CN100368085C - Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene - Google Patents
Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene Download PDFInfo
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- CN100368085C CN100368085C CNB2004100678660A CN200410067866A CN100368085C CN 100368085 C CN100368085 C CN 100368085C CN B2004100678660 A CNB2004100678660 A CN B2004100678660A CN 200410067866 A CN200410067866 A CN 200410067866A CN 100368085 C CN100368085 C CN 100368085C
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Abstract
The present invention relates to a preparation method of a fluid bed catalyst for producing aniline through nitrobenzene gas-phase hydrogenation, which mainly solves the problems of few cuprammonia sources, complicated catalyst preparation, short disposable service life, etc. in the prior art. In the preparation method, copper is used as raw material, silicon dioxide is used as a carrier, and the cuprammonia with the chemical formula of Cu<a>(NH<3>)<b>X<c> is used as steeping liquor, wherein x is selected from at least one of OH<->, NO3<->, SO4<2->, CO3<2->, CH3COO<->, HCOO<-> or (CO2)2<2->; chrome, molybdenum, etc., and active components which are not enforcedly added are added simultaneously; with the technical scheme, the preparation method better solves the problems of the prior art and can be used in industrial production for preparing the aniline through nitrobenzene hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene.
Technical background
Aniline (Aniline; Benzenamine; Aminobenzene), be commonly called as aniline oil, be a kind of important Organic Chemicals and fine-chemical intermediate, reach kind more than 300 by Aniline Production than staple product, it is the important source material of plastics, spices, clothes, medicine and rubber accelerator, age resistor, the stabilizing agent that also is used for explosive, the anti-knock agent in the gasoline etc., and can make solvent.Because the demand to products such as synthetic leather, polyurethane constantly increases, 80% of global aniline output is used for the production of methyl diphenylene diisocyanate (MDI).
Aniline in 1826 is made when indigo by chemist O.Unverdorben destructive distillation first, and Bechamp in 1854 has developed nitrobenzene is reduced into aniline in the presence of iron powder and acetic acid industrialized preparing process, and carries out industrial production in 1857 by Perkin.
The aniline industrial production mainly adopts nitrobenzene (NB) reduction and phenol ammonia to separate technology.At present, each Aniline Production factory of the world mostly uses the nitrobenzene reduction route.Reduction of nitrobenzene is divided into iron powder reducing and hydrogenating reduction again.Hydrogenating reduction is divided into gas phase hydrogenation method and liquid-phase hydrogenatin method again.Gas phase hydrogenation has fluidized-bed process and fixed-bed process again.
According to the document of having delivered, the catalyst system that is used for the nitrobenzene gas phase hydrogenation has copper system, nickel system and precious metal palladium etc.Catalyst carrier has silica gel, zeolite, activated alumina and diatom scholar etc.Copper catalyst has higher activity and selectivity; Raney nickel is often made the multielement composite catalyst, to keep the high selectivity and the activity of reaction, avoids benzene ring hydrogenation.In concrete the production, adopt fixed bed or fluidized-bed reactor usually.
The bibliographical information of having delivered claims that the preparation method of Cu-series catalyst has equi-volume impregnating and ion-exchange usually, and the latter is by ammoniacal copper complex ion Cu (NH
3)
4 2+After the hydroxyl H on microsphere silica gel surface exchange, form stable
Structure is evenly distributed on the silica gel surface, has good decentralization, thereby has very high activity and selectivity.
Cuprammonia is a kind of complicated alkaline solution that has the number of chemical balance, is made up of different kinds of ions and more free ammonia.According to the document introduction of having delivered, the corresponding acid of acid ion is non-oxidizing acid in cuprammonia, and promptly X is OH
-, CO
3 2-, CH
3COO
-, HCOO
-, (CO
2)
2 2-, copper can not directly be dissolved in this class acid, needs oxidants such as blowing air, hydrogen peroxide, could oxidized dissolving, simultaneously with contain the ammonia solution effect and form corresponding cuprammonia; When the corresponding acid of acid ion is acid with strong oxidizing property, promptly X is NO
3 -, SO
4 2-, copper can directly be dissolved in acid and become soluble copper salt, again with contain the ammonia solution complexing and become corresponding cuprammonia.
The Australia scholar is at document Applied Catalysis[1987 (31)] in report be that raw material makes cuprammonia (PH=8～10) with copper nitrate and ammoniacal liquor, be that raw material, employing ion-exchange make Cu/SiO with this solution
2Catalyst, and compare with the catalyst that equi-volume impregnating makes, the former has better reactivity.
The patent US of document American Cyanamid Company 2891094 reports are with Cu (NO
3)
2.3H
2O and concentrated ammonia liquor are initiation material, make cuprammonia, and the catalyst that makes with this solution is used for the aniline production by gas phase hydrogenation of nitrobenzene reaction, and the selectivity of aniline and the conversion ratio of nitrobenzene all are higher than 99.5% for a long time.
The patent US 2822397 of U.S. Unichem is with nickel/aluminium catalyst series, adopt the Fixed Bed Gas Phase hydrogenation method, the mol ratio of nitrobenzene and hydrogen is 1: 9, and load reaches per hour every liter of catalyst, the inlet amount of nitrobenzene is 300 grams, and its nitrobenzene air speed is about 0.5 hour
-1, reaction temperature is 300 ℃, the initial yield of aniline is 99.5%.
Patent US 4265834 is with Pd-V-Mo-Cr-Pb-Bi-Zn/ α-Al
2O
3Be catalyst, adopt tubular reactor, 260～270 ℃ of reaction temperatures, hydrogen is than 1: 6, the initial yield 99.85% of aniline.Shortcoming is that fixed bed is removed difficulty of heat, needs frequently to stop.
Patent GB 1385454 is a catalyst with Cu-Cr-Ba-Mg, fixed bed reactors, and 200～300 ℃ of reaction temperatures, pressure is 0.2～0.4MPa, adopts hydrogen, nitrogen mixture body, ratio is NB: H
2: N
2=1: 7～19: 1.8～2.9, catalyst reaches 1 year entire life after repeatedly regenerating.But this technology nitrobenzene conversion ratio is 85～90% to need recycled, and the hydrogen use amount is bigger.
Patent US 3504035 is a catalyst with Cu-Si or Cu-Al, and Cr, Ba, Zn etc. carry out modification, 200～400 microns of catalyst particle sizes.Adopt fluid bed gas phase hydrogenation method, 250～300 ℃ of reaction temperatures, reaction pressure 0.4～1.0Mpa, the mol ratio of nitrobenzene and hydrogen is 1: 3, the initial yield of aniline is greater than 99%.
Above document has only reported one, the preparation method of two kind of cuprammonia, though and the initial yield of the aniline that has higher, can reach 99.85%, but all less than disclosing its concrete lifetime data.Catalyst in the above-mentioned document is 5.0 hours through the inventor in the nitrobenzene air speed
-1, adopting hydrogen, nitrogen mixture body, mol ratio is NB: H
2: N
2=1: 9～18: under 1.4～2.0 conditions, reach 0.1% as test endpoint with the concentration that detects nitrobenzene NB in the product, accelerate degradation and measure a life-span discovery of catalyst, a life-span is all less than 50 hours, be that reaction unit needs catalyst is carried out frequent regeneration, could satisfy production requirement.
Summary of the invention
Technical problem to be solved by this invention be the preparation catalyst that provides in the prior art the cuprammonia source less, preparation is complicated, the disposable life-span of catalyst is short, cause catalyst regeneration frequent, the problem that influence is produced provides a kind of preparation method of new fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene.The catalyst that uses this method to prepare is used for the manufacturing process of aniline through nitrobenzene hydrogenation process and has the initial yield height of aniline, long characteristics of disposable life-span of catalyst.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene may further comprise the steps:
(1) in the presence of air and ammonia source, reaction temperature is 40～65 ℃, and oxidized metal copper becomes cuprammonia, and cuprammonia is formed expression with mole and comprised following general formula: Cu
a(NH
3)
bX
c
Wherein, the span of a is 1～2;
The span of b is 1～5;
The span of c is 0.5～4;
X is selected from OH
-, NO
3 -, SO
4 2-, CO
3 2-, CH
3COO
-, HCOO
-Or (CO
2)
2 2-In at least a;
(2) carrier silica is selected from aqueous metal salt incipient impregnation at least a among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt with containing, oven dry, roasting;
(3) will obtain catalyst through the silica supports and the cuprammonia hybrid infusion of above-mentioned processing.
In the technique scheme, the value preferable range of a is 1 or 2; The preferred span of b is 2～4; The preferable range of c is 1～2; The preferable range of x is OH
-, CO
3 2-, CH
3COO
-Or (CO
2)
2 2-In at least a.In the cuprammonia, copper content preferable range is 1.70～2.20 mol; The pH value preferable range of cuprammonia is 9～11; The preferable range of cuprammonia proportion is 1.10～1.20.Described slaine is preferably nitrate or ammonium salt.By weight, the liquid-solid ratio of cuprammonia and treated carrier silica is 0.9～2.0, and dipping temperature is 45～95 ℃, and impregnation pressure is 2.66 * 10
-3～0.25MPa is preferably 2.66～3.99 * 10
-3The negative pressure of MPa or the malleation of 0.11～0.25MPa.The impregnation method of cuprammonia and carrier is preferably segmentation dipping or constant temperature dipping.Segmentation dipping optimum condition is 1～4 hour, 85～95 ℃ dippings of 2～5 hours, 60～80 ℃ dippings of 45～60 ℃ of dippings 3～8 hours.Constant temperature dipping optimum condition is 60～95 ℃ of dippings 5～12 hours.
Preparation method of the present invention is as follows:
A) metallic copper is put into reaction pot, impurity such as the oxide on first purifying a spot of other metal of removal and surface thereof, chloride, final copper content needs greater than 99.0% (weight).After adding water, add blowing air behind ammonia, corresponding acid or the ammonium salt-containing again, metallic copper is the oxidized cuprammonia that forms constantly;
B) at least a slaine wiring solution-forming that will contain among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt mixes drying, roasting with carrier silica;
C) will flood a few hours through the silica and the cuprammonia of above-mentioned processing, filter, washing, oven dry gets the catalyst finished product after the roasting.
The raw material of preparation manufacturing process of aniline through nitrobenzene hydrogenation fluid catalyst is:
Copper is cathode copper or copper powder;
Acid is sulfuric acid, glacial acetic acid (weight percent concentration is 36～100%), formic acid, oxalic acid, carbonic acid or carbon dioxide etc.;
Ammonia is ammonia or concentrated ammonia liquor (weight percent concentration is 25%);
Ammonium salt-containing is ammonium salt or hydrogen ammonium salt, and the anion of salt is the acid ion of above-mentioned acid;
The chromium source is chromic nitrate, potassium chromate, ammonium chromate, chromic anhydride or chromium+oxalic acid;
The molybdenum source is an ammonium molybdate;
The barium source is barium nitrate or barium hydroxide;
The zinc source is zinc nitrate, zinc acetate or zinc hydroxide;
The cerium source is cerous nitrate or cerium oxalate;
The nickel source is a nickel nitrate.
Using the specific surface area of catalyst of the inventive method preparation is 200～500 meters
2/ gram, pore volume is 0.2～1.5 centimetre
3/ gram, average pore size is greater than 5 nanometers, and average grain diameter is 40～200 microns.
Examination device of the present invention is 38 * 1800 millimeters stainless steel fluidized-bed reactors of , in adorn 250 milliliters of catalyst.
The examination process conditions are: 180～300 ℃ of reaction temperatures, and 220～270 ℃ of reasonable scopes, the mol ratio of nitrobenzene and hydrogen are 1: 4～12, reasonable scope 1: 6～9, reaction pressure is generally normal pressure, also can operate at pressurized conditions.
Reacted air-flow cools off through condenser, carries out gas-liquid separation, and product is collected in the receiver.Be sampled as one hour, the conversion ratio of gas chromatographic analysis nitrobenzene and the yield of aniline at every turn.
Computing formula:
The present invention is because employing new copper ammoniacal liquor is that maceration extract prepares copper-based catalysts, added the active constituent of chromium, molybdenum etc. and non-imposed adding simultaneously, the inventor is surprised to find that, catalyst not only can keep the higher initial yield of aniline, and the disposable life-span can reach 176 hours, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
After placing 5～10% sodium hydroxide solutions to boil 3 hours the electrolysis copper billet that reclaims, lixiviating liquid soaked 8 hours with 3% rare nitric acid or dilute sulfuric acid again, and disacidify liquid is washed to neutrality, the purifying copper that obtains, and content is greater than 99.5% (weight), and is standby.
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 418 grams, glacial acetic acid 113 grams, stir down logical ammonia to PH greater than 7.0, add above-mentioned copper billet 63.6 grams, blowing air and ammonia maintain the temperature at below 70 ℃, add above-mentioned copper billet 21.8 grams after about 4 hours again, continuation blowing air, ammonia to copper powder react completely, and need 7 hours approximately, cooling, cross a small amount of residue of elimination, obtain cuprammonia (1).By analysis, total copper content (molar concentration) is 2.14 mol, and proportion 1.15, pH value are 10.9.
Take by weighing 1.8 gram (NH
4)
2CrO
4, 1.1 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (A).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mix stirring with carrier (A), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 4 hours, rise to again 85～90 ℃ the dipping 4 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 2]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (B).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 450 gram and mix stirring with carrier (B), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 2 hours, rise to again 85～90 ℃ the dipping 8 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 3]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.1 gram (NH
4)
6Mo
7O
244H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O and 3.0 gram Ni (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (C).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 485 gram and mix stirring with carrier (C), prior to 50～60 ℃ the dipping 2 hours, be warming up to 70～80 ℃ the dipping 3 hours, rise to again 85～90 ℃ the dipping 5 hours, cooling, filter, with 500 milliliters of washed twice of 2.5% weak aqua ammonia, blue with the deionized water washing again to not having, in 100 ℃ of oven dry 12 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 4]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 3.1 gram Ce (NO
3)
36H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (D).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mix stirring with carrier (D), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 5]
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, add entry 364 gram, glacial acetic acid 77.3 grams, stir down logical ammonia to PH greater than 7.5, disposable adding copper powder (weight 99.7%, 100 orders) 68.2 grams (1.07 moles), blowing air and ammonia maintain the temperature at below 70 ℃, need 4～5 hours fully approximately to copper powder dissolving, the a small amount of residue of elimination is crossed in cooling, obtains cuprammonia (2).By analysis, total copper content (molar concentration) is 2.07 mol, and proportion 1.17, pH value are 10.5.
Take by weighing 7.2 gram (NH
4)
2CrO
4, 4.4 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (E).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (2) 485 grams and mix stirring with carrier (E), all the other operations are with [embodiment 3].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 6]
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 350 grams, carbonic hydroammonium 122 grams (1.55 moles), logical ammonia is molten entirely to salt under stirring, add copper powder 65.6 gram (1.03 moles) (weight 99.7%, 100 orders), blowing air and ammonia, maintain the temperature at below 65 ℃, complete to the copper powder dissolving, need 5～6 hours approximately, cooling, cross a small amount of residue of elimination, obtain cuprammonia (3).By analysis, total copper content (molar concentration) is 1.87 mol, and proportion 1.13, pH value are 10.5.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (3) 520 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 7]
The preliminary treatment of copper is with [embodiment 1].
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds 435 gram water, glacial acetic acid (weight 36%) 70.5 gram (0.38 mole), oxalic acid C
2H
2O.H
2O 49.0 gram (0.38 mole), stir down logical ammonia to PH greater than 7.5, add above-mentioned copper billet 54.5 grams (0.86 mole), blowing air and ammonia, maintain the temperature at below 60 ℃, react completely to copper powder, need 8～10 hours approximately, the a small amount of residue of elimination is crossed in cooling, obtains cuprammonia (4).By analysis, total copper content (molar concentration) is 1.79 mol, and proportion 1.18, pH value are 11.0.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (4) 540 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 8]
The preliminary treatment of copper is with [embodiment 1].
1 liter of four-hole boiling flask is joined mechanical agitation, thermometer and condenser pipe respectively, adds entry 435 grams, oxalic acid 49.0 grams (0.38 mole), and ammonium carbonate 37.3 grams (0.38 mole), all the other are operated with embodiment 7, obtain cuprammonia (5).By analysis, total copper content (molar concentration) is 1.85 mol, and proportion 1.12, pH value are 10.5.
Carrier (A) preparation is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (5) 523 grams and mix stirring with carrier (A), all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 9]
The preparation method of cuprammonia (1) is with [embodiment 1].
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.2 gram Ba (NO
3)
2With 2.7 gram Zn (NO
3)
26H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (B).
Take by weighing cuprammonia (1) 450 gram and go into 1 liter of withstand voltage reaction bulb (joining Pressure gauge) and mixes stirrings with carrier (B), flooded 2 hours prior to 50～60 ℃, be warming up to 70～80 ℃ and flooded 2 hours, rise to 85～90 ℃ again and flooded 8 hours, impregnation pressure is 0.2MPa.All the other operations are with [embodiment 2].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 10]
The preparation method of cuprammonia (1) is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 450 gram and mix stirring, at system pressure 3 * 10 with 160 gram silica
-3The MPa dipping, all the other operations are with [embodiment 1].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[embodiment 11]
The preparation method of cuprammonia (1) is with [embodiment 1].
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (1) 530 gram and mixes stirrings with 160 gram silica, flooded 10 hours in 80～85 ℃, all the other operate [embodiment 1] together.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 1]
With 139 gram Cu (NO
3)
23H
2O adds water 400 grams and is dissolved into blue liquid, adds 160 in 50～60 ℃ and restrains the silica incipient impregnations, stirs after 30 minutes, dries 10 hours for 110 ℃, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 2]
With 139 gram Cu (NO
3)
23H
2O, 1.8 gram (NH
4)
2CrO
4, 1.1 the gram (NH
4)
6Mo
7O
244H
2O adds hot water 400 gram dissolvings, adds 160 gram silica incipient impregnations while hot, stirs after 30 minutes, in 110 ℃ of oven dry 8 hours, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 3]
Take by weighing 4.6 gram Cr (NO
3)
39H
2O, 1.1 gram (NH
4)
6Mo
7O
244H
2O, 1.2 gram Ba (NO
3)
2, 2.7 gram Zn (NO
3)
26H
2O, 3.0 gram Ni (NO
3)
26H
2O and 139 gram Cu (NO
3)
23H
2O is dissolved in the 400 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, dries 8 hours for 110 ℃, again in 400 ℃ of roastings 4 hours.Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 4]
The cuprammonia preparation is with [embodiment 5].
Take by weighing 10.8 gram (NH
4)
2CrO
4, 6.6 the gram (NH
4)
6Mo
7O
244H
2O is dissolved in the 450 gram hot water, drops into 160 gram silica while hot, stirs after 30 minutes, in 100 ℃ of oven dry 8 hours, again in 500 ℃ of roastings 4 hours, gets carrier (F).
Join thermometer, mechanical agitation in 1 liter of there-necked flask, take by weighing cuprammonia (2) 485 grams and mix stirring with carrier (F), all the other operations are with [embodiment 3].Under process conditions of the present invention, investigate and the results are shown in [embodiment 12].
[comparative example 5]
Operation is with [embodiment 1], and difference substitutes carrier (A) with silica.
[embodiment 12]
The catalyst of [embodiment 1～11] and [comparative example 1～5] preparation adopts fluid bed gas phase hydrogenation technology, and the nitrobenzene air speed is 5.0 hours
-1, adopting hydrogen, nitrogen mixture body, mol ratio is NB: H
2: N
2=1: 9～18: 1.4～2.0, reach 0.1% (GC analytic approach, area normalization method) as test endpoint with NB concentration in product, the rerum natura of catalyst and disposable life-span are as shown in table 1.
Table 1
| Sequence number | Catalyst is formed % (weight) | Specific surface rice 2/ gram | Pore volume centimetre 3/ gram | The average pore size nanometer | Disposable life-span hour | The initial yield % of aniline | ||||||
| Cu | Cr | Mo | Ni | Ba | Zn | Ce | ||||||
| Embodiment 1 | 19.0 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 435.28 | 0.71 | 6.81 | 148 | 99.92 |
| Embodiment 2 | 18.1 | 0.3 | 0 | 0 | 0.3 | 0.3 | 0 | 427.84 | 0.76 | 7.10 | 160 | 99.94 |
| Embodiment 3 | 17.5 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 415.90 | 0.78 | 7.02 | 176 | 99.96 |
| Embodiment 4 | 18.3 | 0 | 0 | 0 | 0 | 0 | 0.5 | 418.37 | 0.74 | 7.05 | 140 | 99.94 |
| Embodiment 5 | 17.2 | 1.2 | 1.2 | 0 | 0 | 0 | 0 | 395.24 | 0.77 | 7.21 | 108 | 99.92 |
| Embodiment 6 | 19.9 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 450.74 | 0.71 | 6.50 | 124 | 99.94 |
| Embodiment 7 | 19.3 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 441.63 | 0.73 | 6.42 | 132 | 99.92 |
| Embodiment 8 | 19.6 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 440.82 | 0.72 | 6.34 | 116 | 99.90 |
| Embodiment 9 | 15.4 | 0.3 | 0 | 0 | 0.3 | 0.3 | 0 | 375.38 | 0.83 | 7.32 | 100 | 99.91 |
| Embodiment 10 | 18.8 | 0 | 0 | 0 | 0 | 0 | 0 | 451.32 | 0.69 | 8.21 | 92 | 99.90 |
| Embodiment 11 | 17.7 | 0 | 0 | 0 | 0 | 0 | 0 | 412.41 | 0.79 | 6.93 | 88 | 99.85 |
| Comparative example 1 | 18.5 | 0 | 0 | 0 | 0 | 0 | 0 | 60.34 | 0.45 | 5.38 | 26 | 99.51 |
| Comparative example 2 | 18.0 | 0.3 | 0.3 | 0 | 0 | 0 | 0 | 65.49 | 0.31 | 5.01 | 38 | 99.62 |
| Comparative example 3 | 18.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 69.88 | 0.28 | 4.96 | 44 | 99.78 |
| Comparative example 4 | 17.4 | 1.8 | 1.8 | 0 | 0 | 0 | 0 | 405.13 | 0.74 | 7.21 | 82 | 99.88 |
| Comparative example 5 | 19.1 | 0 | 0 | 0 | 0 | 0 | 0 | 430.74 | 0.75 | 7.13 | 74 | 99.83 |
Claims (10)
1. the preparation method of a fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene may further comprise the steps:
(1) in the presence of air and ammonia source, reaction temperature is 40～65 ℃, and oxidized metal copper becomes cuprammonia, and cuprammonia is formed expression with mole and comprised following general formula: Cu
a(NH
3)
bX
c
Wherein, the span of a is 1～2;
The span of b is 1～5;
The span of c is 0.5～4;
X is selected from OH
-, NO
3 -, SO
4 2-, CO
3 2-, CH
3COO
-, HCOO
-Or (CO
2)
2 2-In at least a;
(2) carrier silica is selected from aqueous metal salt incipient impregnation at least a among Cr, Mo, Ba, Zn, Ce, Ni, V, Pb or the Pt with containing, oven dry, roasting;
(3) will obtain catalyst through the silica supports and the cuprammonia hybrid infusion of above-mentioned processing.
2. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, the span that it is characterized in that a is 1 or 2; The span of b is 2～4; The span of c is 1～2; X is selected from OH
-, CO
3 2-, CH
3COO
-, or (CO
2)
2 2-In at least a.
3. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1 is characterized in that in the cuprammonia, and the molar concentration of copper is 1.70～2.20 mol; The pH value of cuprammonia is 9～11; The proportion of cuprammonia is 1.10～1.20.
4. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1 is characterized in that described slaine is nitrate or ammonium salt.
5. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, it is characterized in that by weight, the liquid-solid ratio of cuprammonia and treated silica supports is 0.9～2.0, and dipping temperature is 45～95 ℃, and impregnation pressure is 2.66 * 10
-3～0.25MPa.
6. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 5 is characterized in that impregnation pressure is 2.66～3.99 * 10
-3The negative pressure of MPa.
7. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 5 is characterized in that impregnation pressure is the malleation of 0.11～0.25MPa.
8. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 1, the impregnation method that it is characterized in that cuprammonia and carrier is segmentation dipping or constant temperature dipping.
9. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 8 is characterized in that the segmentation dipping is 1～4 hour, 85～95 ℃ dippings of 2～5 hours, 60～80 ℃ dippings of 45～60 ℃ of dippings 3～8 hours.
10. the preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene according to claim 8 is characterized in that the constant temperature dipping is 60～95 ℃ of dippings 5～12 hours.
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| CN102000612B (en) * | 2009-09-02 | 2013-03-06 | 中国石油化工集团公司 | Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst |
| CN106565504B (en) * | 2015-10-12 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of method of nitrobenzene liquid-phase hydrogenatin aniline |
| CN115532300B (en) * | 2021-06-29 | 2023-11-28 | 中石化南京化工研究院有限公司 | Catalyst for preparing aniline by nitrobenzene hydrogenation, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891094A (en) * | 1955-02-17 | 1959-06-16 | American Cyanamid Co | New catalyst for reducing nitrobenzene and the process of reducing nitrobenzene thereover |
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2004
- 2004-11-05 CN CNB2004100678660A patent/CN100368085C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891094A (en) * | 1955-02-17 | 1959-06-16 | American Cyanamid Co | New catalyst for reducing nitrobenzene and the process of reducing nitrobenzene thereover |
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