CN103819295A - Application of catalyst to selective hydrogenation reaction of aromatic nitro compound - Google Patents
Application of catalyst to selective hydrogenation reaction of aromatic nitro compound Download PDFInfo
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- CN103819295A CN103819295A CN201210468132.8A CN201210468132A CN103819295A CN 103819295 A CN103819295 A CN 103819295A CN 201210468132 A CN201210468132 A CN 201210468132A CN 103819295 A CN103819295 A CN 103819295A
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Abstract
The invention discloses the application of a catalyst to the selective hydrogenation reaction of an aromatic nitro compound. Large-specific surface area iron oxide is used as a carrier of the catalyst, one or more than two of VIII-group or IB-group metals are used as active ingredients of the catalyst, and a co-precipitation method or a dipping method is used for preparing the catalyst, wherein the content of the active ingredients in the catalyst is 0.01 to 20 weight percent. The catalyst has high conversion rate and selectivity for the selective hydrogenation of the aromatic nitro compound; compared with a conventional industrial synthesis route for the selective hydrogenate of the aromatic nitro compound, a reaction process provided by the invention has the remarkable advantages of environment friendliness, simplicity in operation, low cost and the like.
Description
Technical field
The present invention relates to the application of a kind of catalyzer in aromatic nitro compound selective hydrogenation.
Background technology
Aromatic nitro compound selective hydrogenation obtains corresponding functionalization aniline important application in many aspects, such as at aspects such as agricultural chemicals, medicine, dye well high molecular polymers.For the hydrogenation of simple aromatic nitro compound, there is a proven technique industrial, but when the group that is vattability for substituting group, while existence as carbon-carbon double bond, the two keys of carbon carbon triple bond carbon oxygen, carbon nitrogen triple bond etc., optionally by nitroreduction, and retain two keys not by hydrogenation, an or challenging problem.Industrial, for the selective hydrogenation of the aromatic nitro compound that contains vattability group, the general reductive agent that adopts metering, as adopted Na
2s
2o
4, add Fe, Zn, Sn etc. as reductive agent in ammoniacal liquor, but such reductive agent produces the waste of a mole to I haven't seen you for ages in obtaining the target product of a mole, in order to overcome this shortcoming, investigators are take hydrogen as reductive agent, by PbO or H
3pO
2add on loaded Pt catalyzer, although reduced activity, improved for the selectivity of target product, but such catalyzer can produce phenylhydroxylamine intermediate product, even the danger that this by product also may be blasted under very low level.Investigator finds in this catalyst system, to add respectively molysite or alum salt this intermediate product can be converted into target product, but residual a large amount of transition metal salt in the rear solution of reaction, follow-up complex disposal process, is not very economical and environmental protection.Therefore for this class, a kind of heterogeneous catalyst with high reactivity, highly selective is found in anti-emergency requirement.
Many patents and Introduction of Literatures selective hydrogenation load type gold and the platinum catalyst of aromatic nitro compound, different with carrier and preparation method, its activity is also not quite similar.
Document 1 (WO2007116111-A1) is found Au/TiO
2and Au/Fe
2o
3catalyzer shows good selectivity in the selective hydrogenation of aromatic nitro compound, and author studies and finds that the reason of highly selective is that the nitro of aromatic nitro compound can be preferentially adsorbed on Au and TiO
2the interface of carrier, thus nitro is preferentially reduced, show high selectivity.
Document 2 (J.Phys.Chem.C 2009,113,17803-17810) has been prepared Au/Al by the method for sol deposition
2o
3catalyzer, equally to having shown good selectivity and specific activity Au/TiO in such selective hydrogenation
2high.But the shortcoming of Au catalyzer is the ability of dissociating to hydrogen, and therefore the condition of reaction is all harsher, and temperature of reaction is more than 100 ℃, and pressure is also more than 1Mp.
Document 3 (Adv.Synth.Catal.2011,353,1260-1264) adopts one kettle way to prepare a kind of porous ion multipolymer and supports Pt catalyzer, and the loading of Pt is 4.9wt%, and the Pt Nanoparticle Size obtaining is 2-4nm.Be at room temperature R=F, Cl, Br, I, CHO, CN, NH to substituting group
2, CH
3cO, OH etc. show high activity and selectivity, but for substituting group are-C=C-, and the selectivity showing is very low.
Document 4 (Journal of Catalysis 265 (2009) 19-25) utilizes Au catalyzer to have high selectivity for aromatic nitro compound, and Pt is the metal that a kind of hydrogenation activity is good, by the two characteristic combination separately, in such reaction, phenotype has gone out good synergistic effect, and author is at Au/TiO
2in catalyzer, mix 0.01%Pt, at 85 ℃, 8bar PH
2under reaction conditions, can obtain the selectivity of 94.5% transformation efficiency and 93.4%.
Document 5 (WO 2009071727) adopts pickling process to prepare Pt/TiO
2catalyzer, at 40 ℃, 3bar P
h2reaction conditions under, in the selective hydrogenation for 3-nitrostyrolene, in the time that loading is 0.2%, need to react 7h could can obtain 92% productive rate, selectivity is 93.1%.
Summary of the invention
The object of the invention is to the application of a kind of catalyzer in aromatic nitro compound selective hydrogenation.This catalyzer has shown high transformation efficiency and selectivity in reaction, and in catalyzer, active ingredient high dispersing, on carrier, has maximally utilised active metal, has reduced the cost of catalyzer, and reaction conditions gentleness, easy and simple to handle.
For achieving the above object, technical scheme provided by the invention is:
Take high-specific surface area ferric oxide as carrier, take one or two or more kinds in ⅧZu HuoⅠ B family metal as active ingredient, adopt coprecipitation method or pickling process to prepare catalyzer, active component content is 0.01-20wt%.
Active ingredient is for being Pt and/or Ir, and active component content is 0.01-10wt%.
The process of coprecipitation method Kaolinite Preparation of Catalyst is as follows:
1) metal active constituent solubility precursor and iron nitrate are made into mixing solutions, are designated as solution A, concentration 1 × 10
-4-1mol/L, the precipitation agent aqueous solution is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L.
2) solution B stirs at 50 ° C-100 ℃, and solution A is added drop-wise in solution B; Solution A and solution B volume ratio 0.001-1000.
3) drip and finish to continue to stir after 1-10 hour at rear 50 ℃ of-100 ℃ of temperature, then leave standstill 1-10 hour;
4) leave standstill after end, separate solid, solid deionized water suction filtration, by solid drying, drying temperature is 25-120 ℃, be 1-24 hour time of drying;
5) dry rear solid carries out roasting, and maturing temperature is 200 ℃-800 ℃, and roasting time is 1-24 hour;
The specific surface area of described carrier is 50-500m
2/ g;
Described active ingredient presoma is the one in this metal nitrate or halogenide;
Described precipitation agent is the one in sodium carbonate, volatile salt, salt of wormwood, Quilonum Retard, sodium hydroxide, potassium hydroxide.
The process of preparation catalyst is as follows:
Take high-specific surface area Iron oxide support, be added in active metal precursor solution in required ratio, constantly stir, mix, carry out incipient impregnation; Catalyzer is dry, and drying temperature is 25-120 ° of C, and be 1-24 hour time of drying; Dry rear catalyst carries out roasting, and maturing temperature is 200 ℃-800 ℃, and roasting time is 1-24 hour;
The specific surface area of described carrier is 50-500m
2/ g;
Described active ingredient presoma is the one in this metal nitrate or halogenide;
Described carrier is a kind of high-specific surface area Iron oxide support preparing in coprecipitation method, hard template method or soft template method.
Catalyzer for before reacting, all pass through reduction process, reducing atmosphere is hydrogen, reduction temperature is 50 ℃-800 ℃, recovery time 10-120min.
React in airtight autoclave and carry out, the original pressure in reactor when hydrogen room temperature is 0.1-5Mpa, and temperature of reaction is 20-150 ℃, and the reaction times is no less than 10 minutes.
The solvent that described reaction adopts is one or two or more kinds in ethanol, methyl alcohol, toluene, tetrahydrofuran (THF), dodecane, water, and reaction solution concentration of substrate is greater than 0.01mol/L;
Reaction substrate is aromatic nitro compound
substituent R is the one in halogen ,-C=C-,-C ≡ C-,-C ≡ N-, aldehyde radical, phenolic hydroxyl group, carbonyl and other aromatic nitro compound derivatives, as
the number of substituent R is 1-5.
The mol ratio of catalyst activity component and reaction substrate is 1 × 10
-4between 1.
Preferred temperature of reaction is 20-80 ° of C, the preferred original pressure 0.1-1.5Mpa of hydrogen in reactor under room temperature, preferred reaction time 0.5h-3h.
Catalyzer can recycle repeatedly, and its transformation efficiency and selectivity obviously do not decline, and catalyzer easily separates with reaction soln.
Activity test method to catalyzer provided by the invention is as follows:
Reactor is autoclave, reaction substrate is become to certain density reaction solution with interior standard configuration, and every secondary response is got a certain amount of reaction solution with transfer pipet and is reacted, and the original pressure in reactor when hydrogen room temperature is 0.1-5Mpa, temperature of reaction is 20-150 ℃, and the reaction times is no less than 10 minutes.After reaction finishes to be cooled to room temperature, gas chromatographic analysis is carried out in sampling.
The present invention has following effect:
1. aromatic nitro compound selective hydrogenation obtains corresponding function aniline has application at numerous areas, as agricultural, medicine, dye well high molecular polymer etc.Catalyzer provided by the invention can high reactivity, highly selective catalysis obtains functionalization aniline.
2. catalyzer provided by the invention, in the reaction of aromatic nitro compound selective hydrogenation, can recycle repeatedly, and active not obviously reduction.
3. catalyzer provided by the invention, after reaction, is easy to separate from reaction soln, easy and simple to handle.
In a word, the present invention has realized that aromatic nitro compound is efficient, highly selective transforms preparation functionalization aniline, compared with existing industrial catalyst system, catalyzer provided by the invention is green friendly in the process of this class reaction, and active ingredient is utilized, save cost, be expected to be applied industrial.
Embodiment
In following embodiment, X is 1,4/3 or 3/2;
Embodiment 1: the anhydrous sodium carbonate of getting 5.4g is dissolved in the deionized water of 60mL, and gained solution is designated as solution A.Get the iron nitrate solution of 20mL 1M in beaker, add 0.14mL 14.8mg
ptthe H of/ml
2ptCl
6solution, stirs, and gained solution is designated as solution B.Solution A is stirred under 50 ℃ of water-baths, and solution B is added drop-wise in solution A with the speed of 1mL/min.Dropping finishes to continue to stir after 3 hours under rear uniform temp, then leaves standstill 3 hours.With after 500mL deionized water suction filtration, 60 ° of C oven drying 5h, 400 ℃ of roasting 5h of retort furnace after taking out, obtain 0.17%Pt/FeO
xcatalyzer.
Embodiment 2: the anhydrous sodium carbonate of getting 5.4g is dissolved in the deionized water of 60mL, and gained solution is designated as solution A.Get the iron nitrate solution of 20ml 1M in beaker, add 1.4mL 14.8mg
ptthe H of/mL
2ptCl
6solution, stirs, and gained solution is designated as solution B.Solution A is stirred under 50 ° of C water-baths, and solution B is added drop-wise in solution A with the speed of 1mL/min.Dropping finishes to continue to stir after 3 hours under rear uniform temp, then leaves standstill 3 hours.With after 500mL deionized water suction filtration, 60 ℃ of oven drying 5h, 400 ℃ of roasting 5h of retort furnace after taking out, obtain 1.5%Pt/FeO
xcatalyzer.
Embodiment 3: the anhydrous sodium carbonate of getting 5.4g is dissolved in the deionized water of 60mL, and gained solution is designated as solution A.Get the iron nitrate solution of 20mL 1M in beaker, add 2.06mL14.8mg
ptthe H of/mL
2ptCl
6solution, stirs, and gained solution is designated as solution B.Solution A is stirred under 50 ℃ of water-baths, and solution B is added drop-wise in solution A with the speed of 1mL/min.Dropping finishes to continue to stir after 3 hours under rear uniform temp, then leaves standstill 3 hours.With after 500mL deionized water suction filtration, 60 ℃ of oven drying 5h, 400 ℃ of roasting 5h of retort furnace after taking out, obtain 2.5%Pt/FeO
xcatalyzer.
Embodiment 4: the anhydrous sodium carbonate of getting 5.4g is dissolved in the deionized water of 60mL, and gained solution is designated as solution A.Get the iron nitrate solution of 20mL 1M in beaker, add a certain amount of 9.56mg
au/ mLHAuCl
4solution, stirs, and gained solution is designated as solution B.Solution A is stirred under 50 ℃ of water-baths, and solution B is added drop-wise in solution A with the speed of 1mL/min.Dropping finishes to continue to stir after 3 hours under rear uniform temp, then leaves standstill 3 hours.With after 500mL deionized water suction filtration, 60 ℃ of oven drying 5h, obtain Au/FeO
xcatalyzer
Embodiment 5: the anhydrous sodium carbonate of getting 5.4g is dissolved in the deionized water of 60mL, and gained solution is designated as solution A.Get the iron nitrate solution of 20mL 1M in beaker, add a certain amount of 12.00mg
pd/ mLH
2pdCl
4solution, stirs, and gained solution is designated as solution B.Solution A is stirred under 50 ℃ of water-baths, and solution B is added drop-wise in solution A with the speed of 1mL/min.Dropping finishes to continue to stir after 3 hours under rear uniform temp, then leaves standstill 3 hours.With after 500mL deionized water suction filtration, 60 ℃ of oven drying 5h, obtain Pd/FeO
xcatalyzer
Embodiment 6: get 1.2g Al
2o
3after 120 ℃ of oven drying 2h, take out, pipette 0.12ml 14.8mg with transfer pipet
pt/ mL H
2ptCl
6solution, in beaker, adds 0.6g H
2o, stirs.By dried Al
2o
3add in the solution mixing, stir.In 60 ℃ of oven drying 6h, after taking-up at 400 ℃ of roasting 5h of retort furnace.Make 0.17%Pt/Al
2o
3catalyzer.
Embodiment 7: get 1.2g SiO
2after 120 ℃ of oven drying 2h, take out, pipette 0.12ml 14.8mgPt/mL H with transfer pipet
2ptCl
6solution, in beaker, adds 1.4g H
2o, stirs.By dried SiO
2add in the solution mixing, stir.In 60 ℃ of oven drying 6h, after taking-up at 400 ℃ of roasting 5h of retort furnace.Make 0.17%Pt/SiO
2catalyzer.
Application examples:
Catalyzer all passes through 10%H before use
2/ He reduction, reductive condition is that 10 ℃/min is raised to 250 ℃, after reduction 30min, purge 30min with He, take out rapidly and take 0.1g and pour in reaction tubes, (toluene is solvent to add the 3-nitrostyrolene reaction solution of 5ml 0.1M with transfer pipet, o-Xylol is interior mark), reaction conditions is 3bar P
h2, 40 ℃.
Specific experiment result is as follows:
The different loading catalyzer of table one are selected the result of hydrogenation at 3-nitrostyrolene
Along with the increase of loading, the selectivity of target product is not obviously reduced as seen from table, preferably loading is at 0.01%-2.5%, and low levels catalyzer (0.17%Pt/FeO
x) showing higher TOF value compared with other loading catalyzer, low levels catalyzer shows good atom utilization.
At table two differential responses temperature, 3-nitrostyrolene is selected the result of hydrogenation
Can be found out by data in table, along with the raising of temperature of reaction, speed of response is accelerated, and the selectivity of target product is remained on more than 90% simultaneously.
Table three different carriers is selected the result of hydrogenation to 3-nitrostyrolene
As can be seen from Table II with FeO
xfor carrier compares Al
2o
3and SiO
2there is higher activity and selectivity, especially in selectivity, show larger advantage.
Table four 0.17%Pt/FeO
xselect the result of hydrogenation at differential responses substrate
Can find out that by data in table this catalyzer has very high selectivity equally for other substrates.
Table five different metal is selected the result of hydrogenation at 3-nitrostyrolene
Pt, Ir are that active ingredient is good to the selectivity of product as can be seen from the table, and during take Pd as active ingredient, have very high activity, but selectivity are very poor.And Au, Ru catalyzer substantially do not have activity under this reaction conditions.
Claims (10)
1. the catalyzer application in aromatic nitro compound selective hydrogenation, it is characterized in that: described catalyzer is take high-specific surface area ferric oxide as carrier, take one or two or more kinds in ⅧZu HuoⅠ B family metal as active ingredient, adopt coprecipitation method or pickling process preparation, its active component content is 0.01-20wt%.
2. application as claimed in claim 1, is characterized in that: active ingredient is for being Pt and/or Ir, and active component content is 0.01-10wt%.
3. application as claimed in claim 1, is characterized in that: the process of coprecipitation method Kaolinite Preparation of Catalyst is as follows:
1) metal active constituent solubility precursor and iron nitrate are made into mixing solutions, are designated as solution A, concentration 1 × 10
-4-1mol/L, the precipitation agent aqueous solution is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L;
2) solution B stirs at 50 ℃-100 ℃, and solution A is added drop-wise in solution B; Solution A and solution B volume ratio 0.001-1000;
3) drip and finish to continue to stir after 1-10 hour at rear 50 ℃ of-100 ℃ of temperature, then leave standstill 1-10 hour;
4) leave standstill after end, separate solid, solid deionized water suction filtration, by solid drying, drying temperature is 25-120 ℃, be 1-24 hour time of drying;
5) dry rear solid carries out roasting, and maturing temperature is 200 ℃-800 ℃, and roasting time is 1-24 hour;
The specific surface area of described carrier is 50-500m
2/ g;
Described active ingredient presoma is the one in this metal nitrate or halogenide;
Described precipitation agent is the one in sodium carbonate, volatile salt, salt of wormwood, Quilonum Retard, sodium hydroxide, potassium hydroxide.
4. application as claimed in claim 1, is characterized in that: the process of preparation catalyst is as follows:
Take high-specific surface area Iron oxide support, be added in active metal precursor solution in required ratio, constantly stir, mix, carry out incipient impregnation; Catalyzer is dry, and drying temperature is 25-120 ° of C, and be 1-24 hour time of drying; Dry rear catalyst carries out roasting, and maturing temperature is 200 ℃-800 ℃, and roasting time is 1-24 hour;
The specific surface area of described carrier is 50-500m
2/ g;
Described active ingredient presoma is the one in this metal nitrate or halogenide;
Described carrier is a kind of high-specific surface area Iron oxide support preparing in coprecipitation method, hard template method or soft template method.
5. application as claimed in claim 1, is characterized in that:
Catalyzer for before reacting, all pass through reduction process, reducing atmosphere is hydrogen, reduction temperature is 50 ℃-800 ℃, recovery time 10-120min.
6. application as claimed in claim 1, is characterized in that:
React in airtight autoclave and carry out, the original pressure in reactor when hydrogen room temperature is 0.1-5Mpa, and temperature of reaction is 20-150 ℃, and the reaction times is no less than 10 minutes.
7. application as claimed in claim 6, is characterized in that:
The solvent that described reaction adopts is one or two or more kinds in ethanol, methyl alcohol, toluene, tetrahydrofuran (THF), dodecane, water, and reaction solution concentration of substrate is greater than 0.01mol/L;
Reaction substrate is aromatic nitro compound
substituent R is the one in halogen ,-C=C-,-C ≡ C-,-C ≡ N-, aldehyde radical, phenolic hydroxyl group, carbonyl and other aromatic nitro compound derivatives, as
the number of substituent R is 1-5.
8. application as claimed in claim 7, is characterized in that:
The mol ratio of catalyst activity component and reaction substrate is 1 × 10
-4between 1.
9. the application as described in claim 1 or 6, is characterized in that:
Preferred temperature of reaction is 20-80 ° of C, the preferred original pressure 0.1-1.5Mpa of hydrogen in reactor under room temperature, preferred reaction time 0.5h-3h.
10. application as claimed in claim 1, is characterized in that: catalyzer can recycle repeatedly, and its transformation efficiency and selectivity obviously do not decline, and catalyzer easily separates with reaction soln.
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| CN105618083A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of adjuvant-containing catalyst in selective hydrogenation reaction of aromatic nitro compound |
| CN106378147A (en) * | 2016-08-25 | 2017-02-08 | 闽南师范大学 | Magnetic Au/Fe3O4 catalyst, preparation method and application thereof |
| CN111013668A (en) * | 2019-11-20 | 2020-04-17 | 南京工程学院 | Nano platinum catalyst with multilevel structure and one-step preparation method thereof |
| CN111135822A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound |
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| CN114618518A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
| CN116212870A (en) * | 2023-01-04 | 2023-06-06 | 山东大学 | WO (WO) with double-plasma coupling enhancement 3-x -Au, and preparation method and application thereof |
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| CN105618083A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of adjuvant-containing catalyst in selective hydrogenation reaction of aromatic nitro compound |
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| CN111135822A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound |
| CN111013668A (en) * | 2019-11-20 | 2020-04-17 | 南京工程学院 | Nano platinum catalyst with multilevel structure and one-step preparation method thereof |
| CN111644197A (en) * | 2020-05-15 | 2020-09-11 | 北京化工大学 | Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application |
| CN114618518A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
| CN114618518B (en) * | 2020-12-10 | 2023-01-17 | 中国科学院大连化学物理研究所 | Supported bimetallic catalyst and preparation and application thereof |
| CN116212870A (en) * | 2023-01-04 | 2023-06-06 | 山东大学 | WO (WO) with double-plasma coupling enhancement 3-x -Au, and preparation method and application thereof |
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