CN1565736A - Catalyzer for synthesizing pyridine base - Google Patents
Catalyzer for synthesizing pyridine base Download PDFInfo
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- CN1565736A CN1565736A CN 03141458 CN03141458A CN1565736A CN 1565736 A CN1565736 A CN 1565736A CN 03141458 CN03141458 CN 03141458 CN 03141458 A CN03141458 A CN 03141458A CN 1565736 A CN1565736 A CN 1565736A
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- catalyzer
- pyridine base
- pyridine
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Abstract
The invention relates to a catalyst for synthesizing pyridine base for improving the yield of pyridine base. The technology is characterized in that the catalyst with cobalt, lead or metal oxide of their mixture -supported on ZSM-5 zeolite can promoting the reaction of fatty aldehyde, fatty ketone or their mixtures and ammonia.
Description
Technical field
The present invention relates to a kind of pyridine base synthetic catalyzer that is used for, particularly about in gas phase with alkanoic, aliphatic ketone or its mixture and the pyridine base-synthesized catalyzer of ammonia gas react.
Background technology
Pyridine and alkyl pyridine are commonly referred to as pyridine base, it is the important organic raw material of production high added value fine chemical product, be widely used in fields such as medicine, agricultural chemicals, dyestuff, spices, fodder additives, foodstuff additive, rubber ingredients and synthetic materials, of many uses, deep processing has a extensive future.In recent years, the Application Areas of pyridine base constantly enlarges, and demand growth is very fast, to cause extensive concern.Pyridine base mainly comprises pyridine, 2-picoline, 3-picoline, 4-picoline and 2-methyl-5 ethylpyridine etc.
Pyridine is mainly as medicine industry system sulfanilamide (SN), penicillin, vitamin A, cortisone, insect repellent and local anesthetic etc., the condensing agent of stablizer, tenderizer, paint solution, synthetic resins be can also be used for, and synthetic herbicide, sanitas and pyridone etc. are used for.
The 2-picoline can be used for the important industrial chemicals one 2-vinyl pyridine of China Synthetic Rubber Industry, also is used for the raw material of additive, resin of medicine industry system amprolium, long-acting sulfanilamide, Toldrin, local anesthetic, cathartic and light reaching the film agent and fuel intermediate, nitrogen fertilizer potentiating agent, weedicide, livestock insect repellent etc.
The 3-picoline can be used for making vitamins B, Carbamidal, cardiotonic drug, sterilant, also can make solvent, alcotate, water-resisting agent, dyestuff intermediate, resin intermediate, thiofide etc.And most important purposes is to produce nicotinic acid and niacinamide, and nicotinic acid and niacinamide can be used for the additive of fodder industry.
The 4-picoline is mainly used in the raw material and the solvent of organic synthesis.Pharmaceutically, produce treatment tuberculosis medicine vazadrine (reining in sealing) through oxidation, produce detoxifcation medication obidoxime chloride and Trimedoxime N, can also be used to produce the raw material of dyestuff, agricultural chemicals, catalyzer, thiofide, synthetic resins.
2-methyl-5 ethylpyridine is mainly used in preparation nicotinic acid, nicotine, 2-methyl-5-vinylpyrine, fodder additives, spice additive etc.
Pyridine compounds and their obtains by separating in coal tar, the animal oil the earliest, but pyridine and derivative content thereof are limited in kerosene, animal oil or the shale oil, output seldom, form complicated because of it again, and the many materials close with boiling point mix existence, increase difficulty for separating to purify, also improved the cost of product.At the beginning of the forties, along with the world energy sources structure takes place with the variation of oil for coal, the source of pyridine is restricted.Therefore, along with the increase of demand, this method is the incompatibility mass industrialized production, eliminates gradually, and is replaced by synthesis method.
Be used for the earliest that catalyzer that synthesis method prepares pyridine base mostly is the amorphous aluminosilicate catalyzer and through the amorphous aluminosilicate catalyzer of modification, as U.S. Pat 2807618; 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 total recovery 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 molecular sieve of making for binding agent is as pyridine base synthetic catalyzer.Be 1.4 in acetaldehyde/formaldehyde mole ratio, ammonia/aldehyde mol ratio is 1.5, reaction pressure is under the non-pressurized reaction conditions, the pyridine yield of catalyzer is 47%, picoline (comprises the 2-picoline, 3-picoline and 4-picoline) yield be 14%, the total recovery of pyridine and picoline is 61%.See that thus the pyridine base total recovery of this catalyzer is still not ideal enough.
The U.S. Pat 5218122 (1993) that is entitled as " pyridine base synthetic and catalyzer " has disclosed crystal formation zeolite with tungsten, zinc or tin modification as pyridine base synthetic catalyzer.Be 1 in formaldehyde/acetaldehyde mol ratio, ammonia/aldehyde mol ratio is 1.2, under the reaction conditions of 450 ℃ of temperature of reaction, the pyridine yield of tungsten modified catalyst is 32%, the yield of 3-picoline is 16%, the yield of 2-picoline is 1%.Under same reaction conditions, the catalyzer 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 catalyzer 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%.See that thus the pyridine base total recovery of above-mentioned catalyzer is still lower.
Recently, as catalyzer, 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 Chinese patent CN1330068A that is entitled as " method that prepare pyridine bases " 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, thallium, lanthanum and indium etc. enter the zeolite framework modification equally, the total recovery of pyridine base increases, but wherein the highest also only be 72.8%.
This shows that above-mentioned several catalyzer are used for the synthetic of pyridine base, it is very satisfied that its yield can't make us, so remain further to be improved.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of pyridine base in the prior art, and a kind of new pyridine base synthetic catalyzer that is used for is provided.Use this catalyzer to have the high characteristics of pyridine base yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of pyridine base synthetic catalyzer that is used for comprises following active constituent by weight percentage:
A) silica alumina ratio SiO
2/ Al
2O
3It is 10～400 ZSM-5 zeolite 85～99.9%; Be stated from this zeolite
B) be selected from the metal oxide 0.1～15% of cobalt, lead or its mixture in metal;
Be binding agent with aluminum oxide, silicon-dioxide or its mixture in the catalyzer, the binding agent consumption is 0～50% of a catalyst weight.
In the technique scheme, the silica alumina ratio preferable range of used ZSM-5 zeolite is 50～350, and more preferably scope is 100～250.By weight percentage, the consumption preferable range that is selected from the metal oxide of cobalt, lead or its mixture in metal is 0.5～7%, and more preferably scope is 1～4%, and the preferable range of binding agent consumption is 20～40% of a catalyst weight.
Being used for zeolite of the present invention can make required shape by tabletting machine or banded extruder, as sheet shape, bar shaped etc.In moulding process, can under its virgin state, carry out, also can with carry out after tackiness agent such as silicon-dioxide, silicon bath soil, kaolin, nitric acid, water etc. mix, the catalyzer after the moulding can be used for fixed-bed reactor; Obtain slurries after perhaps for example aluminum oxide, silicon-dioxide and composition thereof mix with tackiness agent with zeolite, spray-driedly then obtain a kind of microballoon, as the catalyzer of fluidized-bed reactor.The catalyzer that obtains can be 300 to 800 ℃ of roastings 1～20 hour in air, improving the intensity of catalyzer, and remove the volatile components in the binding agent.
Catalyzer of the present invention be by ion exchange method, pickling process, kneading method, sedimentation or evaporation drying method etc. with metal load to zeolite, drying and high-temperature roasting make then.The adding form of metal can be their ion or compound, as oxide compound, halogenide, vitriol, nitrate, carbonate etc.
The used metal oxide of the present invention adds after the zeolite moulding.
Catalyzer with the present invention's preparation is used for the synthetic of pyridine base compound, can carry out in fixed-bed reactor, also can carry out in fluidized-bed reactor or moving-burden bed reactor.
An example of the inventive method of using fixed-bed reactor is described below.
It is 16 millimeters that catalyzer is loaded in internal diameter, and length is in 500 millimeters the stainless steel reactor.Adopt electrically heated, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as upholder, a certain amount of catalyzer of filling in the reactor, and filling 20～40 purpose inert materials in catalyzer top are made for the usefulness of raw material preheating and vaporization.Feedstock fat aldehyde and/or aliphatic ketone mix with ammonia, from top to bottom by beds, the vapour phase condensation reaction take place, and generate purpose product pyridine and by products such as alkyl pyridine and a spot of many alkyl pyridines.
It is 1 to 5 compound that used alkanoic and/or ketone are generally carbonatoms, as formaldehyde, acetaldehyde, propionic aldehyde, third rare aldehyde, acetone etc.Formaldehyde can formalin (formalin of 37% (weight)) form use.The mol ratio of ammonia and aldehyde is 0.5～5, and preferable range is 1～3.The air speed of reaction gas is 100～10000 hours
-1, preferable range is 300～3000 hours
-1Temperature of reaction is 300～700 ℃, and preferable range is 400～600 ℃.Reaction pressure can be from normal atmosphere with down to several normal atmosphere, and preferable range is normal atmosphere to 2 normal atmosphere.
After reacting as mentioned above, contact with methanol solvate and be dissolved in this solvent from the effusive pyridine base that contains reactant gases of reactor outlet.Carry out the content of each component of quantitative analysis then with the gas chromatography method.Adopt following formula to calculate its yield:
Mole number * 5/ of pyridine in pyridine yield (%)=product (mole number * 2 of the mole number of formaldehyde * 1+ acetaldehyde in the reactant) * 100%
2,3 or 4-picoline yield=product in 2,3 or mole number * 6/ (mole number * 2 of the mole number of formaldehyde * 1+ acetaldehyde in the reactant) * 100% of 4-picoline
Among the present invention, owing to adopt the ZSM-5 zeolite as the catalyst activity main body, the metal oxide of load cobalt, lead or its mixture on the ZSM-5 molecular sieve, when making catalyzer be used for alkanoic, aliphatic ketone or its mixture and ammonia react generation pyridine base, the pyridine base yield reaches as high as 83%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Be silicon source and aluminium source with water glass and Tai-Ace S 150 respectively, the tetrapropyl amine bromide is the masterplate agent, adopts the synthetic former powder of ZSM-5 of hydrothermal synthesis method.Crystallization is carried out in stainless steel cauldron, and stirring velocity is 100～200 rev/mins, and pressure is self pressure of reactive system, and crystallization temperature is 100～150 ℃.With the synthetic former powder of ZSM-5 that obtains of 700 grams after burning amine with 300 gram alumina binder wet mixings after extruded moulding, obtain hydrogen type molecular sieve H-ZSM-5, its silica alumina ratio SiO with the ammonium nitrate solution exchange then
2/ Al
2O
3Be 250.This molecular sieve is as catalyst A.
[embodiment 2]
A certain amount of lead nitrate is dissolved in an amount of water, obtain the certain density lead solution that contains, then the molecular sieve H-ZSM-5 that makes among a certain amount of embodiment 1 is added in this solution and flood, with the product that obtains 110 ℃ of dryings, 550 ℃ of roastings 4 hours, obtaining in the metal lead content was the catalyst B of 2.5% (weight) then.
[embodiment 3]
The preparation method just replaces lead nitrate with Xiao Suangu with embodiment 2, and obtaining in the metal cobalt contents is the catalyzer C of 1.5% (weight).
[embodiment 4]
The preparation method is the silica alumina ratio SiO of ZSM-5 zeolite with embodiment 2
2/ Al
2O
3Be 150, also added Xiao Suangu in addition in solution, obtaining in the metal lead content is that 2.5% (weight) and cobalt contents are the catalyzer D of 1.5% (weight).
[embodiment 5]
With catalyst A, B, C and the D that embodiment 1,2,3 and 4 makes, in continuous flow fixed bed reaction evaluating apparatus, carry out the vapour phase condensation reaction.The loadings of catalyzer: 1.5 grams; Temperature of reaction: 450 ℃; Pressure: 0.1MPa; Air speed: 1000 hours
-1After catalyst loading is intact, under the condition of logical ammonia, be warming up to 450 ℃.Then with the mixing solutions (mol ratio of acetaldehyde/formaldehyde is 2) of formaldehyde and acetaldehyde through micro-fresh feed pump injecting reactor, the mol ratio of ammonia/aldehyde is 1.5.Collect behind the logical people's methanol solution of reaction product, quantitative analysis on the HP4890 gas chromatograph is interior mark with propyl carbinol, and the HP-FFAP capillary column is an analytical column.The evaluation result of each catalyzer sees Table 1, and data are the mean value in the successive reaction 4 hours in the table.
The reactivity worth of table 1 catalyzer
| Catalyzer | Yield (%) | ||||
| Pyridine | The 2-picoline | The 3-picoline | The 4-picoline | Total recovery | |
| ????A | ????40 | ??3 | ??5 | ??11 | ??59 |
| ????B | ????60 | ??6 | ??3 | ??9 | ??78 |
| ????C | ????63 | ??5 | ??4 | ??8 | ??80 |
| ????D | ????68 | ??4 | ??4.5 | ??6.5 | ??83 |
The present invention make with the ZSM-5 zeolite that contains the metal oxide modified that is selected from lead, cobalt or its mixture as pyridine base synthetic catalyzer, have the high advantage of pyridine base yield.
Claims (6)
1, a kind of pyridine base synthetic catalyzer that is used for comprises following active constituent by weight percentage:
A) silica alumina ratio SiO
2/ Al
2O
3It is 10～400 ZSM-5 zeolite 85～99.9%; Be stated from this zeolite
B) be selected from the metal oxide 0.1～15% of cobalt, lead or its mixture in metal;
Be binding agent with aluminum oxide, silicon-dioxide or its mixture in the catalyzer, the binding agent consumption is 0～50% of a catalyst weight.
2,, it is characterized in that the silica alumina ratio SiO of ZSM-5 zeolite according to the described pyridine base synthetic catalyzer that is used for of claim 1
2/ Al
2O
3Be 50～350.
3,, it is characterized in that the silica alumina ratio SiO of ZSM-5 zeolite according to the described pyridine base synthetic catalyzer that is used for of claim 2
2/ Al
2O
3Be 100～250.
4, according to the described pyridine base synthetic catalyzer that is used for of claim 1, it is characterized in that by weight percentage the consumption that is selected from the metal oxide of cobalt, lead or its mixture in metal is 0.5～7%.
5, according to the described pyridine base synthetic catalyzer that is used for of claim 1, it is characterized in that by weight percentage the consumption that is selected from the metal oxide of cobalt, lead or its mixture in metal is 1～4%.
6, according to the described pyridine base synthetic catalyzer that is used for of claim 1, it is characterized in that the binding agent consumption is 20～40% of a catalyst weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141458 CN1565736A (en) | 2003-07-09 | 2003-07-09 | Catalyzer for synthesizing pyridine base |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141458 CN1565736A (en) | 2003-07-09 | 2003-07-09 | Catalyzer for synthesizing pyridine base |
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|---|---|
| CN1565736A true CN1565736A (en) | 2005-01-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460393C (en) * | 2006-11-21 | 2009-02-11 | 浙江大学 | 2,Process for preparing 3-dimethylpyridine |
| CN100574880C (en) * | 2009-02-18 | 2009-12-30 | 中国科学院大连化学物理研究所 | Be used for pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof |
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN115121283A (en) * | 2022-07-21 | 2022-09-30 | 安徽国星生物化学有限公司 | Preparation method of loaded dispersion type monatomic catalyst for pyridine base production |
-
2003
- 2003-07-09 CN CN 03141458 patent/CN1565736A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460393C (en) * | 2006-11-21 | 2009-02-11 | 浙江大学 | 2,Process for preparing 3-dimethylpyridine |
| CN100574880C (en) * | 2009-02-18 | 2009-12-30 | 中国科学院大连化学物理研究所 | Be used for pyridine base-synthesized magnesium-cobalt based catalyst of formaldehyde aceto-aldehyde ammonia and preparation method thereof |
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN108816275B (en) * | 2018-04-19 | 2021-02-05 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing pyridine base from synthesis gas, preparation method and application |
| CN115121283A (en) * | 2022-07-21 | 2022-09-30 | 安徽国星生物化学有限公司 | Preparation method of loaded dispersion type monatomic catalyst for pyridine base production |
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