CN1367040A - Nitrobenzene hydrogenation catalyst with high aniline yield rate - Google Patents
Nitrobenzene hydrogenation catalyst with high aniline yield rate Download PDFInfo
- Publication number
- CN1367040A CN1367040A CN 02100610 CN02100610A CN1367040A CN 1367040 A CN1367040 A CN 1367040A CN 02100610 CN02100610 CN 02100610 CN 02100610 A CN02100610 A CN 02100610A CN 1367040 A CN1367040 A CN 1367040A
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- copper
- cerium
- nitrobenzene
- ceo
- aniline
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Abstract
A solid catalyst for hydrogenation of nitrobenzene to prepare aniline is characterized by that it is a new-type copper-doped composite cerium oxide, and as its structural characteristics give transfer dcapability to strong electrons, it possesses excellent low-temp. hydrogenation catalysis property, and can prevent side reaction at high temp., therefore it can prepare aniline by means of hydrogenation of nitrobenzene under the conditions of 175-250 deg.C, 0.1-1.0 MPa, LHSV=3h(-1) and Hz-nitrobenzene (mole ratio)=4-6, and its per pass yield rate is above 99.99%.
Description
The invention relates to a kind of solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation, ICL is Inter/class:C 07c 209/36.
Aniline is important Organic Ingredients, adopts the iron powder reducing method to produce in early days, and reaction rate is slow, product separates difficulty, is difficult for serialization production, and etching apparatus, and the iron dirt is dyed environment, gradually is eliminated in recent years.The sixties in last century, U.S. Ha Er Kanggong department succeeded in developing phenol ammoniation process technology, adopted the solid phosphoric acid catalyst serialization to produce, and technological process is simple, blowdown is few, catalyst life is long; But production cost is higher, lacks superiority economically.Nitrobenzene production Technology maturation, resource abundance and price are lower, the rapid progress of hydrogen producing technology in addition, therefore at present both at home and abroad industrial production aniline generally adopt the hydrogenation of chloronitrobenzene technology, different persons be the reaction bed type that adopts of different process be fluid bed or fixed bed; Use fixed bed reactors to use gas phase hydrogenation technology or liquid-phase hydrogenatin technology, the core of technical development is the research and development of new catalyst, target directing low reaction temperatures, low reaction pressure and high aniline yield rate are to realize simplifying technological process, to cut down the consumption of energy and material consumption, deduction and exemption environmental pollution and realization long-term operation.
The hydrogenation of chloronitrobenzene catalyst that has been applied to and has has researched and developed mainly contains two classes: and the copper-loaded class of silica [EP 062 542, and 1982; USP 4 448 993, and 1984; JP 7206788,1995; JP 7070001,1995; Direction is bright etc., applied chemistry, 1997,14 (2): 57] and active carbon or alumina load noble metal, especially the palladium class [USP 4 179 470,1979; USP 5 304525, and 1994; DE 4 039 026, and 1992; USP 5 283 365, and 1994; USP 5 616 806, and 1997; USP 5 808 157, and 1998; USP 5 877 350, and 1999; USP 6 080 890,2000 and CN 1056489,1991], last class is mainly used in fluidized-bed process, 250～430 ℃ of general reaction temperatures, reaction pressure 0.3～1.0MPa, whole process aniline yield rate 90～99%; The carried noble metal class only is used for tank reactor or fixed bed reactors, and reaction temperature is generally greater than 300 ℃, and reaction pressure is higher to be 1.0～3.5MPa, the once through yield 45～97% of aniline.
The invention provides a kind of solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation, it is characterized in that it is that a class is mixed copper cerium oxide composite oxides, because copper atom enters the fluorite structure of cerium oxide, architectural feature has given this class catalysis material forceful electric power transmission capacity, has excellent low temperature hydrogenation catalytic performance, thereby avoided the contingent side reaction of high temperature, improved the catalytic hydrogenation selectivity, at 175 ℃～250 ℃ and 0.1～1.0MPa, especially under 180 ℃ and the 0.3MPa normal pressure, as nitrobenzene feed air speed LHSV=3h
-1And H
2Under/nitrobenzene (mol ratio)=4～6 condition, the once through yield of manufacturing process of aniline through nitrobenzene hydrogenation reaches 99.99～100.0%, but and long-term operation.
The invention is characterized in the described copper cerium oxide composite oxides of mixing, thing belongs to fluorite type structure mutually, and chemical formulation is (Cu) CeO
2(x), x represents the mass fraction (%) that contains Cu in these composite oxides in the formula brace, x scope 2～16%, and the catalyst mode that is used as manufacturing process of aniline through nitrobenzene hydrogenation is body facies pattern or support type.
Body facies pattern provided by the invention is mixed the preparation method of copper cerium oxide composite oxide catalysts, it is characterized in that be that roasting is made behind the copper cerium mixed hydroxides with coprecipitator with copper and cerium solution co-precipitation.
Support type provided by the invention is mixed the preparation method of copper cerium oxide composite oxide catalysts, it is characterized in that directly drying or making through coprecipitator roasting after co-precipitation on the carrier forms copper cerium hydroxide behind copper and the cerium solution impregnated carrier oxide.
The solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation provided by the invention, the sintering temperature scope is 400～700 ℃ when the preparation catalyst.
The solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation provided by the invention, the coprecipitator that uses when the preparation catalyst is NaOH and ammoniacal liquor.
The solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation provided by the invention, nitrate, sulfate and chloride that copper that uses when the preparation catalyst and cerium salt are copper and cerium.
Support type provided by the invention is mixed the support oxide described in the preparation method of copper cerium oxide composite oxide catalysts, it is characterized in that specific area 100～250m
2g
-1, pore volume 0.5～0.8mlg
-1Al
2O
3With specific area 100～300m
2g
-1, pore volume 0.4～0.7mlg
-1SiO
2
The solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation that is provided is provided, preparation technology is simple, only uses commercially available industrial chemicals production commonly used.
Following embodiment will be described further catalytic performance and the preparation method who is used for the solid catalyst of manufacturing process of aniline through nitrobenzene hydrogenation provided by the invention, but not thereby limiting the invention.
Embodiment 1
By Cu content is CeO
27.4% (m) calculate and take by weighing copper nitrate and cerous nitrate, add the mixed aqueous solution that deionized water is mixed with copper and cerium, be heated to 60 ℃, add the sodium hydroxide solution of 2mol/L and regulate pH=4～5, co-precipitation obtains copper cerium hydroxide, and 70 ℃ were worn out 3～4 hours, filtration, eccysis Na
+The back is in 120 ℃ of oven dry, and roasting is 4 hours in 450～650 ℃ of air, and what obtain containing Cu 7.4% mixes copper cerium oxide composite oxide catalysts sample 1, and its chemical formulation is (Cu) CeO
2(7.4).
Embodiment 2
Copper and cerium mixed nitrate aqueous solution with embodiment 1, add 1: 1 ammoniacal liquor and be adjusted to pH ≈ 3, obtain the co-precipitation hydroxide of copper and cerium, 70 ℃ of aging filtrations after 3 hours, 120 ℃ of oven dry, roasting is 4 hours in 450～650 ℃ of air, and what obtain containing Cu 7.1% mixes copper cerium oxide composite oxide catalysts sample 2, and its chemical formulation is (Cu) CeO
2(7.1).
Embodiment 3
Replace copper nitrate and cerous nitrate with copper sulphate and cerous sulfate, other step is with embodiment 1, and what obtain containing Cu 7.4% mixes copper cerium oxide composite oxide catalysts sample 3, and its chemical formulation is (Cu) CeO
2(7.4).
Embodiment 4
Replace copper nitrate and cerous nitrate with the chloride of copper and cerium, and be CeO by Cu content
29.3% (m) calculate the amount of taking by weighing, other step is with embodiment 1, what obtain containing Cu 9.3% mixes copper cerium oxide composite oxide catalysts sample 4, its chemical formulation is (Cu) CeO
2(9.3).
Embodiment 5
1: 1 ammoniacal liquor in 60 ℃ and the cerous nitrate aqueous solution to pH=4,70 ℃ aging filtered after 3 hours, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours obtain CeO
2Solid.Take by weighing a certain amount of CeO that makes
2Solid calculates and takes by weighing the copper nitrate that carries Cu 8.2% by the hole saturation and is made into the aqueous solution, the CeO that dipping is taken by weighing
2, spend the night and dry in the shade, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours, what obtain containing Cu 8.2% mixes copper cerium oxide composite oxide catalysts sample 5, and its chemical formulation is (Cu) CeO
2(8.2).
Embodiment 6
Take by weighing a certain amount of cerous nitrate and place porcelain evaporating dishes, 650 ℃ of roastings obtained CeO in 4 hours in air
2Solid.Other step is with embodiment 5, and what obtain containing Cu 8.2% mixes copper cerium oxide composite oxide catalysts sample 6, and its chemical formulation is (Cu) CeO
2(8.2).
Embodiment 7
Take by weighing a certain amount of γ-Al
2O
3Carrier (specific area 180m
2g
-1, pore volume 0.65mlg
-1), by (Cu) CeO of load 10%
2(7.4) mix copper cerium oxide composite oxide catalysts and calculate and take by weighing copper nitrate and cerous nitrate, press maceration extract: γ-Al again
2O
3Volume ratio be to be mixed with volume required copper and cerium mixed aqueous solution at 1: 1, with γ-Al
2O
3Pour into wherein and stir evenly.Sodium hydroxide solution with 2mol/L under stirring is neutralized to pH=5,70 ℃ of placements 2 hours of wearing out, the unnecessary clear liquid of elimination, eccysis Na
+The back is in 120 ℃ of oven dry, and roasting is 4 hours in 500 ℃ of air, obtains catalyst sample 7, and its chemical formulation is (Cu) CeO
2(7.4)/Al
2O
3
Embodiment 8
Carrier is replaced by SiO
2(specific area 267m
2g
-1, pore volume 0.52mlg
-1), all the other obtain catalyst sample 8 with embodiment 7, and its chemical formulation is (Cu) CeO
2(7.4)/SiO
2
Embodiment 9
With embodiment 7, but according to γ-Al
2O
3Water absorption rate and the amount of taking by weighing preparation need the copper and the cerium mixed aqueous solution of volume, and flood the γ-Al of institute's weighing by the hole saturation
2O
3, spend the night and dry in the shade, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain catalyst sample 9, and its chemical formulation is (Cu) CeO
2(7.4)/Al
2O
3
Embodiment 10
Carrier is replaced by SiO
2, other step obtains catalyst sample 10 with embodiment 9, and its chemical formulation is (Cu) CeO
2(7.4)/SiO
2
Embodiment 11
With embodiment 9, but the nitrate that calculates and take by weighing copper and cerium makes load 15% mix copper cerium oxide composite oxides, and composite oxides contain Cu 10.8%, obtain catalyst sample 11, and its chemical formulation is (Cu) CeO
2(10.8)/Al
2O
3
Embodiment 12
By Cu content is CeO
24.3% (m) calculate and take by weighing copper nitrate and cerous nitrate, by the step of embodiment 1 make contain Cu 4.3% mix copper cerium oxide composite oxide catalysts sample 12, its chemical formulation is (Cu) CeO
2(4.3).
Embodiment 13
By Cu content is CeO
22.1% (m) calculate and take by weighing copper nitrate and cerous nitrate, by the step of embodiment 1 make contain Cu 2.1% mix copper cerium oxide composite oxide catalysts sample 13, its chemical formulation is (Cu) CeO
2(2.1).
Embodiment 14
By Cu content is CeO
215.3% (m) calculate and take by weighing copper nitrate and cerous nitrate, by the step of embodiment 1 make contain Cu 15.3% mix copper cerium oxide composite oxide catalysts sample 14, its chemical formulation is (Cu) CeO
2(15.3).
Embodiment 15
In the reaction unit that flows, loading catalyst sample 1 about 5ml after 3 hours, is cooled to 200 ℃ and 0.3MPa, H in 320 ℃ of hydrogen reducings
2/ nitrobenzene mol ratio 4, nitrobenzene feed air speed 3h
-1Under the condition, carried out hydrogenation reaction 6 hours, aniline content 99.99% in 1～6 hour sample analysis product.
Embodiment 16
With embodiment 15, but reaction condition changes to 180 ℃, 0.5MPa, H
2/ nitrobenzene mol ratio 6, nitrobenzene feed air speed 3h
-1, carried out hydrogenation reaction 6 hours, aniline content 100% in 1～6 hour sample analysis product.
Embodiment 17～30
Selected reaction condition is 180 ℃, 0.4MPa, H
2/ nitrobenzene mol ratio 5 and nitrobenzene feed air speed 3h
-1, other step was carried out hydrogenation reaction 8 hours with embodiment 15 to sample catalyst 1～14, and the result converges and lists in table 1.
Table 1
| Embodiment number | Catalyst agent formation and method for making are mixed in the copper cerium oxide aniline and are received sample number and contain Cu% (m) rate, % |
| 17 18 19 20 21 22 23 24 25 26 27 28 29 30 | ??1???????(Cu)CeO 2(7.4), coprecipitation 7.4 100.00 2 (Cu) CeO 2(7.1), ammonia coprecipitation 7.1 99.97 3 (Cu) CeO 2(7.4), coprecipitation 7.4 100.00 4 (Cu) CeO 2(9.3), coprecipitation 9.3 99.99 5 (Cu) CeO 2(8.2), precipitation infusion process 8.2 100.00 6 (Cu) CeO 2(8.2), roasting infusion process 8.2 99.99 7 (Cu) CeO 2(7.4)/Al 2O 3, coprecipitation 7.4 99.94 8 (Cu) CeO 2(7.4)/SiO 2, coprecipitation 7.4 99.95 9 (Cu) CeO 2(7.4)/Al 2O 3, infusion process 7.4 99.96 10 Cu) and CeO 2(7.4)/SiO 2, infusion process 7.4 99.96 11 (Cu) CeO 2(10.8)/Al 2O 3, infusion process 10.8 99.95 12 (Cu) CeO 2(4.3), coprecipitation 4.3 85.23 13 (Cu) CeO 2(2.1), coprecipitation 2.1 72.51 14 (Cu) CeO 2(15.3), coprecipitation 15.3 99.65 |
Claims (10)
1. a solid catalyst that is used for manufacturing process of aniline through nitrobenzene hydrogenation is characterized in that the novel copper cerium oxide composite oxides of mixing of a class.
2. the described copper cerium oxide composite oxides of mixing of claim 1 is characterized in that thing belongs to fluorite type structure mutually, and chemical formulation is (Cu) CeO
2(x), x represents the mass fraction (%) that contains Cu in these composite oxides, x scope 2～16% in the formula brace.
3. the described copper cerium oxide composite oxides of mixing of claim 1 and claim 2 is characterized in that the catalyst mode as manufacturing process of aniline through nitrobenzene hydrogenation is body facies pattern or support type.
4. the described body facies pattern of claim 3 preparation method that mixes copper cerium oxide composite oxide catalysts is characterized in that be that roasting is made behind the copper cerium mixed hydroxides with coprecipitator with copper and cerium solution co-precipitation.
5. the described support type of claim 3 preparation method that mixes copper cerium oxide composite oxide catalysts is characterized in that behind copper and the cerium solution impregnated carrier oxide directly oven dry or makes through coprecipitator roasting after co-precipitation on the carrier forms copper cerium hydroxide.
6. claim 4 and 5 described preparation catalyst sintering temperature scopes are 400～700 ℃.
7. claim 4 and 5 described coprecipitators are NaOH and ammoniacal liquor.
8. claim 4 and 5 described copper and cerium salt are nitrate, sulfate and the chloride of copper and cerium.
9. the described support oxide of claim 5 is characterized in that specific area 100～250m
2g
-1, pore volume 0.5～0.8mlg
-1Al
2O
3With specific area 100～300m
2g
-1, pore volume 0.4～0.7mlg
-1SiO
2
10. the reaction condition of the described manufacturing process of aniline through nitrobenzene hydrogenation of claim 1 is 175 ℃～250 ℃, 0.1～1.0MPa, nitrobenzene feed air speed LHSV=1～3h
-1And H
2/ nitrobenzene (mol ratio)=4～6.
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|---|---|---|---|
| CN 02100610 CN1207264C (en) | 2002-01-25 | 2002-01-25 | Nitrobenzene hydrogenation catalyst with high aniline yield rate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100610 CN1207264C (en) | 2002-01-25 | 2002-01-25 | Nitrobenzene hydrogenation catalyst with high aniline yield rate |
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| Publication Number | Publication Date |
|---|---|
| CN1367040A true CN1367040A (en) | 2002-09-04 |
| CN1207264C CN1207264C (en) | 2005-06-22 |
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ID=4739421
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|---|---|---|---|
| CN 02100610 Expired - Fee Related CN1207264C (en) | 2002-01-25 | 2002-01-25 | Nitrobenzene hydrogenation catalyst with high aniline yield rate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045213B (en) * | 2007-04-30 | 2010-05-19 | 陕西师范大学 | Solid carried ion liquid-nanometer metal particle catalyst, and its preparing method, and application in synthesis of arylamine |
| CN103341362A (en) * | 2013-07-17 | 2013-10-09 | 临邑县鲁晶化工有限公司 | Rare earth-copper catalyst for preparing o-aminoethylbenzene by hydrogenating o-nitroethylbenzene |
| CN103351303A (en) * | 2013-07-17 | 2013-10-16 | 临邑县鲁晶化工有限公司 | Continuation method of manufacturing o-Aminoethylbenzene through hydrogenation by o-Nitroethylbenzene |
| CN103420849A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN106914255A (en) * | 2017-03-29 | 2017-07-04 | 国家纳米科学中心 | A kind of non-alloyed metal composite and its preparation method and application |
| CN112958097A (en) * | 2021-02-08 | 2021-06-15 | 清华大学 | Copper-based supported catalyst for synthesizing aniline by nitrobenzene hydrogenation and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10322992B2 (en) | 2016-12-13 | 2019-06-18 | King Abdulaziz University | Methods of making cerium oxide polyaniline composite nanospheres and methods of use |
-
2002
- 2002-01-25 CN CN 02100610 patent/CN1207264C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045213B (en) * | 2007-04-30 | 2010-05-19 | 陕西师范大学 | Solid carried ion liquid-nanometer metal particle catalyst, and its preparing method, and application in synthesis of arylamine |
| CN103420849A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN103420849B (en) * | 2012-05-16 | 2015-04-08 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN103341362A (en) * | 2013-07-17 | 2013-10-09 | 临邑县鲁晶化工有限公司 | Rare earth-copper catalyst for preparing o-aminoethylbenzene by hydrogenating o-nitroethylbenzene |
| CN103351303A (en) * | 2013-07-17 | 2013-10-16 | 临邑县鲁晶化工有限公司 | Continuation method of manufacturing o-Aminoethylbenzene through hydrogenation by o-Nitroethylbenzene |
| CN106914255A (en) * | 2017-03-29 | 2017-07-04 | 国家纳米科学中心 | A kind of non-alloyed metal composite and its preparation method and application |
| CN112958097A (en) * | 2021-02-08 | 2021-06-15 | 清华大学 | Copper-based supported catalyst for synthesizing aniline by nitrobenzene hydrogenation and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1207264C (en) | 2005-06-22 |
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