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CN101347744B - Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof - Google Patents

Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof Download PDF

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CN101347744B
CN101347744B CN 200810212209 CN200810212209A CN101347744B CN 101347744 B CN101347744 B CN 101347744B CN 200810212209 CN200810212209 CN 200810212209 CN 200810212209 A CN200810212209 A CN 200810212209A CN 101347744 B CN101347744 B CN 101347744B
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silicon
molecular sieve
catalyst
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microsphere
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CN101347744A (en
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戚明珠
李进
徐海鹏
姜友法
冯广军
孙鹏
阳坤
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Dalian Heterogeneous Catalyst Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Youth Chemical Co Ltd
Dalian Heterogeneous Catalyst Co Ltd
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Abstract

The invention provides a pyridine synthesis catalyst which takes microspherical high-silicon ZSM-5 molecular sieve as a carrier and a preparation method thereof. The preparation method adopts hydroxides of silicon source, aluminium source, alkali metal or alkaline earth metal, tetrapropylammonium bromide or tetrapropylammonium hydroxide and water as raw materials for preparing slurry, silicon-aluminum microspheres with the diameter of 30 to 200 um are obtained by spray drying and shaping, then the silicon-aluminum microspheres are arranged in organic amine steam, and the microspherical high-silicon ZSM-5 molecular sieve is obtained by washing, drying and calcination after the hydrothermal synthesis and the crystallization. The microspherical high-silicon ZSM-5 molecular sieve is taken as the carrier, one or more Pb, Sn and Zn elements is/are taken as main agents of active components, VIII family transition elements, IV family transition elements or/and alkaline earth metal elements are taken as auxiliary agents of the active components, wherein, the molar ratio of the total auxiliary agent to the total main agents is 0: 1 to 1: 1, the weight ratio of the active components and the carrier is 0.01 to 0.2; the carrier is impregnated in solution containing active components, and the catalyst of the invention is obtained by drying, calcination and activation, etc. As the synthesis process of the microspherical high-silicon ZSM-5 molecular sieve carrier which is used by the catalyst is shaped, the secondary shaping is unnecessary; at the same time, the catalyst can avoid the impact of a binding agent, thereby having better activity in applications. The yield of pyridine can achieve 77 percent and the total yield of pyridine derivatives can achieve 90 percent under the actionof the catalyst. The catalyst of the invention is especially applicable to the fluidized bed catalytic process.

Description

With microsphere type high-silicon ZSM-5-5 molecular sieve is catalyst for synthesizing pyridine of carrier and preparation method thereof
Technical field
The present invention relates to produce the Catalysts and its preparation method that pyridine uses, particularly being specifically related to a kind of is catalyst for synthesizing pyridine of carrier and preparation method thereof with microsphere type high-silicon ZSM-5-5 molecular sieve.
Background technology
Pyridine and derivative thereof are widely used in fields such as medicine, agricultural chemicals and rubber industry, surfactant, dye industry etc.
The production of early stage pyridine mainly is to extract from the coal coking byproduct, and this kind method productive rate is low, the products therefrom purity difference.Along with the continuous increase of demand, people have developed many synthesis routes, as aldehyde (ketone) ammonia process, and the unsaturated hydrocarbons method, side chain alkylation method, cyanamide process etc., wherein aldehyde (ketone) ammonia process process route is the most ripe.Aldehyde (ketone) ammonia process is by ammonia, aldehydes or ketones gas phase cyclizative condensation, adopts gas and solid phase catalytic to produce pyridine and derivative thereof, only need just can produce various pyridine derivates in same device by changing raw material.This method is used amorphous aluminum silicide (SiO in early days 2-Al 2O 3) make catalyst.But adopt amorphous aluminum silicide to make catalyst, this catalyst regeneration difficulty, selectivity is relatively poor simultaneously.
The ZSM-5 molecular sieve synthesized (US3702886) first by U.S. Mobil company in 1972.Because of it has the attention that special pore passage structure and catalytic performance, good heat endurance and hydrothermal stability are subjected to domestic and international petrochemical industry circle, very important industrial chemical processes such as catalytic cracking, aromatisation, alkylation, disproportionation have been widely used in.Use the ZSM-5 molecular sieve to make catalyst for synthesizing pyridine, the productive rate of pyridine and the selectivity of pyridine are had a greater degree of improvement.
It is catalyst that US4220783 adopts the HZSM-5 molecular sieve, is the raw material pyridine synthesis with formaldehyde, acetaldehyde, methyl alcohol and ammonia, and pyridine and picoline account for 69.8～71% of gross product, and low-boiling products accounts for 4.1～4.5%, and the higher boiling product accounts for 22.9～25.7%.
It is catalyst that CN1506353A adopts the ZSM-5 molecular sieve of silicon modification, is the raw material pyridine synthesis with formaldehyde, acetaldehyde and ammonia, and the molar yield of pyridine and picoline is 65.7%, higher boiling product 32.3%.
It is catalyst that CN1631538A adopts multiple element to help the ZSM-5 molecular sieve of catalysis, is the raw material pyridine synthesis with formaldehyde, acetaldehyde and ammonia, pyridine yield 70%, and the pyridine derivate total recovery can reach 87%.
CN101032693A adopts the ZSM-5 molecular sieve catalyst pyridine synthesis of load bismuth, has increased the pyridine selectivity of catalyst, has reduced the higher boiling product, and pyridine and picoline are up to 88%.
As everyone knows, prepare a kind of applied catalyst, need the molecular sieve powder is added the binding agent moulding, be applied to obtain certain shape and intensity side.Usually moulding has a column, coccoid and cellular etc.And used inorganic binder has aluminium oxide, amorphous silica such as white carbon, Ludox and kaolin etc.The addition of binding agent accounts for 15～30% of adsorbent gross weight usually, have in addition up to 60～90%, this just means the corresponding minimizing of the effective content of molecular sieve in the catalyst; In addition, because nature of binder is different with molecular sieve, in application, cause some adverse side effects sometimes, cause the catalytic performance of catalyst to descend, range of application is restricted.
Summary of the invention
The objective of the invention is to overcome the problem that existing catalyst yield is not high, accessory substance is many, provide a kind of and can improve pyridine and picoline yield, reducing high boiling point by-products produced is the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve.
The present invention also aims to provide a kind of is the preparation method of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve.Concrete technical scheme is as follows, and the percentage composition that adopts in this specification does not have special instruction, is the quality percentage composition:
Provided by the present invention is the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, be to be active component host with in Pb, Sn, the Zn element one or more, with group VIII transition elements, IVB family transition elements or/and alkali earth metal is the active component auxiliary agent, wherein total auxiliary agent is 0:1～1:1 with the mol ratio of total host, and the weight ratio of active component and carrier is 0.01～0.2.
The silica alumina ratio of the carrier microballoons type high silica ZSM-5 molecular sieve carrier that described this catalyst for synthesizing pyridine is used is 50～5000, is preferably 100～500, and microsphere diameter is 30～200 microns.
The used active component auxiliary agent of described this catalyst for synthesizing pyridine is Fe, Co, Ni, Pd, the Ru of group VIII transition elements, Ti, the Zr of IVB family transition elements, or/and the combination of one or more of alkali earth metals such as Mg, Ca, Sr, wherein total auxiliary agent is preferably 0.02:1～1:1 with the mol ratio of total host, and the weight ratio of active component and carrier is preferably 0.02～0.1.
Provided by the invention is the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, adopts the following steps preparation:
1), adopting hydroxide, 4-propyl bromide or TPAOH and the water of silicon source, aluminium source, alkali metal or alkaline-earth metal is raw material, its mol ratio is 1:0.0002～0.02:0.01～0.5:0～0.5:15～60, be mixed with slurries, spray-dried moulding obtains the silicon aluminium microsphere of 30～200 microns of diameters, then with it in organic amine steam, after the synthetic crystallization of hydro-thermal, washing, drying, roasting make microsphere type high-silicon ZSM-5-5 molecular sieve;
2), adopting each active component predecessor preparation molar concentration is the mixed solution of 0.01～0.2mol/L;
3), with infusion process or ion-exchange with active constituent loading on microsphere type high-silicon ZSM-5-5 molecular sieve, under 100～200 ℃ of temperature, dry 6～24h at 350～800 ℃ of roasting 10～40h, places air to naturally cool to room temperature then, obtains catalyst.
The active component predecessor that is adopted among the preparation method of catalyst for synthesizing pyridine of the present invention can be the simple substance or the salt of its any form, as one or more of halide, nitrate, sulfate, acetate.
The synthetic method of microsphere type high-silicon ZSM-5 of the present invention-5 molecular sieve adopts following operating procedure:
1), the preparation of silicon aluminium microsphere
SiO in the silicon source in molar ratio 2: the Al in the aluminium source 2O 3: R: the hydroxide of alkali metal or alkaline-earth metal: H 2O is 1:0.0002～0.02:0.01～0.5:0～0.5:15～60, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, wherein the silicon source is Ludox, gas-phase silica, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, the aluminium source is aluminum sulfate, aluminum nitrate or aluminium chloride, and R is 4-propyl bromide or TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 30～200 microns of diameters;
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds organic amine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: organic amine: H 2O is 1:0.1～10:5～90; To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 130～220 ℃ and 1～6 day, the product that hydrothermal crystallizing is good gets product microsphere type high-silicon ZSM-5-5 molecular sieve after washing, drying, roasting, the organic amine mother liquor of bottom can reuse.
In the synthetic method of described microsphere type high-silicon ZSM-5-5 molecular sieve, in the first step, the SiO in the silicon source 2: the Al in the aluminium source 2O 3: R: the hydroxide of alkali metal or alkaline-earth metal: H 2The optimal value of the mol ratio of O is 1:0.001～0.01:0.02～0.2:0～0.1:10～40, and the silicon source is a Ludox, and the aluminium source is an aluminum sulfate, and R is 4-propyl bromide or TPAOH.
In the synthetic method of described microsphere type high-silicon ZSM-5-5 molecular sieve, organic amine is to be selected from a kind of in fat amine compound, alcamine compound, alkyl diamine compounds, alkyl polyamine compounds, the imine compound or two or more mixture among them in second step.
The general formula of described fat amine compound is (R) NH 2, (R 1R 2) NH or (R 1R 2R 3) N, R, R 1, R 2, R 3Alkyl or cycloalkyl for C1 to C6.
The general formula of described alcamine compound is (HOR) NH 2, (HOR 1) 2NH or (HOR 2) 3N, R, R 1, R 2Alkyl or cycloalkyl for C1 to C6.
The general formula of described alkyl diamine compounds is H 2N (R) NH 2, R is the alkyl or cycloalkyl of C2 to C8.
The general formula of described alkyl polyamine compounds is H 2N (C 2H 4NHC 2H 4) mNH 2, m=1,2.
Described imine compound is pyrrolidines, piperidines, piperazine, cycloheximide, Alkylpiperidine or alkyl piperazine.
In the synthetic method of described microsphere type high-silicon ZSM-5-5 molecular sieve, the optimal value of the temperature and time of hydrothermal crystallizing is respectively 160～200 ℃ and 1～4 day in second step.
In the synthetic method of described microsphere type high-silicon ZSM-5-5 molecular sieve, sintering temperature is 350～800 ℃ in second step, roasting time 1～5 day.
Described microsphere type high-silicon ZSM-5-5 molecular sieve is that the active component predecessor is the simple substance or the salt of its any form in the synthetic method of catalyst for synthesizing pyridine of carrier, as one or more mixture of its halide, nitrate, sulfate, acetate.
Microsphere type high-silicon ZSM-5 of the present invention-5 molecular sieve because the moulding of its building-up process does not need post forming, has been avoided the influence of binding agent simultaneously again, has better activity in therefore using.
Of the present invention is that the catalyst for synthesizing pyridine of carrier is used for the synthetic of pyridine compounds with microsphere type high-silicon ZSM-5-5 molecular sieve, can in fixed bed reactors, carry out, also can in fluidized-bed reactor or moving-burden bed reactor, carry out, be particularly useful for fluid catalytic cracking process.
Selecting for use the continuous fixed bed reactors of stainless steel to carry out provided by the invention is the evaluation of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve.The loadings of catalyst is 200ml, and 40～60 purpose quartz sands are filled at the beds two ends.Raw material formaldehyde, acetaldehyde and ammonia mix, and pass through beds, gas phase air speed 300～1000h after preheating from top to bottom -1, 350～500 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.
Description of drawings
Fig. 1 is the X-ray powder diffraction scintigram (XRD) of example 1 microspheres prepared type high silica ZSM-5 molecular sieve of the present invention.
Fig. 2 is the stereoscan photograph (SEM) of example 1 microspheres prepared type high silica ZSM-5 molecular sieve of the present invention.
The specific embodiment
To come below that the present invention is described further with embodiment, but the present invention is not limited among the following embodiment.
Embodiment 1～9: microsphere type high-silicon ZSM-5-5 molecular sieve synthetic
Embodiment 1:
1), the preparation of silicon aluminium microsphere
The TPAOH solution that in 3.2Kg water, adds 0.023Kg potassium hydroxide and 0.84Kg40% concentration, the Ludox that adds 1.66Kg30% concentration after the stirring and dissolving, and then 0.018Kg aluminum sulfate is dissolved to wiring solution-forming in the 0.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R: potassium hydroxide: H 2O is 1:0.00333:0.2:0.05:35, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 60 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds n-butylamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: n-butylamine: H 2O is 1:4:10.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 190 ℃ and 3 days, the good product of hydrothermal crystallizing after washing, drying, 600 ℃ of roastings after 2 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 300,60 microns of microsphere diameters.
Embodiment 2:
1), the preparation of silicon aluminium microsphere
The TPAOH solution that in 2.2Kg water, adds 0.17Kg NaOH and 0.042Kg40% concentration, the Ludox that adds 1.66Kg30% concentration after the stirring and dissolving, and then 0.0011Kg aluminum sulfate is dissolved to wiring solution-forming in the 0.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R: NaOH: H 2O is 1:0.0002:0.01:0.5:25, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 95 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds MEA and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: MEA: H 2O is 1:10:5.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 220 ℃ and 1 day, the good product of hydrothermal crystallizing after washing, drying, 800 ℃ of roastings after 1 day product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 5000,95 microns of microsphere diameters.
Embodiment 3:
1), the preparation of silicon aluminium microsphere
The TPAOH solution that in 4.17Kg water, adds 2.1Kg40% concentration, the Ludox that adds 1.66Kg30% concentration after the stirring and dissolving, and then 0.11Kg aluminum sulfate is dissolved to wiring solution-forming in the 2.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R:H 2O is 1:0.02:0.5:60, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 30 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds cycloheximide and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: cycloheximide: H 2O is 1:0.1:90.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 130 ℃ and 6 days, the good product of hydrothermal crystallizing after washing, drying, 350 ℃ of roastings after 4 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 50,30 microns of microsphere diameters.
Embodiment 4:
1), the preparation of silicon aluminium microsphere
In 0.72Kg water, add 0.099Kg NaOH and 0.44Kg 4-propyl bromide, the Ludox that adds 1.66Kg30% concentration after the stirring and dissolving, and then 0.011Kg aluminum sulfate is dissolved to wiring solution-forming in the 0.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R: NaOH: H 2O is 1:0.002:0.2:0.3:15, and wherein R is a 4-propyl bromide.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 200 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds hexamethylene diamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: hexamethylene diamine: H 2O is 1:3:25.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 160 ℃ and 4 days, the good product of hydrothermal crystallizing after washing, drying, 650 ℃ of roastings after 3 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 500,200 microns of microsphere diameters.
Embodiment 5:
1), the preparation of silicon aluminium microsphere
In 2.21Kg water, add 0.099Kg NaOH and 0.44Kg 4-propyl bromide, the Ludox that adds 1.66Kg30% concentration after the stirring and dissolving, and then 0.0368Kg aluminum sulfate is dissolved to wiring solution-forming in the 0.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R: NaOH: H 2O is 1:0.00667:0.2:0.3:25, and wherein R is a 4-propyl bromide.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 130 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds diethyl triamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: diethyl triamine: H 2O is 1:2:6.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 200 ℃ and 1 day, the good product of hydrothermal crystallizing after washing, drying, 560 ℃ of roastings after 3 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 150,130 microns of microsphere diameters.
Embodiment 6:
1), the preparation of silicon aluminium microsphere
TPAOH solution in 1.05Kg40% concentration, the Ludox that adds 1.245Kg40% concentration after the stirring and dissolving, and then 0.055Kg aluminum sulfate is dissolved to wiring solution-forming in the 2.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R:H 2O is 1:0.01:0.25:25, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 180 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds 1,4-butanediamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: 1,4-butanediamine: H 2O is 1:2.0:10.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 170 ℃ and 5 days, the good product of hydrothermal crystallizing after washing, drying, 500 ℃ of roastings after 4 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 98,180 microns of microsphere diameters.
Embodiment 7:
1), the preparation of silicon aluminium microsphere
TPAOH solution in 1.05Kg40% concentration, the Ludox that adds 1.245Kg40% concentration after the stirring and dissolving, and then 0.0275Kg aluminum sulfate is dissolved to wiring solution-forming in the 2.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R:H 2O is 1:0.005:0.25:25, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 180 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds 1,4-butanediamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: 1,4-butanediamine: H 2O is 1:2.0:10.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 170 ℃ and 5 days, the good product of hydrothermal crystallizing after washing, drying, 500 ℃ of roastings after 4 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 197,180 microns of microsphere diameters.
Embodiment 8:
1), the preparation of silicon aluminium microsphere
TPAOH solution in 1.05Kg40% concentration, the Ludox that adds 1.245Kg40% concentration after the stirring and dissolving, and then 0.0183Kg aluminum sulfate is dissolved to wiring solution-forming in the 2.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R:H 2O is 1:0.0033:0.25:25, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 180 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds 1,4-butanediamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: 1,4-butanediamine: H 2O is 1:2.0:10.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 170 ℃ and 5 days, the good product of hydrothermal crystallizing after washing, drying, 500 ℃ of roastings after 4 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 291,180 microns of microsphere diameters.
Embodiment 9:
1), the preparation of silicon aluminium microsphere
TPAOH solution in 1.05Kg40% concentration, the Ludox that adds 1.245Kg40% concentration after the stirring and dissolving, and then 0.0137Kg aluminum sulfate is dissolved to wiring solution-forming in the 2.36Kg water, this drips of solution is added in the aforementioned silicon solution, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, SiO in molar ratio 2: Al 2O 3: R:H 2O is 1:0.0025:0.25:25, and wherein R is a TPAOH.The spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 180 microns of diameters.
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds 1,4-butanediamine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: 1,4-butanediamine: H 2O is 1:2.0:10.To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 170 ℃ and 5 days, the good product of hydrothermal crystallizing after washing, drying, 500 ℃ of roastings after 4 days product microsphere type high-silicon ZSM-5-5 molecular sieve, its silica alumina ratio is 386,180 microns of microsphere diameters.
Embodiment 10～31: be the preparation and the evaluation of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve
Embodiment 10:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 6 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 1.
Embodiment 11:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 7 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co2%, Ti0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 1.
Embodiment 12:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 1.
Embodiment 13:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 9 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 1.
The evaluation result of the catalyst that table 1 example 10～13 is prepared
Embodiment The molecular sieve silica alumina ratio Reaction temperature (℃) Reaction velocity (h -1) Acetaldehyde: formaldehyde: ammonia (mol ratio) Pyridine productive rate (%) Pyridine derivate gross production rate (%)
10 98 450 1000 2：1：4 65 71
11 197 450 1000 2：1：4 68 76
12 291 450 1000 2：1：4 75 86
13 386 450 1000 2：1：4 59 74
By data in the table as can be seen, with microsphere type high-silicon ZSM-5-5 molecular sieve of Different Silicon aluminum ratio is that its activity of catalyst of preparing carriers is all than higher, the pyridine derivate gross production rate is more than 70%, silica alumina ratio is that the gross production rate of 291 catalyst pyridine derivate has reached 86% especially, the productive rate of pyridine reaches 75%, has shown extraordinary catalytic activity and selectivity.Following embodiment is the preparing carriers catalyst with microsphere type high-silicon ZSM-5-5 molecular sieve of this silica alumina ratio all.
Embodiment 14:
The 8.29g zinc nitrate is added the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Zn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 15:
The 6.39g plumbi nitras is added the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 16:
The 8.78g butter of tin is dissolved in the hydrochloric acid of 60ml6mol/L, adds the water wiring solution-forming, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours to 115ml.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Sn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 17:
8.29g zinc nitrate and 6.39g plumbi nitras are added the water-soluble wiring solution-forming of separating to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 18:
The 8.78g butter of tin is dissolved in the hydrochloric acid of 60ml6mol/L, the 6.39g plumbi nitras is added dissolving, add the water wiring solution-forming, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours to 115ml.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Sn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 19:
The 8.78g butter of tin is dissolved in the hydrochloric acid of 60ml6mol/L, the 8.29g zinc nitrate is added dissolving, add the water wiring solution-forming, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours to 115ml.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Zn2%, Sn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 20:
The 8.78g butter of tin is dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 21:
8.78g butter of tin, 5.81g ferric trichloride are dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Fe1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 22:
The 8.78g butter of tin is dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 23:
8.78g butter of tin, 8.10g nickel chloride are dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Ni1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 24:
8.78g butter of tin, 3.34g palladium bichloride are dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Pd1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 25:
8.78g butter of tin, 4.10g ruthenium trichloride are dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Ru1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 26:
8.78g butter of tin, 5.81g ferric trichloride, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Fe1%, Ti0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 27:
8.78g butter of tin, 3.53g basic zirconium chloride are dissolved in the hydrochloric acid of 60ml6mol/L, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Zr0.5%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 28:
8.78g butter of tin, 3.53g basic zirconium chloride are dissolved in the hydrochloric acid of 60ml6mol/L, 2.11g magnesium nitrate, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Zr0.5%, Mg0.1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 29:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 2.11g magnesium nitrate, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%, Mg0.1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 30:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 1.18g calcium nitrate, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%, Ca0.1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
Embodiment 31:
8.78g butter of tin, 3.96g titanium tetrachloride are dissolved in the hydrochloric acid of 60ml6mol/L, 0.48g strontium nitrate, 9.88g cobalt nitrate, 8.29g zinc nitrate and 6.39g plumbi nitras are added dissolving, add the water wiring solution-forming to 115ml, embodiment 8 synthetic microsphere type high-silicon ZSM-5-5 molecular sieve 200 grams are immersed in the mixed solution, flooded 24 hours.Under 110 ℃ of temperature, drying 12 hours 600 ℃ of roastings 8 hours, places air to naturally cool to room temperature again, obtains catalyst then.The ratio of active component is in the catalyst: Pb2%, Zn2%, Sn2%, Co1%, Ti0.5%, Sr0.1%.
The catalyst of preparation is applied to the pyridine synthetic reaction.Acetaldehyde, formaldehyde (37% aqueous solution) vaporization are mixed with ammonia, pass through beds, gas phase air speed 1000h after the preheating from top to bottom -1, 450 ℃ of temperature.The product that generates is collected through after the cooling liquid, carries out quantitative analysis with gas-chromatography.Reaction result is as shown in table 2.
The evaluation result of the catalyst that table 2 example 14～31 is prepared
Figure G2008102122099D00131
Reaction condition: gas phase air speed 1000h -1, 450 ℃ of temperature, acetaldehyde: formaldehyde: ammonia (mol ratio) 2:1:4.
Can see that by result in the table different active host has different influences with auxiliary agent for activity of such catalysts and selectivity.The ratio of active component is Pb2%, Zn2%, and Sn2%, Co1%, Ti0.5%, the catalyst of Mg0.1% preparation has reached the highest activity and selectivity, and the gross production rate of its pyridine derivate is 90%, and the productive rate of pyridine reaches 77%.

Claims (9)

1. one kind is the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, it is characterized in that with in Pb, Sn, the Zn element one or more be active component host, with group VIII transition elements, IVB family transition elements or/and alkali earth metal is the active component auxiliary agent, wherein total auxiliary agent is 0: 1～1: 1 with the mol ratio of total host, and the weight ratio of active component and carrier is 0.01～0.2; The silica alumina ratio of microsphere type high-silicon ZSM-5-5 molecular sieve carrier is 50～5000, and microsphere diameter is 30～200 microns; Described catalyst prepares in accordance with the following methods:
1), microsphere type high-silicon ZSM-5-5 molecular sieve is synthetic: adopting hydroxide, 4-propyl bromide or TPAOH and the water of silicon source, aluminium source, alkali metal or alkaline-earth metal is raw material, its mol ratio is 1: 0.0002～0.02: 0.01～0.5: 0～0.5: 15～60, be mixed with slurries, spray-dried moulding obtains the silicon aluminium microsphere of 30～200 microns of diameters, then with it in organic amine steam, after the synthetic crystallization of hydro-thermal, washing, dry, roasting makes microsphere type high-silicon ZSM-5-5 molecular sieve; Described 4-propyl bromide or TPAOH consumption are not 0;
2), adopting each active component predecessor preparation molar concentration is the mixed solution of 0.01～0.2mol/L; Simple substance or salt that described active component predecessor is its any form; Described salt is one or more a mixture of its halide, nitrate, sulfate, acetate;
3), with infusion process or ion-exchange with active constituent loading on microsphere type high-silicon ZSM-5-5 molecular sieve, under 100～200 ℃ of temperature, dry 6～24h at 350～800 ℃ of roasting 10～40h, places air to naturally cool to room temperature then, obtains catalyst.
2. as claimed in claim 1 is the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, and the silica alumina ratio that it is characterized in that this microsphere type high-silicon ZSM-5-5 molecular sieve carrier is 100～500.
3. catalyst for synthesizing pyridine as claimed in claim 1, it is characterized in that used active component auxiliary agent is Fe, Co, Ni, Pd, the Ru of group VIII transition elements, Ti, the Zr of IVB family transition elements, or/and the combination of one or more of Mg, Ca, Sr alkali earth metal, wherein total auxiliary agent is 0.02: 1～1: 1 with the atomic ratio of total host, and the weight ratio of active component and carrier is 0.02～0.1.
One kind as claim 1～3 described any one be the preparation method of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, it is characterized in that may further comprise the steps preparation:
1), microsphere type high-silicon ZSM-5-5 molecular sieve is synthetic: adopting hydroxide, 4-propyl bromide or TPAOH and the water of silicon source, aluminium source, alkali metal or alkaline-earth metal is raw material, its mol ratio is 1: 0.0002～0.02: 0.01～0.5: 0～0.5: 15～60, be mixed with slurries, spray-dried moulding obtains the silicon aluminium microsphere of 30～200 microns of diameters, then with it in organic amine steam, after the synthetic crystallization of hydro-thermal, washing, dry, roasting makes microsphere type high-silicon ZSM-5-5 molecular sieve; Described 4-propyl bromide or TPAOH consumption are not 0;
2), adopting each active component predecessor preparation molar concentration is the mixed solution of 0.01～0.2mol/L; Simple substance or salt that described active component predecessor is its any form; Described salt is one or more a mixture of its halide, nitrate, sulfate, acetate;
3), with infusion process or ion-exchange with active constituent loading on microsphere type high-silicon ZSM-5-5 molecular sieve, under 100～200 ℃ of temperature, dry 6～24h is then at 350～800 ℃ of roasting 10～40h, place air to naturally cool to room temperature, obtain catalyst.
One kind as claimed in claim 4 be the preparation method of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, it is characterized in that the synthetic method of described microsphere type high-silicon ZSM-5-5 molecular sieve adopts following steps:
1), the preparation of silicon aluminium microsphere
SiO in the silicon source in molar ratio 2: the Al in the aluminium source 2O 3: R: the hydroxide of alkali metal or alkaline-earth metal: H 2O is 1: 0.0002～0.02: 0.01～0.5: 0～0.5: 15～60, the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get homogeneous slurry, wherein the silicon source is Ludox, gas-phase silica, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, the aluminium source is aluminum sulfate, aluminum nitrate or aluminium chloride, and R is 4-propyl bromide or TPAOH, the spray-dried moulding of the slurries that make is obtained the silicon aluminium microsphere of 30～200 microns of diameters; Described R consumption is not 0;
2), hydrothermal crystallizing
Place carriage to be placed into the hydro-thermal device first step gained silicon aluminium microsphere, the bottom adds organic amine and water, and its addition is the SiO in the silicon aluminium microsphere in molar ratio 2: organic amine: H 2O is 1: 0.1～10: 5～90; To carry out hydrothermal crystallizing after the sealing of hydro-thermal device, the temperature and time of hydrothermal crystallizing is respectively 130～220 ℃ and 1～6 day, the product that hydrothermal crystallizing is good gets product microsphere type high-silicon ZSM-5-5 molecular sieve after washing, drying, roasting, the organic amine mother liquor of bottom can reuse.
6. microsphere type high-silicon ZSM-5-5 molecular sieve according to claim 5 is the preparation method of the catalyst for synthesizing pyridine of carrier, it is characterized in that, in the first step of the described method for preparing microsphere type high-silicon ZSM-5-5 molecular sieve, and the SiO in the silicon source 2: the Al in the aluminium source 2O 3: R: the hydroxide of alkali metal or alkaline-earth metal: H 2The mol ratio of O is 1: 0.001～0.01: 0.02～0.2: 0～0.1: 15～40, and the silicon source is a Ludox, and the aluminium source is an aluminum sulfate, and R is 4-propyl bromide or TPAOH.
7. microsphere type high-silicon ZSM-5-5 molecular sieve according to claim 5 is the preparation method of the catalyst for synthesizing pyridine of carrier, it is characterized in that, in second step of the described method for preparing microsphere type high-silicon ZSM-5-5 molecular sieve, organic amine is one or more the mixture that is selected from fat amine compound, alcamine compound, alkyl diamine compounds, the alkyl polyamine compounds;
The general formula of described fat amine compound is (R) NH 2, (R 1R 2) NH or (R 1R 2R 3) N, R, R 1, R 2, R 3Alkyl for C1 to C6; The general formula of described alcamine compound is (HOR) NH 2, (HOR 1) 2NH or (HOR 2) 3N, R, R 1, R 2Alkyl or cycloalkyl for C1 to C6; The general formula of described alkyl diamine compounds is H 2N (R) NH 2, R is the alkyl of C2 to C8; The general formula of described alkyl polyamine compounds is H 2N (C 2H 4NHC 2H 4) mNH 2, m=1 or 2.
8. microsphere type high-silicon ZSM-5-5 molecular sieve according to claim 5 is the preparation method of the catalyst for synthesizing pyridine of carrier, it is characterized in that the temperature and time of hydrothermal crystallizing is respectively 160～200 ℃ and 1～4 day in second step of the described method for preparing microsphere type high-silicon ZSM-5-5 molecular sieve; Sintering temperature is 350～800 ℃ in second step, roasting time 1～5 day.
9. according to claim 4 is the preparation method of the catalyst for synthesizing pyridine of carrier with microsphere type high-silicon ZSM-5-5 molecular sieve, it is characterized in that: step 2) described active component predecessor is one or more mixture of its halide, nitrate, sulfate, acetate.
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CN109694088B (en) * 2017-10-23 2021-11-05 惠生工程（中国）有限公司 Preparation method of nano ZSM-5 molecular sieve
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CN110615444B (en) * 2018-06-20 2020-11-20 中国科学院大连化学物理研究所 A kind of mordenite molecular sieve, its preparation method and application
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
CN109607562A (en) * 2019-01-15 2019-04-12 李迎九 A kind of preparation method and application of zeolite
CN111672494B (en) * 2020-06-10 2023-06-02 江苏扬农化工集团有限公司 Preparation method of composite catalyst for synthesizing hexamethylenediamine intermediate and application of the composite catalyst
CN113304747B (en) * 2021-05-07 2022-07-12 万华化学集团股份有限公司 Catalyst for preparing 2-methylpyridine, preparation method and method for preparing 2-methylpyridine by using same
CN115414962B (en) * 2022-09-22 2023-09-15 西北有色金属研究院 Method for preparing molecular sieve supported multi-element alloy nanoparticle material
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