CN1172915C - Method for preparing pyridine alkalis - Google Patents
Method for preparing pyridine alkalis Download PDFInfo
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- CN1172915C CN1172915C CNB001094580A CN00109458A CN1172915C CN 1172915 C CN1172915 C CN 1172915C CN B001094580 A CNB001094580 A CN B001094580A CN 00109458 A CN00109458 A CN 00109458A CN 1172915 C CN1172915 C CN 1172915C
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Abstract
The present invention relates to a method of producing pyridine bases to improve the yield. The method comprises: aliphatic aldehyde, aliphatic ketone or mixtures of the aliphatic aldehyde and the aliphatic ketone which are in gas phases react through a zeolite catalyst, wherein the zeolite catalyst contains titanium and/or cobalt and silicone to be used as component elements of zeolite, and the atom ratio of the silicon to the titanium and/or the cobalt is about from 5 to 1000.
Description
The present invention relates to a kind of by in gas phase with the method for alkanoic, aliphatic ketone or its mixture and ammonia prepared in reaction pyridine bases in the presence of catalyzer.
Known a kind of by in gas phase with the method for alkanoic, aliphatic ketone or its mixture and ammonia prepared in reaction pyridine bases in the presence of catalyzer.Proposed various methods, for example, a kind of method is to use unformed silica alumina as catalyzer; A kind of method is to use zeolite, and for example silico-aluminate etc. is as catalyzer; And some other method.In these catalyzer, zeolite is suitable for the catalyzer of making the preparation pyridine bases, wherein, because its good thermotolerance can at high temperature be carried out gas-phase reaction.
The zeolite that is used as the catalyzer for preparing pyridine base, known except silico-aluminate, for example, impurity silicate such as ferrosilicate, borosilicate and gallium silicate.The private catalyzer of doing of these zeolite coverlets.Perhaps, they can contain the ion and/or the compound of various elements, and for example, copper, zinc, cadmium, bismuth, chromium, molybdenum, tungsten, cobalt, nickel, ruthenium, rhodium, palladium, iridium etc. produce employed catalyzer.
In the preparation of pyridine bases, known main product, pyridine bases is by the combination of raw material (alkanoic and aliphatic ketone) decision.Its typical example is shown in table 1.
Table 1
| Raw material (alkanoic, aliphatic ketone) | Primary product (pyridine bases) |
| Acetaldehyde | α-Jia Jibiding+γ-picoline |
| Acetaldehyde+formaldehyde | Pyridine+beta-picoline |
| Propenal | Beta-picoline |
| Propenal+acetaldehyde | Pyridine |
| Propenal+propionic aldehyde | Beta-picoline |
| Propionic aldehyde+formaldehyde | 3, the 5-lutidine |
| Crotonaldehyde+propionic aldehyde | 3, the 4-lutidine |
| Crotonaldehyde+acetone | 2, the 4-lutidine |
| Formaldehyde+acetone | 2, the 6-lutidine |
| Acetone | 2,4, the 6-collidine |
| Methacrylaldehyde+methyl ethyl ketone | 3,5-lutidine+2,3,5-collidine |
As indicated above, can prepare various pyridine bases by in gas phase, alkanoic, aliphatic ketone or its mixture and ammonia being reacted in the presence of zeolite catalyst.But the productive rate that the method by routine prepares pyridine base is still very low.
For example, hereinafter among the contrast experiment that the described inventor did, acetaldehyde and ammonia promptly use silico-aluminate, ferrosilicate etc. as catalyzer according to the method reaction of above-mentioned routine, produce α-Jia Jibiding and γ-picoline, when using silico-aluminate, the productive rate of α-Jia Jibiding and γ-picoline is respectively 17.6% and 18.5%, and when using ferrosilicate, productive rate is respectively 18.6% and 17.5%, when using gallium silicate, productive rate is respectively 17.3% and 19.3%.
Thereby the productive rate of needed pyridine base is also unsatisfactory in the method for routine, need be further improved productive rate.
The inventor has carried out deep research, produces the method for pyridine bases to find high yield.The result, the inventor finds, (this zeolite catalyst contains titanium and/or cobalt and silicon as the zeolite component at a kind of zeolite catalyst with alkanoic, aliphatic ketone or their mixture and ammonia in gas phase, wherein the atom ratio of silicon and titanium and/or cobalt is about 5 to about 1000) existence when down pyridine bases is produced in reaction, compare as the ordinary method of catalyzer with wherein using, but high productivity produces pyridine bases such as silico-aluminate, ferrosilicate etc.
The invention provides a kind of method of producing pyridine bases, this method comprises, in gas phase, alkanoic, aliphatic ketone or their mixture and ammonia are reacted in the presence of a kind of zeolite catalyst, wherein, this zeolite catalyst contains titanium and/or cobalt and silicon as the zeolite component, and wherein the atom ratio of silicon and titanium and/or cobalt is about 5 to about 1000.
The method of production pyridine bases of the present invention is by using corresponding to alkanoic, aliphatic ketone or their mixture of required pyridine bases and they being carried out with ammonia react in the presence of above-mentioned specific zeolite in gas phase.
This alkanoic is preferably the alkanoic with 1 to 5 carbon atom.Its example comprises saturated alkanoic, formaldehyde for example, and acetaldehyde, propionic aldehyde, butyraldehyde etc., undersaturated alkanoic, for example, propenal, crotonaldehyde, methacrylaldehyde etc.This aliphatic ketone is preferably the aliphatic ketone with 3 to 5 carbon atoms.Its example comprises acetone, methyl ethyl ketone, metacetone etc.Can produce alkanoic or alkenolic dimer, tripolymer, other oligomer and polymer also can be used as raw material.Raw material, i.e. alkanoic and aliphatic ketone and main product, i.e. pyridine bases, between the pass tie up in the above-mentioned table 1 and give an example.
As indicated above, a kind of titanium and/or cobalt and silicon of containing is as the zeolite component, wherein the atom ratio of silicon and titanium and/or cobalt is about 5 to about 1000, and restricted index (constraint index) is used as catalyzer in the reaction of the present invention for about 0.8 to about 12 zeolite.Hereinafter, the above-mentioned zeolite that is used as catalyzer of the present invention is called as titanium and/or cobalt silicate zeolite (titan and/orcobaltsilicate zeolite).The example of titanium and/or cobalt silicate zeolite comprises and contains titanium and the silicon titanosilicate as the zeolite component, contains cobalt and silicon as the cobalt silicate of zeolite component with contain titanium, and cobalt and silicon are as the zeolite of zeolite component.In them one or more can be used as catalyst for reaction of the present invention.Be preferably about 10 to about 500 at the atom ratio that is used for titanium of the present invention and/or cobalt silicate zeolite silicon and titanium and/or cobalt.
Being used for catalyzer of the present invention can be by conventional method preparation.The difference of various titaniums and/or cobalt silicate zeolite is the atom ratio of silicon and titanium and/or cobalt, the difference of crystalline structure etc., and they can easily be prepared.For example, they can be prepared by following document disclosed method: Japanese Patent Application Publication (JP-A) Nos.63-54358,60-12135,56-96720 and 55-7598, the catalyzer magazine, 130,440 (1991), Applied Catalysis A:General, 126,51 (1995), zeolite, 17 (4), 354 (1996) etc.
There is no particular limitation for the crystalline structure of the catalyzer that the present invention is used, though preferred those catalyzer with pentasil type crystal structure that use.Catalyzer with MFI type or MEL type crystal structure is more preferred.
In the present invention, titanium and/or cobalt silicate zeolite can use by its primary state, though titanium and/or cobalt silicate zeolite preferably further contain the ion and/or the compound of one or more elements of a kind of I to XVII of being selected from family element, because can improve the productive rate of pyridine base when used as such.
I to XVII family element is the element in the periodic table of elements of 18 same clan's types of listing in.Its concrete example comprises the Li in the I family element, K, Rb and Cs, the Mg in the II family element, Ca, Sr and Ba, the Sc in the iii group element, Y and lanthanon, La, Ce, Pr, Nd, Er and Yb, the Ti in the IV family element, Zr and Hf, the V in the V group element, Nb and Ta, Cr in the VI family element, Mo and W, the Mn in the VII family element, Tc and Re, the Fe in the group VIII element, Ru and Os, Co in the IX family element, Rh and Ir, the Ni in the X family element, Pd and Pt, Cu and Ag in the XI family element, Zn and Cd in the XII family element, Al in the XIII family element, Ga, In and Tl, Ge in the XIV family element, Sn and Pb, Sb and Bi in the XV family element, Po in the XVI family element, the F in the XVII family element, Cl.Wherein Tl and Pb are preferred.
As the ion and/or the compound of I to XVII family element, can be their ion, their oxide compound, halogenide, vitriol, phosphoric acid salt, nitrate, oxyhydroxide, sulfide, silicate, titanate, borate and carbonate etc.In them one or more can be contained in this titanium and/or cobalt silicate zeolite.Make the method that a kind of titanium and/or cobalt silicate zeolite contain these ions and/or compound comprise ion-exchange techniques, the kneading method, immersion method (impregnation method), dipping method (dipping method), deposition method, evaporation drying method etc., but be not limited to these methods.Concrete example in them is shown in hereinafter.
(1) ion-exchange techniques for example
With a kind of water-soluble salt of above-mentioned element, halogenide for example, nitrate, acetate etc. are dissolved in the water, concentration be 0.01 to 2 gramion/liter.
Then with the alkalimetal ion form, ammonium ion (NH
4 +) form or proton (H
+) titanium and/or the cobalt silicate zeolite of form, preferred NH
4 +The titanium of ionic species and/or cobalt silicate zeolite add in the above-mentioned aqueous solution that obtains, and stir under given temperature, filter then, and repeat this step.
Afterwards, the filtering residue that obtains is at last washed with water.With ionic titanium that contains above-mentioned element and/or the cobalt silicate zeolite drying that obtains like this, calcine if desired.
(2) kneading method for example
Compound and NH with above-mentioned element
4 +Or H
+The titanium of form and/or cobalt silicate zeolite carry out kneading, if desired, and with the water kneading.Then, with the product drying after the kneading, calcine if desired.
(3) dipping method (dipping method) for example
With a kind of water-soluble salt dissolves of above-mentioned element in water.
Then, with NH
4 +Or H
+The titanium of form and/or cobalt silicate zeolite, preferred NH
4 +The titanium of form and/or cobalt silicate zeolite are immersed in this solution.Afterwards, with the Zeolite dehydration of dipping, calcine if desired.
(4) deposition method for example
With NH
4 +Or H
+The titanium of form and/or cobalt silicate zeolite are dispersed in the aqueous solution of water-soluble salt of above-mentioned element.
In this mixture, add ammoniacal liquor, make the oxyhydroxide of above-mentioned element be deposited on NH
4 +Or H
+On the surface of the titanium of form and/or cobalt silicate zeolite, dry then.
Afterwards filtered residue is washed with water and drying, calcine if desired.
(5) the evaporation drying method for example
Compound and NH with a kind of above-mentioned element
4 +Or H
+The titanium of form and/or cobalt silicate zeolite stir in water, make its mixing.
Carry out evaporation drying afterwards, calcine if desired then.
In any one above-mentioned method, calcining is carried out several hrs normally at 350 to 800 ℃ in air, nitrogen and/or carbon dioxide atmosphere.But because catalyzer is heated in reactor in the gas phase contact reacts, the calcining of catalyzer is optional.
One or more preferable range of content that are selected from the ion of the element in I to the XVII family element and/or compound are based on the kind of the kind of titanium and/or cobalt silicate zeolite or the element that wherein contains and form and change.Usually, preferred range is from 0.0005 to 10mg equivalent, and more preferably the contain titanium and/or cobalt and silicon of every 1g are from 0.01 to 5 as the amount of the zeolite of zeolite component.
Be used for titanium of the present invention and/or cobalt silicate zeolite and can be molded into required shape by pelleter or extrusion machine, for example solid cylindricality, hollow cylindrical etc., molded can carrying out with its virgin state, perhaps with a kind of tackiness agent, silicon-dioxide for example, diatomite, kaolin, bentonite, siallites etc., and water, polyoxyethylene glycol and vinylacetate carry out after mixing.Article after the moulding can be used as fixed bed catalyst.
Perhaps, with titanium and/or cobalt silicate zeolite and a kind of tackiness agent, silicon-dioxide for example, diatomite, kaolin, bentonite, siallites etc. and water mix, obtain a kind of slurries, then that this slurries spraying is dry, obtain a kind of spheric microballon, it is used as the liquefied bed catalyzer.For the ion for preparing the element that contains a kind of I to XVII of being selected from family element and/or the titanium and/or the cobalt silicate zeolite of compound, the titanium and/or the cobalt silicate zeolite that are molded into desired shape according to the method described above can pass through above-mentioned ion-exchange techniques, immersion method (impregnation method), dipping method (dipping method) etc. makes it contain this ion and/or compound.In any one above-mentioned method, the catalyzer that obtains can be at 350 to 800 ℃, in air, nitrogen and/or carbon dioxide atmosphere, calcine several hrs, to improve the intensity of formed article, and remove the volatile constituent that contains in the tackiness agent, though since in gas phase contact reacts process in reaction vessel catalyzer be heated, the calcining of catalyzer is not essential.
The method for preparing pyridine base of the present invention can be at fixed-bed reactor, carry out in fluidized-bed reactor or the moving-burden bed reactor.
An example of the method for the present invention of using fixed-bed reactor hereinafter will be described.
Catalyzer of the present invention is loaded in the reaction tubes.The mixed gas of a kind of alkanoic and/or aliphatic ketone and ammonia is introduced in this reaction tubes the promoting the circulation of qi phase reaction of going forward side by side.The mixed gas of alkanoic and/or aliphatic ketone and ammonia also can with water, a kind of rare gas element, nitrogen for example, and/or methyl alcohol is introduced into together.
Alkanoic and/or alkenolic combination and they are compared suitable usage rate and are changed according to needed pyridine base with ammonia.For example, for pyridine and the beta-picoline produced as primary product, acetaldehyde and formaldehyde are used as alkanoic and/or alkenolic combination, and acetaldehyde: formaldehyde: the molar ratio of ammonia is preferably 1: 0.3-3: 0.5-5.In this case, when extra use methyl alcohol, the preferred per 1 mole acetaldehyde of the amount of methyl alcohol is 0.5 mole or still less.Formaldehyde can Fu Er Malin form use.For pyridine and α-Jia Jibiding and the γ-picoline produced as primary product, acetaldehyde is used as alkanoic and/or alkenolic combination, and acetaldehyde: the molar ratio of ammonia is preferably 1: 0.8-3.When acetaldehyde and ammonia reacted according to method of the present invention, the selectivity of α-Jia Jibiding improved.
Alkanoic, aliphatic ketone and ammonia and under the situation of needs, water, a kind of rare gas element, for example nitrogen and/or methyl alcohol were with 100 to 10000 hours
-1, preferred 300 to 3000 hours
-1Air speed pass through catalyzer.Temperature of reaction is from 300 to 700 ℃, preferred 350 to 600 ℃.The pressure of reaction can be from normal atmosphere with down to several normal atmosphere, preferred 1 normal atmosphere to 2 normal atmosphere.
After reacting as mentioned above, the effusive pyridine base that contains reactant gases can be concentrated from reaction tubes.Perhaps contact with a kind of appropriate solvent and be dissolved in this solvent by the reactant gases that will contain pyridine base.Can enriched material or the solution that obtain be distilled, reclaim pyridine.
When the long reaction rear catalyst is damaged, can regenerate according to the catalyst regeneration process of routine.That is, but do not surpassing under the high temperature of catalyzer tolerable temperature, preferably under 350 to 800 ℃ temperature with air by catalyst layer, with the carbon of burnt deposit on catalyzer.If desired, can be with air water vapour, nitrogen, carbonic acid gas etc. dilute.
Embodiment
Hereinafter embodiment further specifies the present invention, but does not limit its scope.
Catalyst preparation example 1
According to being described in the catalyzer magazine, 130,440 (1991) method synthesis of titanium silicon hydrochlorate.
In a pyrex glass reaction vessel of having equipped agitator and dropping funnel, pack into the mixture of tetraethylorthosilicise of the methanol solution of 20% (weight) of the hydroxide four of 566g-just-butyl ammonium (the positive TBuA of hydroxide: 0.436 mole) and 455g (2.18 moles).By the aqueous isopropanol of addition funnel to the tetrabutyl titanate ester that wherein dropwise adds 2300g (tetrabutyl titanate ester: 0.033 mole), stir simultaneously, continued stir about then 30 minutes.In the mixture that obtains, add the distilled water of 790g, stir simultaneously, continue reaction 2 hours, remove ethanol at 75-80 ℃ simultaneously.With the cooling of the reaction mixture that obtains and be transferred in the autoclave, and kept 2 days, stir simultaneously at 170 ℃.Then, with the autoclave cooling, and, obtain a kind of crystallization with the content filtration.With the crystal that obtains ion-exchange water washing, 100 ℃ of dryings 8 hours, then in airflow 550 ℃ of calcinings 16 hours.The incinerating material that obtains is analyzed, and analytical results shows that it is the titanosilicate with MEL type crystal structure, and wherein, Si/Ti (atom ratio) is 50.
The titanosilicate that obtains is added in 1 liter of 5% aqueous ammonium chloride solution, stirred 1 hour at 50 to 60 ℃ then, filter then, carry out ion-exchange.The residue that filtration is obtained carries out ion-exchange three times according to mode same as described above.The residue that finally obtains is washed with water Cl in washings
-Ionic concentration is 1ppm or lower, 110 ℃ of dryings 16 hours, obtains NH then
4 +The titanosilicate of form.It was further calcined 6 hours in air at 550 ℃, obtain H
+The titanosilicate of form.
Catalyst preparation example 2
According to the method that is described in JP-A-63-54358, synthetic cobalt silicate as mentioned below.
The hydroxide four of the tetraethyl orthosilicate (0.48 mole) of 100g and 217.5g 10% (weight)-just-propyl ammonium (hydroxide four-just-propyl ammonium: 0.96 mole) is mixed in an autoclave.In the mixture that obtains, add the acetopyruvic acid cobalt (III) (0.016 mole) of 5.7g and the mixing solutions of ethylene glycol, stir simultaneously, continued stir about then 30 minutes.Afterwards, with the mixture heating up to 105 that obtains ℃, and stirred 120 hours under identical temperature, it is synthetic to carry out hydro-thermal.With the autoclave cooling, the content filtration is obtained a kind of crystal.With the ion-exchange water washing of this crystal, reach 7.3 until the pH of washings.With the product that obtains 120 ℃ of dryings 16 hours, then 550 ℃ of calcinings 4 hours in airflow.The incinerating material is analyzed, and analytical results shows that it is the cobalt silicate with MFI type crystal structure, and wherein, Si/Co (atom ratio) is 25.
The cobalt silicate that obtains is carried out ion-exchange according to the mode identical with catalyst preparation example 1, washing, dry and calcining obtains NH
4 +The cobalt silicate and the H of form
+The cobalt silicate of form.
Catalyst preparation example 3
According to the method synthesizing Si-Al hydrochlorate that is described in JP-A-2-209867.
With the distilled water of 433.4g, the ammonium sulfate of 4.6g, the sulfuric acid of the bromination four of 55.8g-just-propyl ammonium and 40g mixes, and obtains solution A.The distilled water of 320g and No. 3 water glass of 453g are mixed, obtain solution B.The distilled water of 754g and the sodium-chlor mixing of 189g are obtained solution C.With the solution C stainless autoclave of packing into, and to wherein adding solution A and B vigorous stirring simultaneously.The pH of mixture is controlled in 9.5 to 11 the scope.Autoclave is sealed, and temperature is brought up to 160 ℃, continue then to stir, carried out the hydro-thermal Synthetic 20 hour.At this moment, pressure is 0.5 to 0.6Mpa (5-6kg/cm
2).After reaction is finished, mixture is cooled to room temperature, the content in the autoclave is filtered the crystal that produces in obtaining reacting.This crystal is added in the distilled water, and stir and washing, filter then.Repeat above-mentioned washing or filtration, the Cl in filtrate
-Ionic concentration reaches 1ppm or lower.Afterwards, with crystal 110 ℃ of dryings 16 hours, then, 530 ℃ of calcinings 4 hours in airflow.The incinerating material is analyzed, and analytical results shows that it is the Na with MFI type crystal structure
+The cobalt silicate of form, wherein, Si/Al (atom ratio) is 100.
To the Na that obtains
+The cobalt silicate of form carries out ion-exchange according to the mode identical with catalyst preparation example 1, washing, and dry and calcining obtains NH
4 +The cobalt silicate and the H of form
+The cobalt silicate of form.
Catalyst preparation example 4
According to the synthetic ferrosilicate of the method that is described in JP-A-2-209867.
With a kind of iron nitrate by 19g (III) 9-hydrate, the aqueous solution that the chlorination four of 34g-just-propyl ammonium and distilled water are formed is called solution A.Be called solution B with a kind of by the stifling silicon-dioxide of 70g and the suspension of distilled water.A kind of sodium hydroxide and solution of forming of the distilled water of 50g by 7.4g is called solution C.Solution C is packed in the stainless autoclave, and to wherein adding solution A and B stirs simultaneously.Autoclave is sealed, and temperature is brought up to 160 ℃, continue then to stir, carried out hydro-thermal synthetic 60 hours.PH is changed to 11.4 from 12.4.Content in the autoclave is filtered, obtain a kind of solid.With this solid distilled water wash, reach 7.3 until the pH of washings.The solid that obtains is analyzed, and analytical results shows that it is the Na with MFI type crystal structure
+The ferrosilicate of form, wherein, Si/Fe (atom ratio) is 25.
To the Na that obtains
+The ferrosilicate of form carries out ion-exchange according to the mode identical with catalyst preparation example 1, washing, and dry and calcining obtains NH
4 +The cobalt silicate and the H of form
+The ferrosilicate of form.
Catalyst preparation example 5
Prepare Na according to the mode identical with catalyst preparation example 4
+The gallium silicate of form, NH
4 +The gallium silicate of form and H
+The gallium silicate of form only is to use gallium nitrate (III) the 8-hydrate of 19g to replace iron nitrate (III) 9-hydrate in the catalyst preparation example 4.To Na
+The gallium silicate of form is analyzed, and analytical results shows, it is to have the MFI type crystal structure and Si/Ga (atom ratio) is 25.
Embodiment 1
The H that catalyst preparation example 1 is obtained
+Titanosilicate (the H of form
+The Ti/Si of form) in the pressure lower compression of 39Mpa, grinds then, obtain having particle from the unified particle size of 1.0 to 1.7mm (10 to 16 orders).Use these particles to prepare pyridine bases in the following manner as catalyzer.
With the above-mentioned 6g catalyst loading that obtains in glass reaction tube with internal diameter 20mm.The catalyst loading of reaction tubes partly is heated to 380 ℃, and partly feeds 2760ml/ hour ammonia and 2.48g/ hour acetaldehyde to catalyst loading.After beginning to feed acetaldehyde 30 minutes, the reactant gases that flows out reaction tubes was fed in the water 20 minutes, so that the soluble component in the reactant gases is dissolved in the water.The solution that obtains by gas chromatographic analysis.The results are shown in table 3.
The productive rate of pyridine base depends on the total carbon quantity of the acetaldehyde that reacts, and calculates according to the following equation.
Pyridine productive rate (%)=[(the total carbon atom number amount of the pyridine of generation)/(the total carbon atom number amount of the acetaldehyde that reacts)] * 100
α, the productive rate of β or γ-picoline (%)=[(α of generation, the total carbon atom number amount of β or γ-picoline)/(the total carbon atom number amount of the acetaldehyde that reacts)] * 100
Embodiment 2
Prepare pyridine bases, the H that only is to use catalyst preparation example 2 to obtain according to the mode identical with embodiment 1
+Cobalt silicate (the H of form
+The Co/Si of form) H that uses among the replacement embodiment 1
+The titanosilicate of form.The results are shown in table 3.
Comparative Examples 1
Prepare pyridine bases, the H that only is to use catalyst preparation example 3 to obtain according to the mode identical with embodiment 1
+Silico-aluminate (the H of form
+The Al/Si of form) H that uses among the replacement embodiment 1
+The titanosilicate of form.The results are shown in table 3.
Comparative Examples 2
Prepare pyridine bases, the H that only is to use catalyst preparation example 4 to obtain according to the mode identical with embodiment 1
+Ferrosilicate (the H of form
+The Fe/Si of form) H that uses among the replacement embodiment 1
+The titanosilicate of form.The results are shown in table 3.
Comparative Examples 3
Prepare pyridine bases, the H that only is to use catalyst preparation example 5 to obtain according to the mode identical with embodiment 1
+Gallium silicate (the H of form
+The Ga/Si of form) H that uses among the replacement embodiment 1
+The titanosilicate of form.The results are shown in table 3.
Table 3
| The embodiment numbering | Catalyzer | Productive rate (%) | ||||
| Py | αPc | βPc | γPc | Amount to | ||
| Embodiment 1 | H +The Ti/Si of form | 1.2 | 34.2 | 0 | 12.1 | 47.5 |
| Embodiment 2 | H +The Co/Si of form | 1.6 | 27.0 | 0 | 12.8 | 41.4 |
| The comparative example 1 | H +The Al/Si of form | 5.1 | 17.6 | 0 | 18.5 | 41.2 |
| The comparative example 2 | H +The Fe/Si of form | 3.2 | 18.6 | 0 | 17.5 | 39.3 |
| The comparative example 3 | H +The Ga/Si of form | 2.5 | 17.3 | 0 | 19.3 | 39.1 |
Py: pyridine productive rate
α Pc: α picoline productive rate
β Pc: β picoline productive rate
γ Pc: γ picoline productive rate
Embodiment 3
Add the H that obtains in the catalyst preparation example 1 of 13.93g in the solution for preparing in the water of 18.14g to a kind of being dissolved in by lead nitrate with 1.68g
+The titanosilicate of form floods.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the titanosilicate (the titanosilicate 0.73mg equivalent of every 1g) of the Pb of 7% (weight) in air-flow with the product that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned titanosilicate that contains Pb (7%Pb-Ti/Si) that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.
The results are shown in table 4.
Embodiment 4
Add the H that obtains in the catalyst preparation example 2 of 19.4g in the solution for preparing in the water of 14.2g to a kind of being dissolved in by lead nitrate with 0.96g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 0.30mg equivalent of every 1g) of the Pb of 3% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (3%Pb-Co/Si) that contains Pb that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Embodiment 5
To a kind of ammonium tungstate para[5 (NH that passes through 59.54g
4)
2O12WO
35H
2O] be dissolved in the solution for preparing in the water of 200g the H that obtains in the catalyst preparation example 2 that adds 7.44g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 2.46mg equivalent of every 1g) of the W of 7% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (7%W-Co/Si) that contains W that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Embodiment 6
Add the H that obtains in the catalyst preparation example 2 of 7.44g in the solution for preparing in the water of 10.4g to a kind of being dissolved in by zinc nitrate 6-hydrate with 2.55g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 2.30mg equivalent of every 1g) of the Zn of 7% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (7%Zn-Co/Si) that contains Zn that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Embodiment 7
Add the H that obtains in the catalyst preparation example 2 of 7.44g in the solution for preparing in the water of 10.4g to a kind of being dissolved in by thallium trinitrate (TTN) (I) with 0.73g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 0.37mg equivalent of every 1g) of the Tl of 7% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (7%Tl-Co/Si) that contains Tl that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Embodiment 8
Add the H that obtains in the catalyst preparation example 2 of 7.44g in the solution for preparing in the water of 10.4g to a kind of being dissolved in by lanthanum nitrate 6-hydrate with 1.75g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 1.63mg equivalent of every 1g) of the La of 7% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (7%La-Co/Si) that contains La that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Embodiment 9
Add the H that obtains in the catalyst preparation example 2 of 7.44g in the solution for preparing in the water of 10.4g to a kind of being dissolved in by indium sulfate 9-hydrate with 0.96g
+The cobalt silicate of form, and they are mixed.120 ℃ of dryings 5 hours, then, 550 ℃ of calcinings 5 hours, obtaining in metal content was the cobalt silicate (the cobalt silicate 1.97mg equivalent of every 1g) of the In of 7% (weight) in air-flow with the mixture that obtains.
Prepare pyridine bases in the mode identical, only be to use the above-mentioned cobalt silicate (7%In-Co/Si) that contains In that obtains to replace the H that uses among the embodiment 1 with embodiment 1
+The titanosilicate of form.The results are shown in table 4.
Table 4
| The embodiment numbering | Catalyzer | Productive rate (%) | ||||
| Py | αPc | βPc | γPc | Amount to | ||
| Embodiment 3 | 7％Pb-Ti/Si | 1.1 | 52.1 | 0 | 17.0 | 70.2 |
| Embodiment 4 | 3％Pb-Co/Si | 1.1 | 51.6 | 0 | 20.1 | 72.8 |
| Embodiment 5 | 7％W-Co/Si | 1.0 | 28.0 | 0 | 15.5 | 44.5 |
| Embodiment 6 | 7％Zn-Co/Si | 1.0 | 34.9 | 0 | 17.2 | 53.1 |
| Embodiment 7 | 7％Tl-Co/Si | 0.9 | 38.5 | 0 | 14.4 | 53.8 |
| Embodiment 8 | 7％La-Co/Si | 1.8 | 29.9 | 0 | 11.8 | 43.5 |
| Embodiment 9 | 7％In-Co/Si | 1.8 | 29.9 | 0 | 11.8 | 43.5 |
Py: pyridine productive rate
α Pc: α picoline productive rate
β Pc: β picoline productive rate
γ Pc: γ picoline productive rate
Claims (7)
1. method of producing pyridine bases, this method comprises, to have the alkanoic of 1 to 5 carbon atom, the aliphatic ketone with 3 to 5 carbon atoms or their mixture and ammonia in gas phase reacts in the presence of a kind of zeolite catalyst, wherein, this zeolite catalyst contains titanium and/or cobalt and silicon as the zeolite component, and wherein the atom ratio of silicon and titanium and/or cobalt is 5 to 1000.
2. according to the described method for preparing pyridine bases of claim 1, the atom ratio of silicon and titanium and/or cobalt is preferably 10 to 500.
3. according to the described method for preparing pyridine bases of claim 1, wherein, contain titanium and/or cobalt and silicon have the pentasil type as the zeolite of zeolite component crystalline structure.
4. according to the described method for preparing pyridine bases of claim 1, wherein, contain titanium and/or cobalt and silicon have MFI type or MEL type as the zeolite of zeolite component crystalline structure.
5. according to the described method for preparing pyridine bases of claim 1, wherein, make and contain titanium and/or cobalt and silicon further contain one or more elements that are selected from I to the XVII family element as the zeolite of zeolite component ion and/or compound.
6. according to the described method for preparing pyridine bases of claim 6, wherein, the content range that is selected from the ion of one or more elements of I to the XVII family element and/or compound be based on every 1g contain titanium and/or cobalt and silicon as the zeolite of zeolite component from 0.0005 to 10mg equivalent.
7. according to the described method for preparing pyridine bases of claim 1, wherein, described alkanoic, aliphatic ketone or their mixture are acetaldehyde.
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| CNB001094580A CN1172915C (en) | 2000-06-26 | 2000-06-26 | Method for preparing pyridine alkalis |
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|---|---|---|---|
| CNB001094580A CN1172915C (en) | 2000-06-26 | 2000-06-26 | Method for preparing pyridine alkalis |
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| CN1172915C true CN1172915C (en) | 2004-10-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103965098A (en) * | 2014-05-22 | 2014-08-06 | 山东昆达生物科技有限公司 | Energy saving technology in pyridine and 3-methylpyridine preparation processes |
| 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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