CN1241902C - Method of preparing 2, 6-diisoprogyl aniline - Google Patents
Method of preparing 2, 6-diisoprogyl aniline Download PDFInfo
- Publication number
- CN1241902C CN1241902C CN 03150736 CN03150736A CN1241902C CN 1241902 C CN1241902 C CN 1241902C CN 03150736 CN03150736 CN 03150736 CN 03150736 A CN03150736 A CN 03150736A CN 1241902 C CN1241902 C CN 1241902C
- Authority
- CN
- China
- Prior art keywords
- diisopropyl
- spinel
- weight
- oxide
- described preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing 2, 6-diisopropylaniline, which mainly solves the problems of low catalyst applicable space velocity, low conversion rate of 2, 6-diisopropylphenol as a reactant and low selectivity of the 2, 6-diisopropylaniline as a target product existing in the previous art. The present invention nicely solves the problems by adopting the technical scheme that a compound carrier of spinel in a structure of Al2 O3-MgO-K2 O grows at a surface layer of gamma-aluminum oxide as a basal body which loads palladium or the palladium, lanthanum and active constituents of an oxide of the lanthanum to prepare the catalyst. The present invention can be used in the industrial production for producing the 2, 6-diisopropylaniline.
Description
Technical field
The present invention relates to prepare 2, the method for 6-diisopropyl aniline, particularly about 2,6-diisopropyl phenol gas phase catalysis amination preparation 2, the method for 6-diisopropyl aniline.
Background technology
2, the 6-diisopropyl aniline is a kind of important fine-chemical intermediate, is widely used in agricultural chemicals, medicine, plastics, dyestuff and foodstuff additive industry.Its synthetic method mainly contains aniline alkylating method and 2,6-diisopropyl phenol amination method.Alkylation process is divided into liquid phase method and vapor phase process again.The liquid phase method of Bayer company exploitation needs High Temperature High Pressure.Air Products andChemicals company has developed vapor phase process, but selectivity is too poor.The Nobert of BASF AG (EP53819, DE 3425629) has developed gas phase amination legal system and has been equipped with 2, and the 6-diisopropyl aniline adopts the Pd/ spinel catalyst, and temperature of reaction is 200 ℃, and product 2,6-diisopropyl aniline yield only 78% is lower.Disclose in the document " petrochemical complex, 1999,28:585 " a kind of 2, the research of 6-diisopropyl phenol gas phase amination catalysis Pd/ spinel.Be suitable for Pd (1-0%)/MgO-Al in the document
2O
3(spinel) catalyzer is 200～215 ℃ in temperature of reaction, NH
3/ phenol mol ratio is 10, H
2/ phenol mol ratio is 20, and liquid hourly space velocity is 0.1 hour
-1Condition under check and rate, 2,6-diisopropyl phenol transformation efficiency is about 90～93%, 2,6-diisopropyl aniline one way selectivity is about 85～87%, so product yield is the highest has only 81%, product yield is lower.
Summary of the invention
Technical problem to be solved by this invention is to overcome to exist the suitable air speed of the catalyzer that uses lower in the prior art, has only 0.1 hour
-1, product 2, the problem that 6-diisopropyl aniline yield is lower provides a kind of new preparation 2, the method for 6-diisopropyl aniline.This method has and can operate under the higher space velocity condition, and product 2, the characteristics that 6-diisopropyl aniline yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation 2, and the method for 6-diisopropyl aniline, with 2,6-diisopropyl phenol and ammonia are raw material, react under following reaction conditions:
A) under hydro condition, raw material 2, the 6-diisopropyl phenol fixes bed bioreactor with ammonia by gas-solid and contacts with catalyzer, temperature of reaction is 180～250 ℃, reaction pressure is 1.2～1.7MPa, and raw material 2, the weight space velocity of 6-diisopropyl phenol are 0.1～0.6 hour
-1, with molar ratio computing ammonia: 2, the 6-diisopropyl phenol is 5～15: 1, hydrogen: 2, the 6-diisopropyl phenol is 10～50: 1;
B) used catalyzer comprises following component by weight percentage:
1) complex carrier of 98%～99.95% gama-alumina skeleton and surface growth spinel composition; With carry thereon
2) 0.05～2% palladium or its oxide compound;
Wherein spinel structure is aluminum oxide-magnesium oxide-potassium oxide structure, the amount of potassium oxide is 0.01～3.0% of a total catalyst weight in the spinel, magnesian amount is 0.1～5.0% of a total catalyst weight, and the amount of aluminum oxide is 0.5～10.0% of a total catalyst weight.
In the technique scheme, in the parts by weight gama-alumina: spinel is 70～95: 5～30, and preferable range is 85～95: 5～15.The consumption preferable range of potassium oxide is 0.1～1.5% of a total catalyst weight in the spinel, and more preferably scope is 0.5～1.2%; Magnesian consumption preferable range is 0.3～1.0% of a total catalyst weight; The consumption preferable range of aluminum oxide is 2.0～5.0% of a total catalyst weight.The catalyzer preferred version is for also to contain 0.005～1% lanthanum or its oxide compound in the catalyzer by weight percentage, and preferable range is 0.005～0.5% lanthanum or its oxide compound, and more preferably scope is to contain 0.05～0.15% lanthanum or its oxide compound.The complex carrier preferred version is first carbonate or a bicarbonate solution dipping with basic metal or alkaline-earth metal before supported palladium or its oxide compound, and more preferably scheme is earlier with yellow soda ash or sodium hydrogen carbonate solution dipping before supported palladium or its oxide compound.
The raw material that active constituent of the present invention is suitable for is as follows:
Palladium: with oxide compound or its nitrate of Palladous chloride, palladium; Other component is with its oxide compound or its nitrate.
The method for preparing catalyst that uses in the inventive method is as follows:
Make peptizing agent with acetate, a certain amount of boehmite powder, acetate and water uniform mixing extrusion made γ-Al in 4 hours 550 ℃ of following roastings then
2O
3, make the cylindric carrier of 3 millimeters * 5 millimeters of φ, as skeleton, take by weighing Mg (NO again
3)
26H
2O, Al (NO
3)
39H
2O and KNO
3Wiring solution-forming is with solution and γ-Al
2O
3Incipient impregnation, then 120 ℃ down dry, 800～1300 ℃ of roastings 6 hours obtain spinel Al after the cooling
2O
3-MgO-K
2The O carrier takes by weighing Na again
2CO
3Or NaHCO
3Be made into the aqueous solution, impregnated carrier is 5 hours again, and 120 ℃ following dry 16 hours.Take by weighing PdCl
2Press PdCl with dilute hydrochloric acid
2: HCl=1: 2 (mol ratios) are made the acid of chlorine palladium, are diluted to the solution of concentration 0.1 mol then, or claim a certain amount of promotor La (NO again
3)
3Water-soluble, two solution mixed back and above-mentioned carrier incipient impregnation 15 hours, 120 ℃ dry 5 hours down.Be washed with distilled water to no chlorion then, drying makes Pd/ spinel or Pd-La/ spinel catalyst again.
Among the present invention because to adopt with the gama-alumina be skeleton, the Al that on the gama-alumina skeleton, grows
2O
3-MgO-K
2The spinel of O structure by the effect of magnesium oxide and potassium oxide, has further been regulated the acid-basicity that contains the spinel complex carrier as complex carrier.Show by experiment, method of the present invention can significantly improve activity of such catalysts, make used catalyzer be used for 2,6-diisopropyl phenol gas phase amination system 2, during the 6-diisopropyl aniline, 2, the transformation efficiency of 6-diisopropyl phenol and 2, the selectivity of 6-diisopropyl aniline all is significantly improved, and makes catalyzer can adapt to higher space velocity 0.3 hour simultaneously
-1With 0.6 hour
-1Operate under the condition, obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[comparative example 1]
Take by weighing 14 gram acetate, make acetic acid aqueous solution with the dilution of 300 ml waters.Take by weighing 600 gram boehmite powder, do the peptizing agent extruded moulding with the acetic acid aqueous solution that makes, 120 ℃ of dryings are 4 hours then, again under 550 ℃ in retort furnace roasting made gama-alumina in 4 hours, make the cylindric of 3 millimeters * 5 millimeters of φ.Take by weighing Mg (NO
3)
26H
2O and Al (NO
3)
39H
2Water-soluble 20 ml solns of making of O.Dipping 25 gram gamma-aluminium oxide carriers 15 hours, 120 ℃ drying is after 16 hours down, and the carrier that makes behind 900 ℃ of roasting spinels is standby again.With the catalyst weight is benchmark, salic 4.00% in this carrier top layer spinel, magnesium oxide 0.50%.Take by weighing 7.9 gram Na
2CO
3Water-soluble 100 ml solns that make.With 15 milliliters of Na
2CO
3Solution impregnation 12 hours, following dry 11 hours at 120 ℃ then.Take by weighing 0.209 gram PdCl
2, be dissolved in 0.231 and restrain 36%～38% concentrated hydrochloric acid, be diluted to 10 milliliters then.Take by weighing 0.1222 gram La (NO
3)
3Be dissolved in 5 ml waters, then with PdCl
2Solution and La (NO
3)
3Solution mixes, and the above-mentioned carrier that makes of incipient impregnation 15 hours is following dry 5 hours in 120 ℃ again.Be washed with distilled water to no chlorine, promptly made Pd (0.5% weight)-La (0.1% weight)/spinel catalyst down in dry 5 hours at 120 ℃ again.
Take by weighing the catalyzer that makes 20 grams, the stainless steel micro fixed-bed reactor of 20 millimeters of the φ of packing into feeds 2, and the 6-diisopropyl phenol (2,6-DIPP), ammonia and hydrogen.220 ℃ of temperature of reaction, reaction pressure 1.5MPa, liquid hourly space velocity 0.3 hour
-1, NH
3/ 2,6-DIPP (mole)=10, H
2/ 2,6-DIPP (mole)=20,2, the transformation efficiency of 6-diisopropyl phenol are 95.8%, 2, and the selectivity of 6-diisopropyl aniline is 91.9%.
[comparative example 2]
Catalyst preparation process is with comparative example 1, takes by weighing catalyzer 20 grams that make, and the stainless steel micro fixed-bed reactor of 20 millimeters of the φ of packing into feeds 2,6-diisopropyl phenol, ammonia and hydrogen.220 ℃ of temperature of reaction, reaction pressure 1.5MPa, liquid hourly space velocity 0.6 hour
-1, NH
3/ 2,6-DIPP (mole)=10, H
2/ 2,6-DIPP (mole)=20,2, the transformation efficiency of 6-diisopropyl phenol are 94.6%, 2, and the selectivity of 6-diisopropyl aniline is 75.7%.
[embodiment 1]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 4.00% in the spinel of carrier top layer, magnesium oxide 0.50%, potassium oxide 0.50%.2, the transformation efficiency of 6-diisopropyl phenol is 97.2%, 2, and the selectivity of 6-diisopropyl aniline is 75.8%.
[embodiment 2]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 4.00% in the spinel of carrier top layer, magnesium oxide 0.50%, potassium oxide 1.00%.2, the transformation efficiency of 6-diisopropyl phenol is 98.9%, 2, and the selectivity of 6-diisopropyl aniline is 76.5%.
[embodiment 3]
Catalyst preparation process is with embodiment 2,220 ℃ of temperature of reaction, reaction pressure 1.5MPa, liquid hourly space velocity 0.6 hour
-1, NH
3/ 2,6-DIPP (mole)=10, H
2/ 2,6-DIPP (mole)=30,2, the transformation efficiency of 6-diisopropyl phenol are 99.5%, 2, and the selectivity of 6-diisopropyl aniline is 69.3%.
[embodiment 4]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 4.00% in the spinel of carrier top layer, magnesium oxide 0.50%, potassium oxide 1.20%.2, the transformation efficiency of 6-diisopropyl phenol is 99.3%, 2, and the selectivity of 6-diisopropyl aniline is 76.6%.
[comparative example 3]
Catalyst preparation process and examination condition are with comparative example 2, just catalyzer consists of Pd (0.5% weight)-La (0.1% weight)/gamma-alumina catalyst, and 2,6-diisopropyl phenol transformation efficiency is 85.6%, 2, the selectivity of 6-diisopropyl aniline is 61.5%.
[comparative example 4]
Catalyst preparation process and examination condition are with comparative example 2, and just catalyzer consists of Pd (0.5% weight)/spinel catalyst, and 2,6-diisopropyl phenol transformation efficiency is 83.5%, 2, the selectivity of 6-diisopropyl aniline is 65.5%.
[embodiment 5]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 4.00% in the spinel of carrier top layer, magnesium oxide 0.50%, potassium oxide 1.50%.2, the transformation efficiency of 6-diisopropyl phenol is 96.7%, 2, and the selectivity of 6-diisopropyl aniline is 75.6%.
[embodiment 6]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 3.00% in the spinel of carrier top layer, magnesium oxide 0.5%, potassium oxide 1.0%.2, the transformation efficiency of 6-diisopropyl phenol is 97.5%, 2, and the selectivity of 6-diisopropyl aniline is 76.2%.
[embodiment 7]
Catalyst preparation process and examination condition wherein are benchmark with the catalyst weight with comparative example 2, and be salic 5.0% in the spinel of carrier top layer, magnesium oxide 1.0%, potassium oxide 1.5%.2, the transformation efficiency of 6-diisopropyl phenol is 96.8%, 2, and the selectivity of 6-diisopropyl aniline is 75.9%.
[embodiment 8]
Used catalyzer and examining method are with embodiment 2, and just changing temperature of reaction is 180 ℃, and pressure is 1.2MPa, and the liquid phase air speed is 0.3 hour
-1, NH
3/ 2,6-DIPP=15, H
2/ 2,6-DIPP=50.2, the transformation efficiency of 6-diisopropyl phenol is 99.0%, 2, and the selectivity of 6-diisopropyl aniline is 93.8%.
[embodiment 9]
Used catalyzer and examining method are with embodiment 2, and just changing temperature of reaction is 250 ℃, and pressure is 1.7MPa, and the liquid phase air speed is 0.6 hour
-1, NH
3/ 2,6-DIPP=10, H
2/ 2,6-DIPP=20.2, the transformation efficiency of 6-diisopropyl phenol is 99.6%, 2, and the selectivity of 6-diisopropyl aniline is 75.0%.
[embodiment 8]
Used catalyzer and examining method are with embodiment 2, and just changing temperature of reaction is 200 ℃, and pressure is 1.2MPa, and the liquid phase air speed is 0.6 hour
-1, NH
3/ 2,6-DIPP=5, H
2/ 2,6-DIPP=40.2, the transformation efficiency of 6-diisopropyl phenol is 74.7%, 2, and the selectivity of 6-diisopropyl aniline is 94.9%.
Claims (10)
1, a kind of preparation 2, the method for 6-diisopropyl aniline, with 2,6-diisopropyl phenol and ammonia are raw material, react under following reaction conditions:
A) under hydro condition, raw material 2, the 6-diisopropyl phenol fixes bed bioreactor with ammonia by gas-solid and contacts with catalyzer, temperature of reaction is 180～250 ℃, reaction pressure is 1.2～1.7MPa, and raw material 2, the weight space velocity of 6-diisopropyl phenol are 0.1～0.6 hour
-1, with molar ratio computing ammonia: 2, the 6-diisopropyl phenol is 5～15: 1, hydrogen: 2, the 6-diisopropyl phenol is 10～50: 1;
B) used catalyzer comprises following component by weight percentage:
1) complex carrier formed by spinel of 98%～99.95% gama-alumina skeleton and surface growth; With carry thereon
2) 0.05～2% palladium or its oxide compound;
Wherein spinel structure is aluminum oxide-magnesium oxide-potassium oxide structure, the amount of potassium oxide is 0.01～3.0% of a total catalyst weight in the spinel, magnesian amount is 0.1～5.0% of a total catalyst weight, and the amount of aluminum oxide is 0.5～10.0% of a total catalyst weight.
2, according to the described preparation 2 of claim 1, the method for 6-diisopropyl aniline, it is characterized in that in the parts by weight gama-alumina: spinel is 70～95: 5～30.
3, according to the described preparation 2 of claim 2, the method for 6-diisopropyl aniline, it is characterized in that in the parts by weight gama-alumina: spinel is 85～95: 5～15.
4, according to the described preparation 2 of claim 1, the method for 6-diisopropyl aniline is characterized in that complex carrier first carbonate or bicarbonate solution dipping with basic metal or alkaline-earth metal before supported palladium or its oxide compound.
5, according to the described preparation 2 of claim 4, the method for 6-diisopropyl aniline is characterized in that complex carrier floods with yellow soda ash or sodium hydrogen carbonate solution earlier before supported palladium or its oxide compound.
6, according to the described preparation 2 of claim 1, the method for 6-diisopropyl aniline is characterized in that also containing 0.005～1% lanthanum or its oxide compound in the catalyzer by weight percentage.
7, according to the described preparation 2 of claim 6, the method for 6-diisopropyl aniline is characterized in that the consumption of lanthanum by weight percentage or its oxide compound is 0.005～0.5%.
8, according to the described preparation 2 of claim 7, the method for 6-diisopropyl aniline is characterized in that in the consumption of lanthanum or its oxide compound by weight percentage be 0.05～0.15%.
9, according to the described preparation 2 of claim 1, the method of 6-diisopropyl aniline, the amount that it is characterized in that potassium oxide in the spinel is 0.1～1.5% of a total catalyst weight, and magnesian amount is 0.3～1.0% of a total catalyst weight, and the amount of aluminum oxide is 2.0～5.0% of a total catalyst weight.
10, according to the described preparation 2 of claim 9, the method for 6-diisopropyl aniline, the amount that it is characterized in that potassium oxide in the spinel is 0.5～1.2% of a total catalyst weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150736 CN1241902C (en) | 2003-09-03 | 2003-09-03 | Method of preparing 2, 6-diisoprogyl aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150736 CN1241902C (en) | 2003-09-03 | 2003-09-03 | Method of preparing 2, 6-diisoprogyl aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1590365A CN1590365A (en) | 2005-03-09 |
| CN1241902C true CN1241902C (en) | 2006-02-15 |
Family
ID=34597666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03150736 Expired - Fee Related CN1241902C (en) | 2003-09-03 | 2003-09-03 | Method of preparing 2, 6-diisoprogyl aniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241902C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603537A (en) * | 2012-02-21 | 2012-07-25 | 南通市东昌化工有限公司 | Production method of 2,6-dimethylaniline |
-
2003
- 2003-09-03 CN CN 03150736 patent/CN1241902C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1590365A (en) | 2005-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369734B (en) | Method for preparing industrial fructose by isomerizing glucose through chemical catalysis method | |
| EP1629888A1 (en) | Catalyst for the synthesis of dimethyl carbonate from urea and methanol, preparation and use thereof | |
| CN109126792B (en) | Synthesis and application of Cu-Silicate-1 catalyst | |
| CN1156425C (en) | Process for preparing cyclohexanone by dehydrogenating cyclohexanol | |
| CN1204097C (en) | Method for preparing propylene by butene disproportionation | |
| CN1241902C (en) | Method of preparing 2, 6-diisoprogyl aniline | |
| CN1177791C (en) | Process and the manufacture of alpha, alpha-branched carboxylic acids | |
| CN1274414C (en) | Catalyst for preparing 2,6-diiso proplyl aniline | |
| CN115178285B (en) | Catalyst for isomerising glucose into fructose and preparation method thereof | |
| CN1192821C (en) | Catalyst for preparing 2,6-diisopropyl aniline | |
| CN1118325C (en) | Catalyst for synthesizing dimethyl carbonate and its application | |
| CN109096029B (en) | Preparation method of isopropyl benzene | |
| CN103539718B (en) | The production method of indoles | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN103030508B (en) | The method of amylene and ethene producing propylene with dismutation | |
| CN1187119C (en) | Catalyst for preparing 2,6-diisopropyl aniline | |
| CN105268434B (en) | Hydrofining crude terephthalic acid catalyst | |
| RU2120822C1 (en) | Methylmercaptan synthesis catalyst | |
| CN1089276C (en) | Carried hydrotalcite catlyst and the preparation of aliphatic alcohol ether acetate | |
| CN114515600B (en) | Metal hetero element modified titanium nitride-polyaniline catalyst, preparation method and application thereof in synthesizing para-hydroxyanisole | |
| CN115490579B (en) | Preparation method of hydroxyanisole | |
| US4453025A (en) | Process for the preparation of 3,5-xylenol | |
| CN107973682B (en) | Method for preparing propylene by propane dehydrogenation | |
| CN1263714C (en) | Method for preparing propene by disproportionation of butene | |
| CN118287070A (en) | Alcohol oxidation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060215 Termination date: 20110903 |