CN100574880C - Be used for pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof - Google Patents
Be used for pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof Download PDFInfo
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Abstract
A kind of pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof that is used for, this catalyst is by ZSM-11/ZSM-35 composite molecular screen, MgO, Co
3O
4Form with matrix, its mesostroma is aluminium oxide and kaolin; With ZSM-11/ZSM-35 composite molecular screen, MgO, Co
3O
4, after aluminium oxide and kaolin and water mix, spray shaping, drying makes catalyst of the present invention; The present invention has can supply industrial operation, and technology is fairly simple, pyridine base yield advantages of higher.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of pyridine base-synthesized magnesium cobalt-based fluid catalyst and preparation method thereof.
Background technology
Pyridine is that a carbon atom is replaced the formed 6-membered heterocyclic compound in back by nitrogen-atoms on the phenyl ring.Pyridine and alkyl pyridine are commonly referred to as pyridine base, mainly comprise pyridine, 2-picoline, 3-picoline, 4-picoline and 2-methyl-5 ethylpyridine etc.The pyridine series raw material is the important Organic Ingredients of production high added value fine chemical product as chemical industrial product, is widely used in fields such as medicine, agricultural chemicals, dyestuff, spices, feed addictive, food additives, rubber chemicals and synthetic material.
It is raw material that nineteen twenty-four Chichbabin has proposed with aldehyde and ammonia, produces the commercial run of pyridine base in enormous quantities, and process is updated catalyst, and productive rate is brought up to about 80% by the 40%-50% of the fifties.Along with the development of industrial gas oil, consider cost of material, having occurred with ketone, alcohol, alkene, alkynes etc. again is the pyridine base-synthesized method of catalytic material, but technology is still immature and productive rate is lower.At present, 95% pyridine base remains with aldehyde and ammonia as raw material in the world, is synthesized into through catalysis.
Be used for the earliest that catalyst that synthetic method prepares pyridine base mostly is the amorphous aluminosilicate catalyst and through the amorphous aluminosilicate catalyst of modification, as U.S. Pat 2507618; The SiO of report such as US3946020 and US3932431
2-Al
2O
3Compound and through halogen and PO
4 3-The SiO of modification
2-Al
2O
3Compound, but the gross production rate of its pyridine base generally not high (＜50%).
The U.S. Pat 4861894 (1989) that is entitled as " with crystal formation molecular sieve pyridine synthesis and alkyl pyridine with ZSM-5 structure " has disclosed with SiO
2/ Al
2O
3Mol ratio is that 225 high silica ZSM-5 zeolite is former powder, SiO
2The catalyst that the molecular sieve of making for binding agent synthesizes as pyridine base.Be 1.4 in acetaldehyde/formaldehyde mole ratio, ammonia/aldehyde mol ratio is 1.5, reaction pressure is under the reaction condition of normal pressure, the pyridine productive rate of catalyst is 47%, picoline (comprises the 2-picoline, 3-picoline and 4-picoline) productive rate be 14%, the gross production rate of pyridine and picoline is 61%.
The U.S. Pat 5218122 (1993) that is entitled as " pyridine base synthetic and catalyst " has disclosed crystal formation zeolite with tungsten, zinc or tin modification as the synthetic catalyst of pyridine base, be 1 in formaldehyde/acetaldehyde mol ratio, ammonia/aldehyde mol ratio is 1.2, under the reaction condition that reaction temperature is 450 ℃, the pyridine yield of tungsten modified catalyst is 32%, the yield of 3-picoline is 16%, and the yield of 2-picoline is 1%.Under same reaction condition, the catalyst of zinc or tin modification, its pyridine yield is 34%, and the yield of 3-picoline is 14%, and the yield of 2-picoline is 1%.Use the catalyst of zinc and tin modification simultaneously, its pyridine yield is 34%, and the yield of 3-picoline is 16%, and the yield of 2-picoline is 1%.
The U.S. Pat 5395940 (1995) that is entitled as " pyridine and 3-picoline synthetic " has disclosed with specific crystal formation zeolite such as MCM-22 or MCM-49 as pyridine and the synthetic catalyst of 3-picoline.In acetaldehyde/formaldehyde/ammonia mol ratio is that the yield of pyridine is 9.3% under the reaction condition of 427 ℃ of 1.4/1/3.6, reaction temperature, and the yield of 3-picoline is 4.1%, and the yield of 2-picoline is 0.6%, and the yield of 4-picoline is 0.9%.Though in pyridine that said method is synthetic and the 3-picoline content of 2-picoline and 4-picoline all seldom, the total recovery of pyridine and 3-picoline is too low, does not have the possibility of any commercial Application.
Recently, as catalyst, wherein the atom ratio of silicon and titanium and/or cobalt is about 5 to about 1000 as the crystal formation zeolite of zeolite component for Japan's Chinese patent that is entitled as " method that prepare pyridine bases " (publication number CN1330068A and 1172915C) of wide flourish KCC and U.S. Pat 6281362 employing titaniferous and/or cobalt and silicon.But because titanium and/or cobalt are to synthesize in molecular sieve structure, enter the skeleton of molecular sieve, be lower than 50% with the pyridine base total recovery of this zeolites as catalysts.After making lead, tungsten, zinc, he, lanthanum and indium etc. enter the zeolitic frameworks modification equally, the total recovery of pyridine base increases, and wherein the highest can reach 72.5%.
Lu Guanzhong etc. carry out modification at the mixture that Chinese patent CN1263741C and CN1565736A have disclosed with plumbous and cobalt to the ZSM-5 catalyst, at the continuous-flow fixed bed, and air speed: 1000h
-1, formaldehyde/acetaldehyde mol ratio is 1/2, ammonia/aldehyde mol ratio is 4.5, under the reaction condition that reaction temperature is 450 ℃, and the ZSM-5 (SiO of plumbous (2.5w%) and cobalt (1.5w%) modification
2/ Al
2O
3Mol ratio is 150) catalyst, successive reaction 4 hours, the pyridine yield is 68%, and the yield of 3-picoline is 4.5%, and the yield of 2-picoline is 4%.Other condition is identical, just reaction velocity 3000h
-1, ammonia/aldehyde mol ratio is 4.5, its pyridine yield is 55.5%, and the yield 25% of 3-picoline, the yield 0.5% of 2-picoline, the yield of 4-picoline are 0, total recovery is 81%.
Xiao its people etc. have disclosed with lead at Chinese patent CN1631536A, and cobalt and palladium carry out modification to the ZSM-5 catalyst, at the continuous-flow fixed bed, and air speed: 1000h
-1, formaldehyde/acetaldehyde/ammonia mol ratio is 1/2/4, under the reaction condition that reaction temperature is 450 ℃, and plumbous (2w%), the ZSM-5 (SiO of cobalt (10w%) and palladium (0.01w%) modification
2/ Al
2O
3Mol ratio is 150) catalyst, the pyridine yield is 55%, and total recovery is 72%, and the regeneration period is 24 hours.Other condition is identical, plumbous (12.5w%), the ZSM-5 (SiO of cobalt (2w%) and palladium (0.2w%) modification
2/ Al
2O
3Mol ratio is 150) catalyst, the pyridine yield is 70%, and total recovery is 87%, and the regeneration period is 48 hours.
Chinese patent CN200710021347.4 discloses a kind of Catalysts and its preparation method of producing pyridine base.This catalyst is for to load on bismuth on the ZSM-5 molecular sieve carrier; Its composition comprises that mass percent is the ZSM-5 molecular sieve carrier of 90-99.9% and the bismuth of load 10-0.1% thereon.Catalyst of the present invention has increased the selectivity of pyridine base, has reduced high boiling point by-products producedly, can make the total recovery of pyridine and picoline be up to 88%.
Summary of the invention
The purpose of this invention is to provide a kind of pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof that is used for.
The invention provides a kind of pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for, the percentage by weight of the whole catalyst of each ingredients constitute is in this catalyst: ZSM-11/ZSM-35 composite molecular screen 30-45%, MgO 0.5-2.5% (preferred 1.0-2.0%), Co
3O
40.5-5.0% (preferred 1.0-3.0%), all the other are aluminium oxide and kaolin.
The pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for provided by the invention, ZSM-11 and ZSM-35 weight ratio are 0.05-20 in the described ZSM-11/ZSM-35 composite molecular screen.
The pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for provided by the invention, described aluminium oxide derives from aluminium colloidal sol, and its content is the heavy % of 15-35; Kaolin content is the heavy % of 20-50.
The invention provides the Preparation of catalysts method that is used for the pyridine base-synthesized titanium base of formaldehyde aceto-aldehyde ammonia, concrete steps are: with the heavy %ZSM-11/ZSM-35 composite molecular screen of 30-45, and the heavy %MgO of 0.5-2.5, the heavy %Co of 0.5-5.0
3O
4, the heavy % aluminium oxide of 15-35, heavy % kaolin of 20-50 and water mix, solid/water weight ratio in the mixture=0.2-0.5, spray shaping and drying make catalyst of the present invention; Wherein the inlet temperature in the spray condition is 450-650 ℃, and exhaust temperature is 120-250 ℃, and atomisation pressure is 0.5-10Mpa, and baking temperature is 400-650 ℃, and the time is 2-4 hour.
The present invention has can supply industrial operation, and technology is fairly simple, pyridine base yield advantages of higher.
The specific embodiment
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
Comparative example 1
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %, below identical, no longer narration), kaolin, deionized water mix the back spray shaping, drying makes catalyst A.Wherein spray condition is 450 ℃ of inlet temperatures, 150 ℃ of exhaust temperatures, atomisation pressure 2.0Mpa, 500 ℃ of baking temperatures, 2 hours.The catalyst A that makes, wherein the weight content of ZSM-11 molecular sieve and aluminium oxide is respectively 40% and 22%.
Comparative example 2
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, Mg (NO
3)
2, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, and drying makes catalyst B.Wherein spray condition is 450 ℃ of inlet temperatures, 150 ℃ of exhaust temperatures, atomisation pressure 2.0Mpa, 500 ℃ of baking temperatures, 2 hours.The catalyst B that makes, ZSM-11 molecular sieve wherein, the weight content of MgO and aluminium oxide is respectively 40%, 1% and 22%.
Comparative example 3
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, and drying makes catalyst C.Wherein spray condition is 450 ℃ of inlet temperatures, 150 ℃ of exhaust temperatures, atomisation pressure 2.0Mpa, 500 ℃ of baking temperatures, 2 hours.The catalyst C that makes, wherein 70 heavy %ZSM-11/30 weigh %ZSM-35 composite molecular screen, Co
3O
4Be respectively 40%, 3% and 22% with the weight content of aluminium oxide.
Embodiment 1
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, and drying makes catalyst D.Wherein spray condition is 450 ℃ of inlet temperatures, 150 ℃ of exhaust temperatures, atomisation pressure 2.0Mpa, 500 ℃ of baking temperatures, 2 hours.The catalyst D that makes, wherein 70 heavy %ZSM-11/30 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 39%, 1% with the weight content of aluminium oxide, 3% and 22%.
Embodiment 2
With the heavy %ZSM-35 composite molecular screen of a certain amount of 50 heavy %ZSM-11/50, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, and drying makes catalyst E.Wherein spray condition is 500 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, atomisation pressure 8Mpa, 580 ℃ of baking temperatures, 2 hours.The catalyst E that makes, wherein 50 heavy %ZSM-11/50 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 35%, 0.7% with the weight content of aluminium oxide, 4.5% and 19%.
Embodiment 3
With the heavy %ZSM-35 composite molecular screen of a certain amount of 10 heavy %ZSM-11/90, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, drying, and steam treatment makes catalyst F.Wherein spray condition is 650 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, atomisation pressure 0.8Mpa, 450 ℃ of baking temperatures, 4 hours.Make catalyst F, wherein 10 heavy %ZSM-11/90 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 33%, 1% with the weight content of aluminium oxide, 2% and 30%.
Embodiment 4
With the heavy %ZSM-35 composite molecular screen of a certain amount of 90 heavy %ZSM-11/10, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, drying, and steam treatment makes catalyst G.Wherein spray condition is 620 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, atomisation pressure 5Mpa, 620 ℃ of baking temperatures, 2 hours.The catalyst G that makes, wherein 90 heavy %ZSM-11/10 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 41%, 2% with the weight content of aluminium oxide, 3% and 25%.
Embodiment 5
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, drying, and steam treatment makes catalyst H.Wherein spray condition is 500 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, atomisation pressure 5Mpa, 500 ℃ of baking temperatures, 3 hours.The catalyst H that makes, wherein 70 heavy %ZSM-11/30 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 39%, 2% with the weight content of aluminium oxide, 4% and 32%.
Embodiment 6
With the heavy %ZSM-35 composite molecular screen of a certain amount of 70 heavy %ZSM-11/30, Mg (NO
3)
2, Co (NO
3)
26H
2O, aluminium colloidal sol, kaolin, deionized water mix the back spray shaping, drying, and steam treatment makes catalyst I.Wherein spray condition is 500 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, atomisation pressure 5Mpa, 500 ℃ of baking temperatures, 3 hours.The catalyst I that makes, wherein 70 heavy %ZSM-11/30 weigh %ZSM-35 composite molecular screen, MgO, Co
3O
4Be respectively 39%, 2.5% with the weight content of aluminium oxide, 0.8% and 30%.
The application of embodiment and comparative example
Embodiments of the invention and comparative example are in the application of formaldehyde aceto-aldehyde ammonia aspect pyridine base-synthesized.Dress 800g catalyst in fixed fluidized bed reaction tube is at N
2Be warmed up to 500 ℃ of activation under the atmosphere, then at N
2Atmosphere drops to reaction temperature, under condition as shown in table 1, react, raw material is formaldehyde, acetaldehyde and ammonia mixture, by beds, issues angry condensation reaction mutually in certain air speed and temperature from bottom to top, generate purpose product pyridine and picoline etc., each reaction 40 minutes, water steam stripping then, continuous three times, carry out quantitatively with gas-chromatography, reaction result is averaged.
By the result of table 1 as seen, adopt ZSM-11/ZSM-35 merely, ZSM-11/ZSM-35+Mg, ZSM-11/ZSM-35+Co make catalyst (C), the total molar yield of pyridine base all are lower than ZSM-11/ZSM-35+Mg+Co catalyst of the present invention for catalyst A in the table 1, B.Catalyst D provided by the invention, E, F, G, H and I all have pyridine base productive rate preferably.
Table 1 pyridine catalyst evaluation result
| Catalyst | Mole yield percentage (pyridine; The 2-methyl; The 3-methyl) | Total molar yield, % | Pyridine/3-picoline ratio |
| A | 31.34；0.88；12.81 | 45.83 | 2.45 |
| B | 35.56；0.84；18.31 | 54.71 | 1.65 |
| C | 48.04；0.94；12.94 | 61.92 | 3.15 |
| D | 56.07；0.50；15.22 | 71.78 | 3.13 |
| E | 52.05；0.63；13.64 | 66.50 | 3.24 |
| F | 54.37；0.75；15.27 | 70.64 | 3.02 |
| G | 54.04；0.55；16.03 | 70.62 | 2.86 |
| H | 52.08；0.64；14.79 | 67.50 | 2.99 |
| I | 52.11；0.76；13.30 | 66.16 | 3.33 |
Reaction condition: 450 ℃ of temperature; Acetaldehyde/formaldehyde/ammonia mol ratio 1/1/2; Weight space velocity 0.3h
-1Fluid bed, catalyst 800g.
Claims (8)
1, a kind of pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for is characterized in that: this catalyst contains the heavy %ZSM-11/ZSM-35 composite molecular screen of 30-45, the heavy %MgO of 0.5-2.5, the heavy %Co of 0.5-5.0
3O
4, all the other are aluminium oxide and kaolin.
2, according to the described pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for of claim 1, it is characterized in that: ZSM-11 and ZSM-35 weight ratio are 0.05-20 in the described ZSM-11/ZSM-35 composite molecular screen.
3, according to the described pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for of claim 1, it is characterized in that: the content of described MgO is the heavy % of 1.0-2.0.
4, according to the described pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for of claim 1, it is characterized in that: described Co
3O
4Content be the heavy % of 1.0-3.0.
5, according to the described pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for of claim 1, it is characterized in that: described aluminium oxide derives from aluminium colloidal sol, and its content is the heavy % of 15-35.
6, according to the described pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia that is used for of claim 1, it is characterized in that: described kaolin content is the heavy % of 20-50.
7, the described Preparation of catalysts method of claim 1 is characterized in that: with the heavy %ZSM-11/ZSM-35 composite molecular screen of 30-45, and the heavy %MgO of 0.5-2.5, the heavy %Co of 0.5-5.0
3O
4, the heavy % aluminium oxide of 15-35, heavy % kaolin of 20-50 and water mix, solid/water weight ratio in the mixture=0.2-0.5, spray shaping and drying make catalyst.
8, according to the described Preparation of catalysts method of claim 7, it is characterized in that: the inlet temperature in the described spray condition is 450-650 ℃, and exhaust temperature is 120-250 ℃, and atomisation pressure is 0.5-10Mpa, baking temperature is 400-650 ℃, and the time is 2-4 hour.
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| CN100577286C (en) * | 2009-02-18 | 2010-01-06 | 中国科学院大连化学物理研究所 | Titanium-based catalyst for synthesizing pyridine base with formaldehyde, acetaldehyde and ammonia, as well as preparation method thereof |
| CN101856622B (en) * | 2009-12-16 | 2012-06-13 | 中国科学院大连化学物理研究所 | Pyridine base-synthesized cocrystallized zeolite catalyst and preparation method thereof |
| CN102698792B (en) * | 2012-05-31 | 2013-04-17 | 潍坊绿霸化工有限公司 | Molecular sieve catalyst for producing pyridine base and preparation method thereof |
| CN106831547B (en) * | 2017-01-04 | 2019-04-12 | 安徽国星生物化学有限公司 | A method of using MgAPO-41 molecular sieve as catalyst preparation pyridine |
| CN108479847B (en) * | 2018-03-20 | 2020-09-01 | 中国科学院大连化学物理研究所 | Preparation method of molecular sieve catalyst for reaction of acrolein, propionaldehyde and ammonia gas |
| CN109174168B (en) * | 2018-10-26 | 2021-06-29 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing 2-methylpyridine by pyridine alkylation, preparation method and application |
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| CN1330068A (en) * | 2000-06-26 | 2002-01-09 | 广荣化学工业株式会社 | Method for preparing pyridine alkalis |
| WO2005000816A1 (en) * | 2003-06-27 | 2005-01-06 | Council Of Scientific And Industrial Research | Process for the production of pyridine and picolines |
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