CN109331862A - A kind of propenal aldehyde acetal/aniline reaction prepares catalyst of quinoline and preparation method thereof - Google Patents
A kind of propenal aldehyde acetal/aniline reaction prepares catalyst of quinoline and preparation method thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention provides a kind of propenal aldehyde acetal/aniline condensation quinoline catalyst, the molecular sieve inorganic porous material complex carrier and double base active metal component that the catalyst is modified by graphene are formed;The molecular sieve inorganic porous material is one of HZSM-5, HY, USY, HBeta or a variety of;The double base active metal component is any two kinds in Mg, Co, Ag, Cr, Ni, Mn, Cu, Zn and Fe.The invention is modified inorganic porous material using graphene to obtain a kind of complex carrier, graphene is inserted into the interlayer of inorganic porous material by hydrothermal method, on the one hand it improves its specific surface area and improves its pore-size distribution, on the other hand, carrier after graphene modified is due to being rich in various active group, the load capacity and intensity of load of active metal are improved to a certain extent, the performance of catalyst is improved, propenal aldehyde acetal conversion ratio and quinoline derivatives yield can be up to 100% and 74% or more respectively.
Description
Technical field
The invention belongs to chemical industry catalysis technical fields, prepare quinoline more particularly to a kind of propenal aldehyde acetal/aniline reaction
Catalyst of derivative and preparation method thereof.
Background technique
Quinolines are a kind of extremely important nitrogen-containing heterocycle compounds, they synthetic dyestuffs, pesticide, medicine,
The chemical fields such as antioxidant, extractant, feed addictive and corrosion inhibiter have very extensive application.Especially in recent years, generation
It is developed in boundary many with quinolines newtype drug as main component, such as antitumor class, antimalarial class, treatment asthma
The drugs such as class, antibacterial anti-inflammatory class and hypertension class;In addition, quinolines can synthesize acid dyes Huang 3 and directly Huang
Equal welds, and niacin is obtained by oxidation reaction;And quinolines, which can also be used in preparation, has uniqueness electrically
It can such as be made by 8-hydroxyquinoline and fatty acid molysite with nanostructure/meso-hole structure organic functional material of optical property
For at sensible heat material.
Currently, being industrially to produce quinolines using chemical synthesis route;The synthesis road to have grown up
Line mainly includes liquid phase synthesizing method and gas phase synthesis method.Liquid phase synthesizing method mainly has: 1) Skraup method: this method be earliest exploitation and
Using most permanent method, be aniline, glycerol and oxidant (such as ferric trichloride, nitrobenzene or diarsenic pentoxide) are placed in it is dense
Heating is reacted to obtain quinoline jointly in sulfuric acid;But the strong acid corrosivity that the method is long there are reaction time, energy consumption is high, uses it is strong and
The problems such as serious pollution environment, it is difficult to for being mass produced;2) Doebner-Von Miller method: the method is by arylamine and aldehyde
Class/α, beta-unsaturated aldehyde carry out heating reaction under oxidant and acid condition and generate corresponding substituted quinoline derivatives,
Such as 4- methylquinoline and 2- phenyl -4- carboxyl quinoline;3) Conrad-Limpach method: the method is mainly by arylamine and 'beta '-ketoester
The synthesis of quinoline class compound under acid catalysis and heating condition;4) Combes method: the method is mainly by arylamine and beta-dicarbonyl
Object is closed to occur to be condensed and generate quinolines under acid catalysis and heating condition;It can be replaced by the method with synthesis of alkyl
The compounds such as oxyquinoline, ethoxycarbonyl oxyquinoline and other oxyquinolines;5) Friedlander method: the method mainly will be adjacent
Aminobenzaldehyde/ketone is reacted under the conditions of acid/base with the compound containing methylene ketone structure and obtains various substitutions
The quinolines of position;6) Povarov method: the method mainly generates multifarious quinoline by arylamine, aldehyde and alkyne reaction
Quinoline ring derivatives;7) Pfitzinger method: the method mainly passes through isatin (isatin) and methyl or methylene ketone in parent
Synthesis of quinoline class compound under the induction of core reagent (usually sodium hydroxide);8) other liquid-phase synthesis process: as used arylamine
The quinoline that 3- halogen/sulphur replaces is obtained by electrophilic cyclisation, aromatization with acetylenic halide;And use 2- (amino methyl) benzene
Amine reacts under oxygen atmosphere with aryl ketones obtains 2- aryl quinoline product etc..Above-mentioned liquid-phase catalysis reaction method is quinolate at present
Close the most commonly used method of object industrialized production;However but there are many shortcomings that being difficult to avoid that in this method, be mainly manifested in: anti-
Should during using a large amount of organic solvent, reaction time is long, operating process tedious steps are more, target product yield needs to be mentioned
It is high;Catalyst is severe with very big corrosive strong acid or noble metal complexes, reaction condition expensive and be more toxic
Carve (such as some need reaction under high pressure condition), post catalyst reaction is difficult to separate and recover and generate the waste liquid of pollution environment.Cause
This, in face of increasingly strict environmental requirement and the more and more vigorous quinolines market demand, exploitation has environmentally protective
The quinoline compound technique for preparing of clean and safe production characteristic becomes inevitable.
Gas phase synthesis method has and does not use due to that can be effectively prevented from many drawbacks of bring in Traditional liquid phase reaction process
The significant advantages such as solvent, operation step be few, reaction process is simple, product and catalyst are easily isolated and recycle, more accord with
The trend for closing green chemistry, shows more preferably industrial applications potentiality.Campanati is catalyzed second two with montmorillonite K10
Pure and mild 2- ethyl aniline reaction;By improving the inlet amount of reaction temperature and ethylene glycol, while being passed through during the reaction a small amount of
Water, can get 41% 2- methyl -8- ethyl quinolinium yield.The patent report of McAteer et al. shows through formaldehyde, C2-
Three component reaction of C4 aldehydes and arylamine can get the quinolines of higher yields.Such as on BEA molecular sieve catalyst, first
The 3- methylquinoline that aldehyde, propionic aldehyde and aniline reaction obtain may be up to 67.7%.Subrahmanyam et al. uses HZSM-5,
The alkylation gas phase selectivity synthesis 2- of the catalysts such as CrHY, CeHY, LaHY, LaKHY and CeHZSM-5 quinoline and methanol
Methylquinoline;Especially on the modified LaKHY catalyst of two-component, methylquinoline is selectively 91.5%, and yield is up to
60.6%.Reddy et al. uses CuO-ZnO/Al2O3、MoO3-V2O5/Al2O3And NiO-MoO3/Al2O3Equal catalysts benzene
Amine and glycerine reaction generate quinoline, in the range of reaction temperature of 623-723K, in CuO-ZnO/Al2O3Quinoline is received on catalyst
Rate is up to 65%.Brosius et al., as catalyst, is catalyzed acetaldehyde and aniline synthesis using unmodified and F modified BEA zeolite
2-/4- methylquinoline.Especially F modified BEA zeolite catalyst can improve total receipts of quinoline compound to a certain extent
Rate and the distribution for changing product.Kamiguchi et al. uses metal halogen cluster compound catalysed aniline and acetone vapor- phase synthesis 1,2-
Dihydro -2,2, the catalytic performance of 4- trimethylquinoline, as [(Nb6Cl12)Cl2(H2O)4]·4H2O catalyst 300-400 DEG C with
On activated after, solid acid catalyst to target product have maximum selectivity.Existing research report confirmation, vapor phase method
Synthesis of quinoline class compound has preferable catalytic effect;It simultaneously can be neatly using different reactants as reaction raw materials.
But these current methods remain deficiency;It is mostly saturation/unsaturation aldehyde ketone of raw material from petroleum-based products in terms of raw material;
In terms of catalyst, there is catalytic activity that not high enough, catalytic active component is easy to run off and causes to be catalyzed for non-molecular sieve catalysts
The disadvantages of agent inactivates;The active poor and easy in inactivation of metal oxide catalyst;Though metal-organic framework materials catalyst has
Good reactivity, but material itself preparation difficulty it is big, at high cost, structural stability is poor the disadvantages of.
Summary of the invention
The purpose of the present invention is to provide catalyst and preparation sides that a kind of propenal aldehyde acetal/aniline prepares quinoline
Method, the inorganic porous composite material carrier and double activated metal component that catalyst of the invention is modified by graphene are formed;It adopts
With catalyst of the present invention, the synthetic reaction of quinoline is carried out, propenal aldehyde acetal conversion ratio and quinoline derivatives are received
Rate is greatly improved, and catalyst preparation is simple, performance is stablized, and has very good industrial applications prospect.
To achieve the above object, the present invention is achieved by the following scheme:
A kind of catalyst of propenal aldehyde acetal/aniline condensation quinoline, what the catalyst was modified by graphene
Molecular sieve inorganic porous material complex carrier and double base active metal component composition.
Preferably, the mass fraction of graphene is in the modified molecular sieve inorganic porous material complex carrier of the graphene
5-30%;The molecular sieve inorganic porous material is selected from one of HZSM-5, HY, USY, HBeta or a variety of.
Preferably, the double base active metal component is any in Mg, Co, Ag, Cr, Ni, Mn, Cu, Zn and Fe
Two kinds, the content of double base active metal component accounts for the 2-20wt% of catalyst.
Preferably, the modified molecular sieve inorganic porous material complex carrier of the graphene the preparation method comprises the following steps: weighing point
Son sieve inorganic porous material powder is placed in the NaOH solution that concentration is 0.5-4.5mol/L, then in 20-90 DEG C of water bath condition
Lower strong stirring 30-120min;Graphene oxide is added under stirring, after stirring 15-30min, with the acetic acid of 50wt%
Solution adjusts its Ph=9-10, continues to stir 30min;Then gained suspension is placed in crystallizing kettle and in 100-160 DEG C of perseverance
Crystallization 1-8 days in incubator, after reaction, cooling, suction filtration, washing, filter cake is dry in 120 DEG C of baking ovens, and in N2Atmosphere is protected
2-11h, i.e. the molecular sieve inorganic porous material of acquisition graphene doping are calcined in 400-700 DEG C of high-temperature heating in the tube furnace of shield
Complex carrier.
Preferably, molecular sieve inorganic porous material powder/NaOH solution solid-to-liquid ratio is 1: 4-1: 30, the concentration of NaOH solution
For 1.5-2.5mol/L, bath temperature is 35-65 DEG C, mixing time 60-80min, and the crystallization temperature of suspension is 110-145
DEG C, crystallization time 2-4d, in N2The maturing temperature of the tube furnace of atmosphere protection is 480-610 DEG C, calcining time 3-6h.
In addition, the preparation method of the catalyst, specific steps are also claimed in the present invention are as follows: by two kinds of active metal groups
The soluble salt divided is soluble in water simultaneously, forms the clear solution that concentration is 0.002-1.5mol/L, then adds excessive urea
Enter above-mentioned solution, stir into clear solution, is later impregnated in the modified molecular sieve inorganic porous material complex carrier of graphene
In above-mentioned solution, and stir process 0.5-8 hours at room temperature;Suspended matter after stirring is heated to reflux at a temperature of 70-120 DEG C
2-12 hours, the suspended matter after reflux filtered at room temperature, and gained sediment is washed with distilled water to neutrality;It is deposited in above-mentioned
It is dried at a temperature of 80-120 DEG C, and in N2Atmosphere protection tube furnace in 400-650 DEG C roasting temperature 2-10 hours, that is, obtain
Obtain the catalyst.
Preferably, the concentration of the aqueous solution of the soluble salt containing active component is 0.02-0.2mol/L;Its metal group
Point/the ratio between the amount of urea substance is 1: 8-1: 15;The stir process time is 1.5-4.5 hours at room temperature;Suspended matter after stirring
The temperature being heated to reflux is 85-100 DEG C;Maturing temperature and time be 450-600 DEG C roasting temperature 4-8 hours.
Preferably, the propenal aldehyde acetal raw material is propylene methylal, acryl acetal, methacrylaldehyde contracting two
One of propyl alcohol is a variety of.
Application of the catalyst in propenal aldehyde acetal/aniline condensation quinoline is also claimed in the present invention.
Compared with prior art, the beneficial effects of the present invention are:
(1) the use graphene of the invention is modified inorganic porous material to obtain a kind of compound load
Graphene, the interlayer of inorganic porous material is inserted by hydrothermal method by body, on the one hand improves the table of inorganic porous material
Surface properties improve its specific surface area and improve its pore-size distribution, on the other hand, carrier after the modification of graphene due to
Rich in various active group, the load capacity and intensity of load of active metal are improved to a certain extent, enable active component
It is enough to be preferably distributed on carrier, the whole catalytic performance of catalyst is improved, propenal aldehyde acetal conversion ratio and quinolines are derivative
Object yield can be up to 100% and 74% or more respectively;
(2) the logical catalyst catalytic performance of the present invention is high and stablizes, and preparation method is simple and efficient, while active component is not easy to flow
It loses;
(3) present invention can carry out semicontinuous or continuous production using fixed bed mobility reaction device.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g USY molecular sieve powder is weighed
It is placed in the NaOH solution of the 1.5mol/L of 120mL;75min is stirred strongly under 65 DEG C of water bath conditions;Then, in stirring
The 1.5g graphene oxide of lower addition;After stirring 15min, its PH to 9 is adjusted using 50% acetum;Continue to stir
30min;The suspension is placed in crystallizing kettle and the crystallization 2d in 110 DEG C of insulating boxs;After the completion of crystallization process, cooling, suction filtration,
Washing, filter cake are dry in 120 DEG C of baking ovens;And in N2In the tube furnace of atmosphere protection in 550 DEG C of high-temperature heatings calcine 4h to get
The molecular screen material complex carrier gh-USY of graphene doping;
(2) preparation of catalyst: the nickel nitrate of 1.6g and 2.3g zinc nitrate hexahydrate are dissolved in water simultaneously, are configured to
The clear solution of 100mL;Above-mentioned solution is added in 11.6g urea, clear solution is stirred into, takes the above-mentioned resulting gh-USY- of 10g
5 carriers are impregnated in above-mentioned solution, and stir process 2 hours at room temperature, and the suspended matter after stirring heats at a temperature of 95 DEG C
Reflux 4 hours;Suspended matter after reflux filters at room temperature, and gained sediment is washed with distilled water to neutrality;And it is dried in 120 DEG C
Dry and N2Atmosphere protection tube furnace in 550 DEG C roasting temperature 4 hours, obtain ZnNi/gh-USY catalyst.Catalyst warp
After tabletting is granulated, the particle of screening 30-40 mesh is for being catalyzed reaction.
Embodiment 2
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g Beta molecular sieve powder is weighed
End is placed in the NaOH solution of the 1.5mol/L of 120mL;Wherein, molecular sieve/NaOH solution solid-to-liquid ratio 1: 12, in 60 DEG C of water-bath items
65min is stirred under part strongly;Then, the 1.5g graphene oxide being added under stirring;After stirring 25min, 50% is used
Acetum adjust its PH to 9;Continue to stir 40min;The suspension is placed in crystallizing kettle and brilliant in 120 DEG C of insulating boxs
Change 4d;After the completion of crystallization process, cooling, suction filtration, washing, filter cake drying in 120 DEG C of baking ovens;And in N2The tubular type of atmosphere protection
The molecular screen material complex carrier gh-Beta adulterated in furnace in 550 DEG C of high-temperature heating calcining 4h to get graphene;
(2) preparation of catalyst: the nickel nitrate of 1.6g and 2.3g zinc nitrate hexahydrate are dissolved in water simultaneously, are configured to
The clear solution of 100mL;Above-mentioned solution is added in 15.0g urea, clear solution is stirred into, takes the above-mentioned resulting gh-Beta of 10g
Carrier is impregnated in above-mentioned solution, and stir process 2 hours at room temperature, and the suspended matter after stirring heats at a temperature of 95 DEG C
Reflux 4 hours;Suspended matter after reflux filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C
Drying and N2Atmosphere protection tube furnace in 550 DEG C roasting temperature 4 hours, obtain ZnNi/gh-Beta catalyst.Catalysis
Agent is after tabletting is granulated, and the particle of screening 30-40 mesh is for being catalyzed reaction.
Embodiment 3
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g HY molecular sieve powder is weighed
It is placed in the NaOH solution of the 1.8mol/L of 150mL;Wherein, molecular sieve/NaOH solution solid-to-liquid ratio 1: 15, in 60 DEG C of water bath conditions
Lower strong stirring 80min;Then, the 0.5g graphene oxide being added under stirring;After stirring 15min, 50% is used
Acetum adjusts its PH to 10;Continue to stir 30min;The suspension is placed in crystallizing kettle and brilliant in 120 DEG C of insulating boxs
Change 3d;After the completion of crystallization process, cooling, suction filtration, washing, filter cake drying in 120 DEG C of baking ovens;And in N2The tubular type of atmosphere protection
The molecular screen material complex carrier gh-HY adulterated in furnace in 550 DEG C of high-temperature heating calcining 4h to get graphene;
(2) preparation of catalyst: the nickel nitrate of 1.6g and 2.1g silver nitrate are dissolved in water simultaneously, are configured to the clear of 120mL
Clear solution;Above-mentioned solution is added in 14.0g urea, clear solution is stirred into, takes the above-mentioned resulting gh-HY carrier of 12g, be impregnated in
In above-mentioned solution, and stir process 2 hours at room temperature, the suspended matter after stirring are heated to reflux 5 hours at a temperature of 90 DEG C;It returns
Suspended matter after stream filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C of drying and N2Atmosphere
In the tube furnace of protection in 550 DEG C roasting temperature 4 hours, obtain AgNi/gh-HY catalyst.Catalyst after tabletting is granulated,
The particle of 30-40 mesh is screened for being catalyzed reaction.
Embodiment 4
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g Beta molecular sieve powder is weighed
End is placed in the NaOH solution of the 2.0mol/L of 160mL;Wherein, molecular sieve/NaOH solution solid-to-liquid ratio 1: 16, in 65 DEG C of water-bath items
60min is stirred under part strongly;Then, the 1.8g graphene oxide being added under stirring;After stirring 20min, 50% is used
Acetum adjust its PH to 9;Continue to stir 30min;The suspension is placed in crystallizing kettle and brilliant in 120 DEG C of insulating boxs
Change 4d;After the completion of crystallization process, cooling, suction filtration, washing, filter cake drying in 120 DEG C of baking ovens;And in N2The tubular type of atmosphere protection
The molecular screen material complex carrier gh-Beta adulterated in furnace in 550 DEG C of high-temperature heating calcining 4h to get graphene;
(2) preparation of catalyst: the copper nitrate of 1.9g and 2.6g magnesium nitrate are dissolved in water simultaneously, are configured to the clear of 100mL
Clear solution;Above-mentioned solution is added in 16.0g urea, stirs into clear solution, the above-mentioned resulting gh-Beta carrier of 10g is taken, is soaked
Stain is in above-mentioned solution, and stir process 3 hours at room temperature, and it is small that the suspended matter after stirring is heated to reflux 5 at a temperature of 98 DEG C
When;Suspended matter after reflux filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C drying and
N2Atmosphere protection tube furnace in 550 DEG C roasting temperature 4 hours, obtain CuMg/gh-Beta catalyst.Catalyst is through pressing
After piece is granulated, the particle of screening 30-40 mesh is for being catalyzed reaction.
Embodiment 5
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g HZSM-5 molecular sieve is weighed
Powder is placed in the NaOH solution of the 1.8mol/L of 200mL;Wherein, molecular sieve/NaOH solution solid-to-liquid ratio 1: 20, in 60 DEG C of water-baths
Under the conditions of stir 70min strongly;Then, the 1.5g graphene oxide being added under stirring;After stirring 20min, use
50% acetum adjusts its PH to 9;Continue to stir 30min;The suspension is placed in crystallizing kettle and in 110 DEG C of insulating boxs
Middle crystallization 3d;After the completion of crystallization process, cooling, suction filtration, washing, filter cake drying in 120 DEG C of baking ovens;And in N2Atmosphere protection
The molecular screen material complex carrier gh-USY adulterated in tube furnace in 550 DEG C of high-temperature heating calcining 4h to get graphene;
(2) preparation of catalyst: the nickel nitrate of 2.3g zinc nitrate hexahydrate and 1.6g are dissolved in water simultaneously, are configured to
The clear solution of 150mL;And above-mentioned solution is added in 13.2g urea, clear solution is stirred into, the above-mentioned resulting gh- of 10g is taken
HZSM-5 carrier is impregnated in above-mentioned solution, and stir process 2 hours at room temperature, and the suspended matter after stirring is in 90 DEG C of temperature
Under be heated to reflux 5 hours;Suspended matter after reflux filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And
In 120 DEG C of drying and N2Atmosphere protection tube furnace in 550 DEG C roasting temperature 4 hours, obtain ZnNi/gh-HZSM-5 urge
Agent.Catalyst is after tabletting is granulated, and the particle of screening 30-40 mesh is for being catalyzed reaction.
Comparative example 1
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
Comparative example 1 is not the difference from embodiment 1 is that carrier uses graphene to be modified.
The preparation of catalyst: the nickel nitrate of 1.6g and 2.3g zinc nitrate hexahydrate are dissolved in water simultaneously, are configured to 100mL's
Clear solution;Above-mentioned solution is added in 11.6g urea, clear solution is stirred into, takes 10g USY molecular sieve dust carrier, is impregnated
In above-mentioned solution, and stir process 2 hours at room temperature, the suspended matter after stirring are heated to reflux 4 hours at a temperature of 95 DEG C;
Suspended matter after reflux filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C of drying and N2Atmosphere
Enclose in the tube furnace of protection in 550 DEG C roasting temperature 4 hours, obtain ZnNi/USY catalyst.Catalyst after tabletting is granulated,
The particle of 30-40 mesh is screened for being catalyzed reaction.
Comparative example 2
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
Comparative example 2 is the difference from embodiment 1 is that only take a kind of metal to be loaded.
(1) preparation of the modified molecular sieve inorganic porous material complex carrier of graphene: 10g USY molecular sieve powder is weighed
It is placed in the NaOH solution of the 1.5mol/L of 120mL;75min is stirred strongly under 65 DEG C of water bath conditions;Then, in stirring
The 1.5g graphene oxide of lower addition;After stirring 15min, its PH to 9 is adjusted using 50% acetum;Continue to stir
30min;The suspension is placed in crystallizing kettle and the crystallization 2d in 110 DEG C of insulating boxs;After the completion of crystallization process, cooling, suction filtration,
Washing, filter cake are dry in 120 DEG C of baking ovens;And in N2In the tube furnace of atmosphere protection in 550 DEG C of high-temperature heatings calcine 4h to get
The molecular screen material complex carrier gh-USY of graphene doping;
(2) preparation of catalyst: 2.3g zinc nitrate hexahydrate is dissolved in water, is configured to the clear solution of 100mL;By 6.0g
Above-mentioned solution is added in urea, stirs into clear solution, takes the above-mentioned resulting gh-USY-5 carrier of 10g, be impregnated in above-mentioned solution,
And stir process 2 hours, the suspended matter after stirring are heated to reflux 4 hours at a temperature of 95 DEG C at room temperature;Suspension after reflux
Object filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C of drying and N2The tubular type of atmosphere protection
In furnace in 550 DEG C roasting temperature 4 hours, obtain ZnNi/gh-USY catalyst.Catalyst screens 30-40 after tabletting is granulated
Purpose particle is for being catalyzed reaction.
Comparative example 3
A kind of preparation method of the catalyst of propenal aldehyde acetal/aniline condensation quinoline, includes the following steps:
The difference of comparative example 3 and embodiment 1 is only that carrier is graphene.
The preparation of catalyst: the nickel nitrate of 1.6g and 2.3g zinc nitrate hexahydrate are dissolved in water simultaneously, are configured to 100mL's
Clear solution;Above-mentioned solution is added in 11.6g urea, clear solution is stirred into, takes 10g graphene powder carrier (gh), is impregnated
In above-mentioned solution, and stir process 2 hours at room temperature, the suspended matter after stirring are heated to reflux 4 hours at a temperature of 95 DEG C;
Suspended matter after reflux filters at room temperature, and gained sediment is simultaneously washed with distilled water to neutrality;And in 120 DEG C of drying and N2Atmosphere
Enclose in the tube furnace of protection in 550 DEG C roasting temperature 4 hours, obtain ZnNi/gh catalyst.Catalyst after tabletting is granulated,
The particle of 30-40 mesh is screened for being catalyzed reaction.
The activity rating of catalyst:
Catalyst according to the present invention prepares quinoline reaction using as follows for propenal aldehyde acetal/aniline condensation
Program carries out.Using fixed bed continuous reactor, catalyst is placed in the middle part of reactor, controls reactor with thermocouple and temperature controller
Temperature.Using do not add any reaction dissolvent propenal aldehyde acetal and aniline mixture as reaction raw materials, which is contained in
In storage tank, squeezed into reactor after first passing through gasification in advance by feed pump, while water is beaten after overflash through another feed pump
Enter reactor;And it is continuously brought into catalyst bed by inert carrier gas (for example, nitrogen, argon gas or helium) and is condensed
Reaction.Enter from the mixture of reaction products flowed out in reactor through collecting gas phase respectively in the cooling gas-liquid separator of room temperature
And liquid-phase reaction product.The collection of sample be each setting at a temperature of constant reaction 90 minutes after carry out, when sample collection
Between 60 minutes.Collected sample is detected the component of product mixtures by gas chromatograph and mass spectrograph and is formed.Methacrylaldehyde contracting
Aldehyde/aniline condensation prepares the condition of quinoline reaction are as follows: propenal aldehyde acetal/aniline molal weight ratio is 1: 3;Material liquid
Flow velocity 0.03ml/min;Water flow velocity 0.03ml/min;Raw material and 240 DEG C of water vapor temperature;Inert carrier gas pressure 0.3MPa, flow velocity
20ml/min;440 DEG C of reaction temperature.
Embodiment 1-5 catalyst propenal aldehyde acetal/aniline quinoline result
Reaction condition: aniline and the total liquid hourly space velocity 1.0h of acryl acetal-1, water liquid hourly space velocity 1.0h-1;Aniline and
Propenal aldehyde acetal molar ratio is 3: 1;Flow rate of carrier gas (nitrogen) 20ml/min, 440 DEG C of reaction temperature.
Embodiment 2.ZnNi/gh-Beta is catalyzed propenal aldehyde acetal/aniline quinoline result
Reaction condition: 1. aniline and the total liquid hourly space velocity 1.0h of propenal aldehyde acetal-1, water liquid hourly space velocity 1.0h-1;Aniline and third
Olefine aldehydr acetal molar ratio is 3: 1;440 DEG C of reaction temperature;Flow rate of carrier gas (nitrogen) 20ml/min.
Comparative example 1-3 catalyst propenal aldehyde acetal/aniline quinoline result
Reaction condition: aniline and the total liquid hourly space velocity 1.0h of acryl acetal-1, water liquid hourly space velocity 1.0h-1;Aniline and
Propenal aldehyde acetal molar ratio is 3: 1;Flow rate of carrier gas (nitrogen) 20ml/min, 440 DEG C of reaction temperature.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (9)
1. a kind of propenal aldehyde acetal/aniline condensation quinoline catalyst, which is characterized in that the catalyst is by graphite
The modified molecular sieve inorganic porous material complex carrier of alkene and double base active metal component composition.
2. catalyst according to claim 1, which is characterized in that the modified molecular sieve inorganic porous material of the graphene
The mass fraction of graphene is 5-30% in complex carrier;The molecular sieve inorganic porous material be selected from HZSM-5, HY, USY,
One of HBeta or a variety of.
3. -2 described in any item catalyst according to claim 1, which is characterized in that the double base active metal component be selected from
Any two kinds in Mg, Co, Ag, Cr, Ni, Mn, Cu, Zn and Fe;The content of double base active metal component accounts for the 2- of catalyst
20wt%.
4. catalyst according to claim 3, which is characterized in that the modified molecular sieve inorganic porous material of the graphene
Complex carrier the preparation method comprises the following steps: weigh molecular sieve inorganic porous material powder be placed in concentration be 0.5-4.5mol/L NaOH it is molten
In liquid, 30-120min is then stirred strongly under 20-90 DEG C of water bath condition;Graphene oxide is added under stirring, stirs
After 15-30min, its Ph=9-10 is adjusted with the acetum of 50wt%, continues to stir 30min;Then gained suspension is set
Crystallization 1-8 days in crystallizing kettle and in 100-160 DEG C of insulating box, after reaction, cooling, suction filtration, washing, filter cake is 120
It is dry in DEG C baking oven, and in N22-11h is calcined in 400-700 DEG C of high-temperature heating in the tube furnace of atmosphere protection, i.e. acquisition graphite
The molecular sieve inorganic porous material complex carrier of alkene doping.
5. catalyst according to claim 4, which is characterized in that molecular sieve inorganic porous material powder/NaOH solution is solid
Liquor ratio g/mL is 1: 4-1: 30, and the concentration of NaOH solution is 1.5-2.5mol/L, and bath temperature is 35-65 DEG C, and mixing time is
60-80min, the crystallization temperature of suspension are 110-145 DEG C, crystallization time 2-4d, in N2The roasting of the tube furnace of atmosphere protection
Burning temperature is 480-610 DEG C, calcining time 3-6h.
6. a kind of preparation method of any one of claim 1-5 catalyst, which is characterized in that specific steps are as follows: by two kinds
The soluble salt of active metal component is soluble in water simultaneously, forms concentration as the clear solution of 0.002-1.5mol/L, then incited somebody to action
Above-mentioned solution is added in the urea of amount, stirs into clear solution, later that the modified molecular sieve inorganic porous material of graphene is compound
Carrier impregnation is in above-mentioned solution, and stir process 0.5-8 hours at room temperature;Suspended matter after stirring is in 70-120 DEG C of temperature
Under be heated to reflux 2-12 hours, the suspended matter after reflux filters at room temperature, and gained sediment is washed with distilled water to neutrality;It will
It is above-mentioned be deposited in 80-120 DEG C at a temperature of dry, and in N2In 400-650 DEG C of roasting temperature 2- in the tube furnace of atmosphere protection
10 hours, that is, obtain the catalyst.
7. preparation method according to claim 6, which is characterized in that the aqueous solution of the soluble salt containing active component
Concentration be 0.02-0.2mol/L;The ratio between its metal component/urea substance amount is 1: 8-1: 15;At room temperature when stir process
Between be 1.5-4.5 hours;The temperature that suspended matter after stirring is heated to reflux is 85-100 DEG C;Maturing temperature and time are 450-
600 DEG C roasting temperature 4-8 hours.
8. catalyst described in -5 according to claim 1, which is characterized in that the propenal aldehyde acetal raw material is methacrylaldehyde contracting two
One of methanol, acryl acetal, methacrylaldehyde two propyl alcohol of contracting are a variety of.
9. a kind of any one of claim 1-5 catalyst answering in propenal aldehyde acetal/aniline condensation quinoline
With.
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