CN101570509B - Method for preparing pyridine N-oxide - Google Patents
Method for preparing pyridine N-oxide Download PDFInfo
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- CN101570509B CN101570509B CN2008101053693A CN200810105369A CN101570509B CN 101570509 B CN101570509 B CN 101570509B CN 2008101053693 A CN2008101053693 A CN 2008101053693A CN 200810105369 A CN200810105369 A CN 200810105369A CN 101570509 B CN101570509 B CN 101570509B
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Abstract
The invention discloses a method for preparing pyridine N-oxide, which is characterized in that the pyridine N-oxide is prepared by mixing pyridine, oxygen, hydrogen, diluent gas, solvent and catalyst for contact reaction at 0-180 DEG C and 0.1-3.0 MPa, wherein the mol ratio of the pyridine to the oxygen to the hydrogen to the diluent gas is 1:0.1-10:0.1-10:0-100, the mass ratio of the pyridine to the catalyst is 0.5-50:1, and the mass ratio of the solvent to the catalyst is 20-1000:1, and in addition, the catalyst is microporous titanium silicon material or compound containing the microporoustitanium silicon material, an oxide formed by the microporous titanium silicon material has the formula of xTio2.100SiO2.yEmOn.zE, wherein x is equal to 0.001-50.0, y+z is equal to 0.005-20.0, y/z is less than 5, E can be one or more of such noble metals as Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and Au, and both m and n are the numbers meeting the need of the oxidation of the E. The grains of the epoxy propanol can be in hollow structures or concavo-convex structures, and the method ensures the high conversion rate, the good selectivity and the long operation period of the pyridine.
Description
Technical field
The present invention relates to produce the method for N-pyridine oxide, further say the method that N-pyridine oxide is produced in a kind of pyridine oxidation that the present invention relates to.
Background technology
N-pyridine oxide is the medicine of using always, the midbody of Chemicals.It can increase surface adsorption as a kind of new non-ionic surfactants, reduces surface viscosity, stable foam.Different based on reaction mechanism, the preparation of N-pyridine oxide can be divided into direct oxidation method and catalytic oxidation.The oxygenant that direct oxidation method is commonly used has hydrogen peroxide and Peracetic Acid.Hydrogen peroxide oxidation process has that process is simple, mild condition, advantage that yield is high.Shortcoming is big as the Glacial acetic acid min. 99.5 demand of medium, and troublesome poeration must add a large amount of sodium hydroxide neutralizations when reaction finishes; And length consuming time causes the production efficiency of intermittent operation low.It is short that the Peracetic Acid oxidation style has the reaction times, the advantage that the Glacial acetic acid min. 99.5 usage quantity is little; But Stability of Acetic acid peroxide is poor, and high temperature is prone to decompose, and influences the oxidation productive rate, and the peroxy acid explosive, also is the synthetic middle problem that exists.The method of traditional preparation process N-pyridine oxide is to make catalyzer with acetate, excessive H
2O
2Behind the pyridine oxide, with chloroform extraction, drying, underpressure distillation and get, but 3 insufficient aspects are arranged: 1. the reaction times reaches 12h, and energy consumption is big; 2. need in the reaction to add a large amount of acetate, need a large amount of anhydrous Na after the reaction again
2CO
3Neutralize, cause aftertreatment loaded down with trivial details; 3. because of N-pyridine oxide polarity is strong, the solubleness in water is quite big, and the effect of chloroform extraction is not fine.
In recent years, many investigators constantly are devoted to improve the method for pyridine oxidation, and the key of catalytic oxidation is to select appropriate catalyst for use.Catalyzer has Zeo-karb, peroxy acid/acid anhydride, pertungstate, heteropolyacid and titanium-silicon molecular sieve TS-1 etc.The ydrogen peroxide 50 consumption of cation exchange resin processes is little, but speed of response is slow, and reaction is difficult to carry out thoroughly.Peroxy acid/acid anhydride method has cost height, complex technical process, environmental pollution important disadvantages.Pertungstate method productive rate is higher, but the catalyzer price is too high, requires hydrogen peroxide that higher concentration is arranged simultaneously.Heteropolyacid has very high activity, and the reaction times is shorter; Owing to have the character of acid, avoided adding a large amount of acetic acid in the reaction simultaneously, than direct oxidation method bigger improvement is arranged, but heteropolyacid has been soluble in water, the catalyst recovery difficulty, and cost an arm and a leg.The TS-1 molecular sieve not only has catalytic activity, stability and reusability preferably as catalyzer, and has greatly reduced the generation of by product, has reduced pollution and the corrosion on Equipment of oxidising process to environment.Yet relevant use TS-1 Preparation of Catalyst N-pyridine oxide processing condition study report in great detail seldom.
Simultaneously because H
2O
2Extremely unstable, meet heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, in packing, storage, transportation, will take special security measures.Receive the limitation of cost and safety-problems, and preparation H
2O
2Need the independent equipment and the recycle system, expensive bigger, the situ production expense is very high, before not having stricter environmental regulation appearance, adopts H
2O
2The technology industriallization certain economic obstacle is arranged.
Summary of the invention
The object of the invention is exactly the deficiency to prior art, and it is that catalyzer, hydrogen and oxygen exist down that the micropore titanium-silicon material with uniqueness is provided, and is prepared the method for N-pyridine oxide by pyridine.
The preparation method of N-pyridine oxide provided by the invention; It is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure; With pyridine, oxygen, hydrogen, diluents, solvent and catalyst mix contact reacts; The mol ratio of pyridine and oxygen, hydrogen, diluents is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of pyridine and catalyzer are (0.1～50): 1, and the mass ratio of solvent and catalyzer is (20～1000): 1; Said catalyzer is a kind of micropore titanium-silicon material or the compsn that contains this micropore titanium-silicon material, and the composition of micropore titanium-silicon material is expressed as xTiO with the form of oxide compound
2100SiO
2YE
mO
nZE; Wherein the x value is 0.001～50.0, (y+z) value is 0.005～20.0 and y/z＜1; E representes to be selected from one or more precious metals among Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and the Au, and m and n satisfy the required number of E oxidation state, and this material grains partly or entirely is a hollow structure.
In the method for catalyzed oxidation hexanaphthene provided by the invention, said micropore titanium-silicon material discloses in application number is 200710064981.6 one Chinese patent application, in the representation of oxide compound; The preferred 0.005-25 of x value, (y+z) are worth preferred 0.01-10, one or more among the preferred Pd of precious metal E, Pt and the Au, more preferably Pd and/or Pt; When precious metal is two or more; The value of said y be every kind of precious metal y value with, the value of said z be every kind of precious metal z value and, for example; When selected precious metal was Pt and Pd, the composition of this material was expressed as xTiO with the form of oxide compound
2100SiO
2Y
1PtOy
2PdOz
1Ptz
2Pd, i.e. y=y
1+ y
2, z=z
1+ z
2The crystal grain of this material is all or part of to be hollow structure, and the radical length of the cavity part of hollow crystal grain is 2～300 nanometers, is preferably 10～200 nanometers; This material is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 50 milligrams/gram, is preferably at least 70 milligrams/gram; There is hysteresis loop between the adsorption isothermal line of its low temperature conditioning absorption and the desorption isotherm; The shape of cavity part is not changeless, can be different shapes such as rectangle, circle, irregular cycle, irregular polygon, or one or more the combination in these shapes; Its crystal grain can be single crystal grain or the gathering crystal grain that is gathered into by a plurality of crystal grain.
Said micropore titanium-silicon material, crystal grain all or portion be hollow structure, help the diffusion of reactant and product molecule, the synergy of precious metal and HTS is improved, overcome precious metal accumulative drawback.
, application number discloses two kinds of preparing methods of above-mentioned said micropore titanium-silicon material in being 200710064981.6 one Chinese patent application simultaneously.
One of method is HTS, protective material, noble metal source and reductive agent to be joined to change hydrothermal treatment consists in the reaction kettle in the solution that contains alkali source behind the mixing over to earlier, filters, washs, is drying to obtain, and more particularly comprises:
(1) earlier HTS, protective material, noble metal source and reductive agent are joined mixing in the solution that contains alkali source; It consists of HTS (gram): protective material (mole): alkali source (mole): reductive agent (mole): noble metal source (gram is in precious metal simple substance): water (mole)=100: (0.0001-5.0): (0.005-5.0): (0.005-15.0): (0.005-10.0): (200-10000);
(2) mixture of step (1) gained is changed in the reaction kettle under the hydrothermal treatment consists condition, react again, and reclaim product and promptly get micropore titanium-silicon material of the present invention.
Wherein, Form in the step (1) and be preferably HTS (gram): protective material (mole): alkali source (mole): reductive agent (mole): noble metal source (gram is in precious metal simple substance): water (mole)=100: (0.005-1.0): (0.01-2.0): (0.01-10.0): (0.01-5.0): (500-5000).
Said HTS comprises the HTS of all kinds structure in the step (1), like TS-1, and TS-2, Ti-BETA, Ti-MCM-22 etc. are preferably TS-1.
The said protective material of step (1) is meant polymkeric substance or tensio-active agent; Wherein polymkeric substance can be Vestolen PP 7052, polyoxyethylene glycol, PS, SE, Vilaterm etc. and verivate thereof, and tensio-active agent can be AS, cats product and nonionogenic tenside.
The said reductive agent of step (1) can be hydrazine, hydroborate, Trisodium Citrate etc., and wherein hydrazine can be Hydrazine Hydrate 80, hydrazine hydrogen chloride, hydrazonium sulfate etc., and hydroborate can be Peng Qinghuana, POTASSIUM BOROHYDRIDE 97MIN etc.
The said noble metal source of step (1) is selected from the inorganics or the organism of above-mentioned precious metal, can be other complex compound of oxide compound, halogenide, carbonate, nitrate salt, ammonium salt, ammonia chloride salt, oxyhydroxide or precious metal etc.With the palladium is example, and the palladium source can be inorganic palladium source and/or organic palladium source.Wherein inorganic palladium source can be other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.
The said alkali source of step (1) is inorganic alkali source or organic alkali source.Wherein inorganic alkali source is ammoniacal liquor, sodium hydroxide, Pottasium Hydroxide, hydrated barta etc.; Organic alkali source is urea, quaternary amine alkali compounds, fat amine compound, alcamine compound or the mixture be made up of them.
Said its general formula of quaternary ammonium hydroxide compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1-4 carbon atom, preferably propyl group.
Its general formula of said fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene group, n=1 or 2 with 1-6 carbon atom; Said fat amine compound is ethamine, n-Butyl Amine 99, tetramethylenediamine or hexanediamine.
Its general formula of said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3; Said alcamine compound is monoethanolamine, diethylolamine or trolamine.
The said hydrothermal treatment consists condition of step (2) is under temperature 80-200 ℃ and autogenous pressure hydrothermal treatment consists 2-360 hour; The process of said recovery product is well known to those skilled in the art; Do not have special feature, generally include processes such as crystallization product washing, dryings.
Two of method comprises the steps:
(1) titanium source, silicon source, alkali source, protective material, noble metal source and water are mixed the back in 120～200 ℃ of hydrothermal crystallizings 6 hours～10 days; After drying is filtered in taking-up, roasting gets middle crystalline material; The mole of mixture consists of the silicon source: titanium source: alkali source: noble metal source: protective material: water=100: (0.005-50.0): (0.005-20.0): (0.005-10.0): (0.005-5.0): (200-10000), wherein the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, noble metal source is in simple substance;
(2) the middle crystalline material with step (1) gained changes in the last filtrating of step (1); After the mol ratio of the noble metal source that is added in adding and the step (1) is the reductive agent of 0.1-10; In reaction kettle under temperature 80-200 ℃ and autogenous pressure hydrothermal treatment consists 2-360 hour, and reclaim product and promptly get micropore titanium-silicon material of the present invention.
Wherein, the mole of step (1) mixture is formed the silicon source that is preferably: titanium source: alkali source: noble metal source: protective material: water=100: (0.01-10.0): (0.01-10.0): (0.01-5.0): (0.01-1.0): (500-5000).
The said silicon of step (1) source is silica gel, silicon sol or organosilicon acid esters, preferably organosilicon acid esters; Said its general formula of organosilicon acid esters is R
4 4SiO
4, R wherein
4Preferably have the alkyl of 1-4 carbon atom, be more preferably ethyl.
The said titanium of step (1) source is inorganic titanium salt or organic titanate, preferably organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
5)
4, R wherein
5For having the alkyl of 1-6 carbon atom, more preferably has the alkyl of 2-4 carbon atom.
Said alkali source is the mixture that quaternary amine alkali compounds or quaternary amine alkali compounds and fat amine compound, alcamine compound are formed in the step (1).Wherein, said its general formula of quaternary ammonium hydroxide compounds is (R
6)
4NOH, R
6For having the alkyl of 1-4 carbon atom, preferably propyl group.Its general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be selected from alkyl or alkylidene group, n=1 or 2, for example ethamine, n-Butyl Amine 99, tetramethylenediamine, hexanediamine etc. with 1-6 carbon atom.Its general formula of said alcamine compound is (HOR
8)
mNH
(3-m)R wherein
8Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3, for example monoethanolamine, diethylolamine, trolamine etc.
The said protective material of step (1) is meant polymkeric substance or tensio-active agent; Wherein polymkeric substance can be Vestolen PP 7052, polyoxyethylene glycol, PS, SE, Vilaterm etc. and verivate thereof, and tensio-active agent can be AS, cats product and nonionogenic tenside.
The said noble metal source of step (1) is selected from the organism or the inorganics of precious metal, can be other complex compound etc. of their oxide compound, halogenide, carbonate, nitrate salt, ammonium salt, chlorination ammonium salt, oxyhydroxide or precious metal.With the palladium source is example; Can be inorganic palladium source and/or organic palladium source; Wherein inorganic palladium source can be other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.
Said reductive agent can be azanol, hydrazine, hydroborate, Trisodium Citrate etc. in the step (1), and wherein hydrazine can be Hydrazine Hydrate 80, hydrazine hydrogen chloride, hydrazonium sulfate etc., and hydroborate can be Peng Qinghuana, POTASSIUM BOROHYDRIDE 97MIN etc.
The method that pyridine oxidation under hydrogen and oxygen provided by the invention exists prepares N-pyridine oxide can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, behind pyridine, solvent, catalyzer adding reactor drum, add oxygen, hydrogen, diluents continuously; And continuous mode can adopt fixed-bed reactor when carrying out, and behind the catalyzer of packing into solvent, pyridine, oxygen, hydrogen, diluents is added continuously; Also can adopt slurry bed reactor, catalyzer, solvent making beating back are added pyridine, oxygen, hydrogen, diluents continuously, the while is separated product constantly.Adopting under periodical operation or the operate continuously mode, reacting total gas space velocity is 10～10000h
-1, be preferably 100～5000h
-1
Method provided by the invention can also adopt closed still reaction, and soon catalyzer, solvent, pyridine and oxygen, hydrogen, diluents add simultaneously and mix afterreaction in the still.
In the method provided by the invention, the raw material optimum ratio is following: the mol ratio of pyridine and oxygen is preferably 1: (0.2～5.0), the mol ratio of pyridine and hydrogen is preferably 1: (0.2～5.0), the mass ratio of solvent and catalyzer is preferably (20～500): 1.
In the method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.3～2.5MPa.
In the method provided by the invention, diluents can be added, also diluents can be do not added according to practical situation.
In preparation method provided by the invention, said diluents can be rare gas elementes such as nitrogen, argon gas, helium, neon, also can be gases such as carbonic acid gas, methane, ethane, propane.
In the method provided by the invention, said solvent is selected from alcohols or ketone or nitrile, acids, ester class or their mixing such as acetone, butanone such as water or methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, is preferably methyl alcohol and/or water.
In the method provided by the invention, catalyzer is micropore titanium-silicon material or the compsn that contains micropore titanium-silicon material, and wherein said compsn is selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by micropore titanium-silicon material and other and forms.
The preparation method of N-pyridine oxide provided by the invention is in the presence of hydrogen, with molecular oxygen as oxidant; In virgin gas, need not to add any suppressor factor or initiator, adopt the hollow micropore titanium-silicon material that contains precious metal, especially contains palladium, increased the velocity of diffusion of reactant and product as catalytic active component; Reduced the generation of side reactions such as open loop, over oxidation; Especially under the high situation of selectivity, the transformation efficiency of its pyridine is better, and the steady running time keeps longer.
Description of drawings
Fig. 1 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 1 sample A.
Fig. 2 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 2 sample B.
Fig. 3 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 3 sample C.
Fig. 4 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 4 sample D.
Fig. 5 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 5 sample E.
Fig. 6 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 6 sample F.
Fig. 7 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 7 sample G.
Fig. 8 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 8 sample H.
Fig. 9 is transmission electron microscope (TEM) photo of embodiment 1 sample A.
Figure 10 is transmission electron microscope (TEM) photo of embodiment 2 sample B.
Figure 11 is transmission electron microscope (TEM) photo of embodiment 3 sample C.
Figure 12 is transmission electron microscope (TEM) photo of embodiment 4 sample D.
Figure 13 is transmission electron microscope (TEM) photo of embodiment 5 sample E.
Figure 14 is transmission electron microscope (TEM) photo of embodiment 6 sample F.
Figure 15 is transmission electron microscope (TEM) photo of embodiment 7 sample G.
Figure 16 is transmission electron microscope (TEM) photo of embodiment 8 sample H.
Embodiment
Following embodiment and Comparative Examples will be done explanation further to the present invention, but therefore not limit content of the present invention.
Among Comparative Examples and the embodiment, used reagent is commercially available chemically pure reagent.
Used HTS is by prior art Zeolites among Comparative Examples and the embodiment, 1992, and the TS-1 sieve sample of the method preparation described in the Vol.12 943-950 page or leaf.
The adsorption-desorption isothermal curve of the low temperature nitrogen absorption of sample is on the static n2 absorption apparatus of the ASAP2405 of U.S. Micromeritics company, to measure according to ASTM D4222-98 standard method.
The benzene adsorptive capacity of sample is measured and is adopted conventional static adsorptive method, and condition determination is 25 ℃, P/P
0=0.10, adsorption time 1 hour.
The transmission electron microscope photo (TEM) of sample is at the Dutch Tecnai G of FEI Co.
2Obtain acceleration voltage 20kV on the F20S-TWIN type transmission electron microscope.
In Comparative Examples and embodiment:
Pyridine transformation efficiency (%)=(molar weight-unreacted pyridine molar weight of pyridine in feeding intake)/molar weight * 100 of pyridine in feeding intake;
Total molar weight * 100 that transform of the molar weight/pyridine of N-pyridine oxide in N-pyridine oxide selectivity (%)=product.
The preparation process of the micropore titanium-silicon material A that uses in embodiment 1～8 explanation method provided by the invention, B, C, D, E, F, G, H.
Embodiment 1
Get in the aqueous solution (mass percent concentration 10%) that nitric acid ammonia palladium complex solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01 grams per milliliter (in the palladium atom) and an amount of Hydrazine Hydrate 80 and cetyl trimethylammonium bromide join TPAOH and mix; HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): Hydrazine Hydrate 80 (mole): nitric acid ammonia palladium complex (gram is in palladium): water (mole)=100: 0.005: 0.5: 3.0: 2.0: 1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 150 ℃ temperature and autogenous pressure, and gains are filtered, use water washing, after the seasoning, and under 180 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material A that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 4TiO
2100SiO
20.01PdO0.09Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 1), the benzene adsorptive capacity is 65mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Fig. 9).
Embodiment 2
Get in the aqueous solution (mass percent concentration 15%) that palladium chloride solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01 grams per milliliter (in the palladium atom) and appropriate hydrochloric acid hydrazine and Vestolen PP 7052 join sodium hydroxide and mix; HTS (gram) wherein: Vestolen PP 7052 (mole): sodium hydroxide (mole): hydrazine hydrogen chloride (mole): Palladous chloride (gram is in palladium): water (mole)=100: 0.9: 1.8: 0.15: 0.1: 4600.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 24 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, use water washing, after the seasoning, and under 110 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material B that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 8TiO
2100SiO
20.006Pd00.008Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 2), the benzene adsorptive capacity is 68mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 10).
Embodiment 3
With positive tetraethyl orthosilicate, tetrabutyl titanate, concentration is to mix in the acid chloride solution of 0.01 grams per milliliter (in the palladium atom) and the aqueous solution (mass percent concentration is 10%) that tween 80 joins TPAOH and tetramethylenediamine; Wherein mole is formed the silicon source: titanium source: TPAOH: tetramethylenediamine: palladium source: protective material: water=100: 0.03: 0.5: 0.1: 0.05: 0.02: 550, and the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into sealed reactor then, hydrothermal treatment consists is 72 hours under 120 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Added behind an amount of Hydrazine Hydrate 80 under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours, gains are filtered, use water washing, after the seasoning; And under 150 ℃, continued dry 3 hours, promptly get the micropore titanium-silicon material C that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 0.008TiO
2100SiO
20.01PdO0.2Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 3), the benzene adsorptive capacity is 56mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 11).
Embodiment 4
With positive tetraethyl orthosilicate, tetrabutyl titanate, concentration is to mix in the ammonia chloride palladium solution of 0.01 grams per milliliter (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that X 2073 joins TPAOH; Add under the high degree of agitation in batches; Continue to stir for some time; Wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100: 2.0: 5.2: 2.0: 0.5: 2500, the silicon source was with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 150 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Added behind the appropriate hydrochloric acid hydrazine under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours, with the gains filtration, use water washing, after the seasoning; And under 120 ℃, continued dry 3 hours, promptly get the micropore titanium-silicon material D that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 19TiO
2100SiO
20.5PdO1.3Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 4), the benzene adsorptive capacity is 74mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 12).
Embodiment 5
Get in the aqueous solution (mass percent concentration 10%) that acid chloride solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01 grams per milliliter (in the palladium atom) and right amount of boron sodium hydride and tween 80 join tetramethylenediamine and mix; HTS (gram) wherein: tween 80 (mole): tetramethylenediamine (mole): Peng Qinghuana (mole): acid chloride (gram is in palladium): water (mole)=100: 0.1: 0.02: 0.05: 0.03: 520.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 120 ℃ temperature and autogenous pressure, and gains are filtered, use water washing, after the seasoning, and under 150 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material E that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 0.1TiO
2100SiO
20.1PdO0.75Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 5), the benzene adsorptive capacity is 78mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 13).
Embodiment 6
Get in the aqueous solution (mass percent concentration 10%) that ammonia chloride palladium solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01 grams per milliliter (in the palladium atom) and an amount of hydrazonium sulfate and X 2073 join TPAOH and mix; Add under the high degree of agitation in batches; Continue to stir for some time; HTS (gram) wherein: X 2073 (mole): TPAOH (mole): hydrazonium sulfate (mole): ammonia chloride palladium (gram is in palladium): water (mole)=100: 0.5: 0.1: 8.5: 4.8: 2000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 240 hours under 90 ℃ temperature and autogenous pressure, and gains are filtered, use water washing, after the seasoning, and under 120 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material F that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 0.04TiO
2100SiO
20.6PdO5.1Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 6), the benzene adsorptive capacity is 73mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 14).
Embodiment 7
With positive tetraethyl orthosilicate, tetraethyl titanate, concentration is that acid chloride solution and the cetyl trimethylammonium bromide of 0.01 grams per milliliter (in the palladium atom) joins in the TPAOH (mass percent concentration 13%) and mix; Silicon source wherein: titanium source: alkali source: palladium source: protective material: water=100: 8.2: 7.5: 0.1: 0.05: 800, the silicon source was with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Added behind the appropriate hydrochloric acid hydrazine under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours, with the gains filtration, use water washing, after the seasoning; And under 150 ℃, continued dry 3 hours, promptly get the micropore titanium-silicon material G that contains precious metal.Through characterizing, its form of forming with oxide compound can be expressed as 23TiO
2100SiO
20.04PdO0.8Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 7), the benzene adsorptive capacity is 62mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 15).
Embodiment 8
Get in the aqueous solution (mass percent concentration 14%) that nitric acid ammonia palladium that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01 grams per milliliter (in the palladium atom) and nitric acid ammonia platinum complex solution and Hydrazine Hydrate 80 and cetyl trimethylammonium bromide join TPAOH and mix; HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): Hydrazine Hydrate 80 (mole): nitric acid ammonia platinum (gram; In platinum): nitric acid ammonia palladium (gram is in palladium): water (mole)=100: 0.1: 1.2: 2.0: 0.8: 1.2: 1800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, use water washing, after the seasoning, and under 180 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material H that contains two precious metals.Through characterizing, its form of forming with oxide compound can be expressed as 4TiO
2100SiO
20.3PdO0.9Pd0.1PtO0.7Pt the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 8), the benzene adsorptive capacity is 77mg/g, and the transmission electron microscope photo demonstrates it and is hollow structure (Figure 16).
Comparative Examples 1
This Comparative Examples is to utilize the dipping method supported palladium to prepare load type palladium/HTS (0.5%Pd/TS-1) catalyzer.
Get titanium-silicon molecular sieve TS-1 sample 10 grams and 15 ml waters and join the PdCl that 5 ml concns are 0.01 grams per milliliter
2In the aqueous solution; Being 40 ℃ in temperature stirred 24 hours down; Proper seal therebetween; Natural drying at room temperature is 48 hours then, promptly obtains load type palladium/HTS (0.5%Pd/TS-1) catalyzer (need be in nitrogen hydrogen mixed gas atmosphere before reacting be 300 ℃ condition under reduction activation 3 hour in temperature).
Comparative Examples 2
This Comparative Examples is to utilize the dipping method supported palladium to prepare load type palladium/HTS (2%Pd/TS-1) catalyzer.
Get titanium-silicon molecular sieve TS-1 sample 10 grams and join the PdCl that 20 ml concns are 0.01 grams per milliliter
2In the aqueous solution; Being 40 ℃ in temperature stirred 24 hours down; Proper seal therebetween; Natural drying at room temperature is 48 hours then, promptly obtains load type palladium/HTS (2%Pd/TS-1) catalyzer (need be in nitrogen hydrogen mixed gas atmosphere before reacting be 300 ℃ condition under reduction activation 3 hour in temperature).
Embodiment 9-18 explanation is process and the result that catalyzer carries out N-pyridine oxide preparation provided by the invention with the micropore titanium-silicon material A-H of embodiment 1-8 preparation.
Embodiment 9
With pyridine, oxygen, hydrogen (4% volume; All the other are nitrogen), solvent and A be 1: 1: 1 according to the mol ratio of pyridine and oxygen, hydrogen; The mass ratio of solvent methanol and catalyzer is 200, is that 60 ℃ of pressure are under the 0.3MPa in temperature, is 2000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 8.0%; The N-pyridine oxide selectivity is 95%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 7.3%; The N-pyridine oxide selectivity is 92%.
Embodiment 10
Is 1: 2: 2 with pyridine, oxygen, hydrogen, nitrogen, solvent and B according to the mol ratio of pyridine and oxygen, hydrogen, nitrogen: 5, and the mass ratio of solvent methanol and catalyzer is 20, is that 30 ℃ of pressure are under the 1.5MPa in temperature, is 4000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.5%; The N-pyridine oxide selectivity is 93%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 6.5%; The N-pyridine oxide selectivity is 91%.
Embodiment 11
With pyridine, oxygen (80% volume; All the other are carbonic acid gas), hydrogen, solvent and C be 1: 5: 2 according to the mol ratio of pyridine and oxygen, hydrogen; The mass ratio of solvent methanol and catalyzer is 400, is that 40 ℃ of pressure are under the 0.5MPa in temperature, is 2000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 6.2%; The N-pyridine oxide selectivity is 94%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 5.3%; The N-pyridine oxide selectivity is 91%.
Embodiment 12
With pyridine, oxygen, hydrogen (4% volume; All the other are methane), solvent and D be 1: 2: 5 according to the mol ratio of pyridine and oxygen, hydrogen; The mass ratio of solvent methanol and catalyzer is 80, is that 120 ℃ of pressure are under the 2.5MPa in temperature, is 5000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.2%; The N-pyridine oxide selectivity is 96%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 6.5%; The N-pyridine oxide selectivity is 95%.
Embodiment 13
Is 1: 0.5: 4 with pyridine, oxygen, hydrogen, solvent and E according to the mol ratio of pyridine and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 20, is that 20 ℃ of pressure are under the 1.5MPa in temperature, is 500h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.3%; The N-pyridine oxide selectivity is 93%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 6.6%; The N-pyridine oxide selectivity is 91%.
Embodiment 14
With pyridine, oxygen (10% volume; All the other are argon gas), hydrogen, solvent and F be 1: 3: 0.5 according to the mol ratio of pyridine and oxygen, hydrogen; The mass ratio of solvent methanol and catalyzer is 150, is that 80 ℃ of pressure are under the 2.0MPa in temperature, is 800h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.2%; The N-pyridine oxide selectivity is 94%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 6.8%; The N-pyridine oxide selectivity is 90%.
Embodiment 15
Is 1: 4: 2 with pyridine, oxygen, hydrogen, solvent and G according to the mol ratio of pyridine and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 400, is that 40 ℃ of pressure are under the 1.4MPa in temperature, is 1500h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 6.3%; The N-pyridine oxide selectivity is 94%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 5.8%; The N-pyridine oxide selectivity is 91%.
Embodiment 16
Is 1: 2: 3 with pyridine, oxygen, hydrogen, solvent and H according to the mol ratio of pyridine and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 70, is that 25 ℃ of pressure are under the 1.0MPa in temperature, is 200h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.5%; The N-pyridine oxide selectivity is 96%.
The result who reacts 72 hours is following: the pyridine transformation efficiency is 7.0%; The N-pyridine oxide selectivity is 92%.
Embodiment 17
The present embodiment explanation utilizes the A of embodiment 1 preparation to be process and the result that catalyzer reacts in the tank reactor of sealing.
Is 1: 5: 4 with pyridine, oxygen, hydrogen, solvent methanol and A according to the mol ratio of pyridine and methyl alcohol, oxygen, hydrogen: 4, and the mass ratio of methyl alcohol and catalyzer is 50, is that 60 ℃ of pressure are to react under the 0.6MPa in temperature.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 8.1%; The N-pyridine oxide selectivity is 95%.
It is following to react the result who carries out 10 hours: the pyridine transformation efficiency is 18.3%, and the N-pyridine oxide selectivity is 89%.
Embodiment 18
The present embodiment explanation utilizes the B of embodiment 2 preparations to be process and the result that catalyzer reacts in the tank reactor of sealing.
Is 1: 25: 2 with pyridine, oxygen, hydrogen, solvent methanol and B according to the mol ratio of pyridine and methyl alcohol, oxygen, hydrogen: 2, and the mass ratio of methyl alcohol and catalyzer is 120, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 7.2%, and the N-pyridine oxide selectivity is 94%.
It is following to react the result who carries out 10 hours: the pyridine transformation efficiency is 18.6%; The N-pyridine oxide selectivity is 88%.
Comparative Examples 3,4 explanations utilize the comparative catalyst of Comparative Examples 1,2 preparations to carry out the condition and the result of pyridine oxidizing reaction.
Comparative Examples 3
This Comparative Examples is to utilize the load type palladium/HTS (0.5%Pd/TS-1) of Comparative Examples 1 preparation to do the reaction process that catalyzer carries out.
Is 1: 1: 1 with pyridine, oxygen, hydrogen, solvent methanol and catalyzer according to the mol ratio of pyridine and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 50, is that 60 ℃ of pressure are under the 1.5MPa in temperature, is 1000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 4.4%; The N-pyridine oxide selectivity is 90%.
It is following to react the result who carries out 8 hours: the pyridine transformation efficiency is 1.2%; The N-pyridine oxide selectivity is 82%.
Comparative Examples 4
This Comparative Examples is to utilize the load type palladium/HTS (2%Pd/TS-1) of Comparative Examples 2 preparations to do the process that catalyzer reacts.
Is 1: 2: 2 with pyridine, oxygen, hydrogen, solvent methanol and catalyzer according to the mol ratio of pyridine and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 200, is that 20 ℃ of pressure are under the 2.2MPa in temperature, is 500h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is following: the pyridine transformation efficiency is 3.5%; The N-pyridine oxide selectivity is 91%.
It is following to react the result who carries out 8 hours: the pyridine transformation efficiency is 1.4%; The N-pyridine oxide selectivity is 78%.
Can find out from the result of Comparative Examples 3,4 and embodiment 9-18: method pyridine transformation efficiency of the present invention obviously improves, and the selectivity of N-pyridine oxide is high, and the steady running cycle is long.
Claims (7)
1. the preparation method of a N-pyridine oxide; It is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure; With pyridine, oxygen, hydrogen, diluents, solvent and catalyst mix contact reacts; The mol ratio of pyridine and oxygen, hydrogen, diluents is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of pyridine and catalyzer are (0.1～50): 1, and the mass ratio of solvent and catalyzer is (20～1000): 1; Said catalyzer is a kind of micropore titanium-silicon material or the compsn that contains this micropore titanium-silicon material, and the composition of micropore titanium-silicon material is expressed as xTiO with the form of oxide compound
2100SiO
2YE
mO
nZE; Wherein the x value is 0.001～50.0, (y+z) value is 0.005～20.0 and y/z＜1, and E representes to be selected from one or more precious metals among Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and the Au, and m and n satisfy the required number of E oxidation state; This material grains partly or entirely is a hollow structure; Said diluents is selected from nitrogen, argon gas, helium, neon, perhaps is selected from carbonic acid gas, methane, ethane, propane, and said solvent is a methyl alcohol.
2. according to the method for claim 1, it is characterized in that said precious metal E is Pt and/or Pd.
3. according to the method for claim 1, it is characterized in that said x value is 0.005～25.0, (y+z) value is 0.01～10.0.
4. according to the method for claim 1, it is characterized in that the said compsn that contains micropore titanium-silicon material is selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by micropore titanium-silicon material and other and forms.
5. according to the method for claim 1, the mol ratio that it is characterized in that raw material pyridine and oxygen is 1: (0.2～5.0), the mol ratio of pyridine and hydrogen are 1: (0.2～5.0), the mass ratio of solvent and catalyzer are (20～500): 1.
6. according to the method for claim 1, it is characterized in that temperature of reaction is 20～120 ℃, reaction pressure is 0.3～2.5MPa.
7. according to the method for claim 1, it is characterized in that adopting periodical operation or operate continuously mode, reacting total gas space velocity is 10～10000h
-1
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