CN1171854C - Catalyst for preparing phenylamine or alkylphenylamine - Google Patents
Catalyst for preparing phenylamine or alkylphenylamine Download PDFInfo
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- CN1171854C CN1171854C CNB011126566A CN01112656A CN1171854C CN 1171854 C CN1171854 C CN 1171854C CN B011126566 A CNB011126566 A CN B011126566A CN 01112656 A CN01112656 A CN 01112656A CN 1171854 C CN1171854 C CN 1171854C
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- catalyzer
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- metallic palladium
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Abstract
The present invention relates to a catalyst for preparing phenylamine or alkylphenylamine, which mainly solves the problems of low raw material space velocity and low yield of an amine compound as a product, which exist in the previous art. The present invention nicely solves the problems by adopting the technical scheme through the adoption of aluminum oxide as a carrier for loading metals of palladium and tin and/or cerium or compounds of the palladium and the tin and/or the cerium and through the non-forcible addition of metals selected from ferrum, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese, or compounds of the metals. When used in an amination reaction of phenol or an amination reaction of alkylphenol, the present invention has the characteristics of high raw material space velocity and high yield of the phenylamine or the alkylphenylamine as a product. The present invention can be used in the industrial production of the phenylamine or the industrial production of the alkylphenylamine.
Description
The present invention relates to be used to prepare the catalyzer of aniline or alkyl benzene amine, particularly, prepare the catalyzer of aniline or alkyl benzene amine about being raw material with phenol or alkylphenol.
Aniline is a kind of important industrial chemical, can be used as the raw material of thiofide, dyestuff, mordant, medicine, explosive raw material and ditan urethane (MDI).Alkyl substituted benzene amine during as raw material, can increase the effectiveness of photographic developer, agriculture reagent and medicine as Tolylamine, cumidine, methyl cumidine, xylidine, diisopropyl aniline.
The production method of aniline or alkyl benzene amine is in the prior art: (1) uses the hydrogen reducing aromatic nitro compound; (2) halogenated aromatic compound and ammoniacal liquor reaction under the high temperature of certain pressure; (3) ammonia and phenol or alkyl substituted phenol reaction.
Utilize the method for aromatic nitro compound to have following shortcoming: (1) needs with a large amount of sulfuric acid or the nitric acid nitrating agent as aromatic substance, in it and a large amount of alkali of reactions steps needs, as sodium hydroxide, thereby has produced the brackish water of high density.In addition, be as described in the Japanese patent application of the clear 48-67229 of JP as publication number, in the step that forms nitro-compound, produce nitrogen oxide gas, thereby caused atmospheric pollution.When nitrated alkylphenol, except obtaining required nitro compound beyond the region of objective existence, also can produce various isomer by products, because isomer is difficult to segregation, so purified petroleum benzin amine is difficult to obtain.
Utilize the method (2) of halogenated aromatic compound that a critical problem is arranged, promptly, therefore when the preparation halogenated aromatic compound, expensive corrosion protection equipment must be installed owing to used the chlorine of highly corrosive.And even under higher temperature and pressure, chlorobenzene and ammonia react, productive rate are still very low, seldom select this technology in the actual production, unless halogenated aromatic compound is to contain nitro on the contraposition position of chlorobenzene, i.e. and p-Nitrophenyl chloride.
Same method (1) and (2) are opposite, become the main method of preparation aniline gradually based on the method (3) of phenol or alkyl substituted phenol and ammonia react.This method only needs phenol and ammonia by fixed-bed reactor, produces aniline or alkyl benzene amine in the presence of catalyzer.This method has simple to operate, does not produce advantages such as causing air-polluting nitrogen oxide gas and large amount of sewage.
The typical method that a kind of phenol and ammonia react prepare aniline is disclosed among the clear 42-23571 of document JP.Catalyst system therefor is selected from SiO in the document
2-Al
2O
3, ZrO
2-Al
2O
3, TiO
2-Al
2O
3, zirconium white-silica phosphate and tungstates.Point out in the document that slightly acidic solid acid such as gamma-alumina catalyst are inappropriate, because its is active low, and strongly-acid solid acid such as silica-alumina catalyzer are effectively as the catalyzer of this amination reaction.Though these strongly-acid solid acid catalysts such as silica-alumina demonstrate higher initial activity to amination reaction, some unwanted side reactions have been produced, as aniline decomposition etc.The clear 48-67229 of document JP attempts to solve above-mentioned these problems.In the document, the strength of acid that phenol and aminating agent react employed catalyzer is lower than the strength of acid (PKa＜-8.0) of silica-alumina catalyzer, and promptly adopting the strength of acid scope is the titanium dioxide titania-zirconia or the titania-silica solid acid catalyst of PKa5.6～-3.0.But be to use these catalyzer, when temperature of reaction must be elevated to 400 to 500 ℃, could finish amination reaction effectively, but the rising temperature of reaction can be quickened the decomposition of aminating agent or ammonia, produce nitrogen, its reaction process is as follows:
Because the generation of nitrogen causes the reactor embrittlement, the useful life of reactor is shortened, this method is difficult to be applied in the industrial production.
The clear 46-23052 of document JP discloses the aminating method of a kind of phenol.This method is used a kind of mixed catalyst, contains a kind of dewatered solid an acidic catalyst and a kind of hydrogenation catalyst.The aminating method of a kind of phenol is disclosed among the clear 46-23053 of document JP.The catalyzer that this method is used contains aluminum oxide or silicon-dioxide, also contains a kind of oxide compound of selecting from magnesium oxide, boron oxide and Thorotrast.In the above two kinds of cases, the catalyst activity time length only is 50 to 100 hours, and the problem of catalyst activity reduction is still unresolved.
A kind of phenyl amines catalyzer is disclosed among the clear 71-23052 of document JP.This catalyzer is a kind of special gama-alumina, the PKa value with Hammett acidity scale indicator be measured as+3.3～+ 6.8, total acid content is assigned 0.5 milligramequivalent/gram, the micropore with ink ampuliform in drying regime.The characteristics of this catalyzer are to be difficult for inactivation, but that shortcoming is an air speed is low excessively, and liquid hourly space velocity (LHSV) only is about 0.02 to about 0.06 hour
-1
A kind of aluminium oxide catalyst that is used for the ammonification of phenol gas phase is disclosed among document FR1405816 and the document DE3147734.Its weak point is that air speed is low excessively, liquid hourly space velocity LHSV＜0.1 hour
-1, do not report the stability of catalyzer in the document, and product aminated compounds yield is lower.
A kind of Pd/ aluminum oxide or Pd/ magnesium-aluminium spinel catalyzer are disclosed in the document EP 0053819.The amination reaction that is used for phenol.The data of relevant air speed are not provided in the document, can only learn that its weight space velocity WHSV is about 0.05～0.2 hour according to measuring and calculating
-1Adopt catalyzer that this method makes at weight space velocity WHSV greater than 0.1 hour
-1The time, phenol transformation efficiency and phenyl amines selectivity all have bigger decline, and product yield is lower.
Provide a kind of Synthetic 2 among the document Chinese patent CN1207329A, the catalyzer of 6-xylidine.In fact this catalyzer is exactly Pd/ magnesium-aluminium spinel catalyzer.Preparation of catalysts method and application method only are provided in the document, catalyzer have not been made any improvement.In the document, raw material 2, the input speed of 6-xylenol is 0.1～0.15 hour
-1But product yield is lower (WHSV).
A kind of phenol gas phase amination catalysis has been described in the document U.S. Pat 5091579.This catalyzer is the gama-alumina of load fluorine, is a kind of acidulous catalyst.The advantage of this catalyzer is that stability is high, and shortcoming is to use under low-speed, and its liquid hourly space velocity LHSV is 0.094 hour
-1, and product yield is lower.
The objective of the invention is to exist the raw material air speed lower in the above-mentioned document in order to overcome, the shortcoming that product aminated compounds yield is low provides a kind of new catalyzer that is used to prepare aniline or alkyl benzene amine.It is big that this catalyzer has raw material charging air speed, product aniline or the high characteristics of alkyl benzene amine yield.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer that is used to prepare aniline or alkyl benzene amine is a carrier with the aluminum oxide, and load comprises following component on carrier:
A) count metallic palladium or its compound of 0.1～10% vehicle weight with metallic palladium;
B) metal of tin or tin and cerium or its compound, its consumption is 0.1～2 in the weight ratio of metal and metallic palladium;
C) metal of at least a chosen from Fe, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese or its compound, its consumption is 0～3 in the weight ratio of metal and metallic palladium.
In the technique scheme, the charge capacity of metallic palladium or its compound is 0.1～2% of a vehicle weight in the metal preferable range, and more preferably scope is 0.1～1% of a vehicle weight.The metal of tin or tin and cerium or its compound, its consumption is 0.1～1 in the weight ratio preferable range of metal and metallic palladium.The metal of at least a chosen from Fe, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese or its compound, its consumption is 0.1～2 in the weight ratio preferable range of metal and metallic palladium, more preferably scope is 0.2～1.2.The alkyl benzene amine preferred version is 2, the 6-diisopropyl aniline.
The raw material for preparing catalyzer use of the present invention is as follows:
Palladium component: with palladium metal, Palladous chloride or the acid of chlorine palladium.
Tin, cerium: with metal nitrate or its oxide compound.
Iron, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese: with metal, oxide compound or its nitrate.
Method for preparing catalyst among the present invention can adopt blending method or the preparation of following method:
Take by weighing a certain amount of pseudo-boehmite dry glue powder, add the peptization aqueous acid, mix and pinch evenly, become plastic, extruded moulding on banded extruder, the bar after the moulding descended dry 2～6 hours or dried in the shade naturally at 90～150 ℃, placed stoving oven then, be warming up to 500～1000 ℃, make alumina supporter.Weighing sodium carbonate solution, the oxide impregnation alumina supporter, 100～150 ℃ of following dried overnight, take by weighing Palladous chloride and become the acid of chlorine palladium with diluted hydrochloric acid dissolution, and the nitrate solution that is selected from tin, cerium, iron, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese of catalyzer institute expense and above-mentioned carrier incipient impregnation, drying and the roasting that makes, obtain required catalyzer.
The appreciation condition of catalyzer of the present invention is as follows:
With the catalyzer that the makes internal diameter of packing into is in 14 millimeters the stainless steel tube, heat with resistance wire, the mid-thermocouple measurement temperature of reaction of insulation jacket, insulation jacket is inserted the thermopair control reaction temperature outward, and the catalyzer Stainless Steel Helices of packing into up and down feeds phenol or alkylphenol, hydrogen and ammonia, temperature of reaction is 200 ℃, and reaction pressure is 0.1～2MPa (gauge pressure), and catalyst loading is 0.1～0.5 hour
-1(weight space velocity), temperature of reaction are 200～300 ℃.
Phenol described in the present invention or alkylphenol are not limited to phenol or 2, the 6-xylenol, it comprises phenol, alkylphenol such as cresylol, adjacent-,-and the isomer of right-ethylphenol and isopropyl-phenol, contain the alkylphenol of at least one alkyl substituent, as xylenol, carvacrol, methyl butyl phenol, diethyl phenol, the ethyl isopropyl-phenol, ethyl-butyl phenol, diisopropyl phenol, sec.-propyl butylphenol and dibutyl phenol.Also can comprise the phenol of arbitrary proportion and the mixture of alkylphenol, preferred phenol and xylenol and diisopropyl phenol.
Among the present invention, owing in palladium/aluminium oxide catalyst system, add tin or/and the metal of cerium or its compound, the amination ability of phenol or alkylphenol is improved greatly, reduced side reaction simultaneously, in catalyst system, add iron, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or the manganese component of non-imposed adding, further help active and optionally raising, the yield that makes the purpose product from the past about 60～70%, the highlyest brought up to 92.8%, and applicable 0.1～0.5 hour of raw material weight air speed
-1, obtained effect preferably.
The invention will be further elaborated below by embodiment.
[embodiment 1]
Take by weighing pseudo-boehmite dry glue powder 180 gram, add 4.2 gram phosphoric acid and 85 gram distilled water, fully mix and pinch into plastic, extrusion, 120 ℃ dry 4 hours down, then 700 ℃ of following roastings 2 hours, pelletizing makes alumina supporter.
Taking by weighing 250 gram alumina supporters is placed in the beaker standby.Take by weighing 7.9 gram yellow soda ash and be made into 100 ml water solution, impregnated carrier, 120 ℃ are dry down.Take by weighing Palladous chloride (content of palladium is 59%) 2.12 grams again, add 100 milliliters in dilute hydrochloric acid and nitric acid tin 0.8 gram, dissolving back impregnated carrier, 120 ℃ of dryings 2 hours, then 500 ℃ of following roastings 2 hours, making catalyzer, to carry the palladium amount be 0.5% (weight), and carrying a tin amount is 0.1% (weight), and tin: palladium is 0.2: 1.
With catalyzer 20 grams that make, the internal diameter of packing into is in the stainless steel tube of 14 millimeters of Φ, with the mid-thermocouple measurement temperature of reaction of resistance wire heat tracing chuck, insulation jacket is inserted the thermopair control reaction temperature outward, the catalyzer Stainless Steel Helices of packing into up and down, feed 2,6-diisopropyl phenol, hydrogen and ammonia.Ammonia flow is 100 ml/min, and hydrogen flowing quantity is 38 ml/min, and weight space velocity is 0.2 hour
-1, temperature of reaction is 200 ℃, reaction pressure is 1.5MPa, and 2, the transformation efficiency of 6-diisopropyl phenol is 96.32%, 2, and 6-diisopropyl aniline selectivity is 89.24%, 2, and 6-diisopropyl aniline yield is 85.96%.
[embodiment 2]
The method, step and the catalyzer that prepare catalyzer are formed with embodiment 1, and just with reaction raw materials 2, the 6-diisopropyl phenol is changed into phenol, and reaction result is: phenol conversion 95.2%, aniline selectivity are 86.1%, and aniline yield rate is 81.96%.
[comparative example 1]
Preparation of catalysts step and method are with embodiment 1, and just catalyzer does not add component tin in forming, and reaction result is: 2, the transformation efficiency of 6-diisopropyl phenol is 94.23%, 2, and 6-diisopropyl aniline selectivity is 73.60%, 2,6-diisopropyl aniline yield is 69.35%.
[embodiment 3]
Preparation of catalysts step, method and catalyzer are formed with embodiment 1, just with reaction raw materials 2, the 6-diisopropyl phenol changes into 2, the 6-xylenol, reaction result is: 2,6-xylenol transformation efficiency is 98.5%, 2,6-xylidine selectivity is 90.00%, 2, and 6-xylidine yield is 88.65%.
[embodiment 4～13]
Preparation of catalysts step, method and catalyzer are formed with embodiment 1, just change component and content in the catalyzer, make different catalyzer E respectively
1～E
9, reaction result is listed in the table below 1.
Table 1
| The catalyzer numbering | E 1 | E 2 | E 3 | E 4 | E 5 | E 6 | E 7 | E 8 | E 9 | |
| Loaded metal kind and content, % (weight) | Pd | 0.1 | 0.5 | 0.5 | 1.0 | 0.5 | 0.5 | 2.0 | 0.5 | 0.5 |
| Sn | 0.1 | 0.25 | 0.5 | 0.30 | 0.35 | 0.2 | 0.4 | 0.35 | ||
| Ce | 0.2 | 0.1 | ||||||||
| La | 0.25 | 0.25 | 0.25 | 0.25 | ||||||
| Fe | 0.56 | 0.2 | ||||||||
| Cd | 0.1 | 0.05 | ||||||||
| Cu | 0.2 | |||||||||
| 2,6-diisopropyl phenol transformation efficiency, % | 90.72 | 95.74 | 95.63 | 96.40 | 95.40 | 96.30 | 97.41 | 95.80 | 96.20 | |
| 2,6-diisopropyl aniline yield, % | 80.13 | 88.87 | 83.49 | 94.11 | 82.52 | 93.83 | 94.01 | 92.80 | 93.61 | |
Claims (7)
1, a kind of catalyzer that is used to prepare aniline or alkyl benzene amine is a carrier with the aluminum oxide, and load comprises following component on carrier:
A) count metallic palladium or its compound of 0.1～10% vehicle weight with metallic palladium;
B) metal of tin or tin and cerium or its compound, its consumption is 0.1～2 in the weight ratio of metal and metallic palladium;
C) metal of at least a chosen from Fe, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese or its compound, its consumption is 0～3 in the weight ratio of metal and metallic palladium.
2,, it is characterized in that the charge capacity of metallic palladium or its compound is counted 0.1～2% of vehicle weight with metallic palladium according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 1.
3,, it is characterized in that the charge capacity of metallic palladium or its compound is counted 0.1～1% of vehicle weight with metallic palladium according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 2.
4, according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 1, it is characterized in that metal or its compound of tin or tin and cerium, its consumption is 0.1～1 in the weight ratio of metal and metallic palladium.
5, according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 1, the metal or its compound that it is characterized in that at least a chosen from Fe, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese, its consumption is 0.1～2 in the weight ratio of metal and metallic palladium.
6, according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 5, the metal or its compound that it is characterized in that at least a chosen from Fe, lanthanum, cadmium, copper, silver, bismuth, molybdenum, magnesium or manganese, its consumption is 0.2～1.2 in the weight ratio of metal and metallic palladium.
7,, it is characterized in that alkyl benzene amine is 2, the 6-diisopropyl aniline according to the described catalyzer that is used to prepare aniline or alkyl benzene amine of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011126566A CN1171854C (en) | 2001-04-18 | 2001-04-18 | Catalyst for preparing phenylamine or alkylphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011126566A CN1171854C (en) | 2001-04-18 | 2001-04-18 | Catalyst for preparing phenylamine or alkylphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1381440A CN1381440A (en) | 2002-11-27 |
| CN1171854C true CN1171854C (en) | 2004-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011126566A Expired - Fee Related CN1171854C (en) | 2001-04-18 | 2001-04-18 | Catalyst for preparing phenylamine or alkylphenylamine |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898138B (en) * | 2009-05-25 | 2011-11-30 | 中国石油化工股份有限公司 | Method for preparing vulcanized dehydrogenation catalyst |
| CN102557963A (en) * | 2011-12-29 | 2012-07-11 | 湖南化工研究院 | Method for preparing 2,6-diisopropyl aniline |
| CN109422655B (en) * | 2017-08-24 | 2021-10-29 | 中国石油化工股份有限公司 | Method for preparing aniline by directly ammoniating phenol |
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