有限公司 | Method for preparing o-fluoroaniline by hydrogenating o-fluoronitrobenzene |
| CN104130129B (en) * | 2014-08-12 | 2016-03-23 | 西安凯立新材料股份有限公司 | A kind of o-fluoronitrobenzene Hydrogenation is for the method for adjacent fluoroaniline |
| CN106000409A (en) * | 2016-05-19 | 2016-10-12 | 陕西师范大学 | Iron-base composite oxide catalyst for producing styrene by CO2 oxidative dehydrogenation of ethylbenzene |
| CN106000409B (en) * | 2016-05-19 | 2018-12-04 | 陕西师范大学 | For CO2Aoxidize the iron-based composite oxide catalysts of ethyl benzene dehydrogenation preparation of styrene |
| CN108067223A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of catalyst that carvol processed is aoxidized for carveol molecular oxygen catalysis and preparation method thereof |
| CN108067223B (en) * | 2016-11-15 | 2020-11-24 | 中国科学院大连化学物理研究所 | Catalyst for preparing carvone by catalyzing and oxidizing carvol molecular oxygen and preparation method thereof |
| CN108659219A (en) * | 2018-06-08 | 2018-10-16 | 扬州大学 | A kind of preparation method of polyaniline |
| CN108993496A (en) * | 2018-10-30 | 2018-12-14 | 泰山医学院 | A kind of preparation method for treating dyskinesia drug ropinirole intermediate |
| CN108993496B (en) * | 2018-10-30 | 2021-01-15 | 山东第一医科大学(山东省医学科学院) | Preparation method of ropinirole intermediate for treating dyskinesia |
| CN113578359A (en) * | 2021-05-31 | 2021-11-02 | 中国科学院金属研究所 | Hollow nitrogen-doped nano carbon sphere loaded high-dispersion palladium-based catalyst, preparation method thereof and application thereof in ethylbenzene dehydrogenation |
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