CN106831527A - Pyrroles and preparation method thereof - Google Patents
Pyrroles and preparation method thereof Download PDFInfo
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- CN106831527A CN106831527A CN201710066673.0A CN201710066673A CN106831527A CN 106831527 A CN106831527 A CN 106831527A CN 201710066673 A CN201710066673 A CN 201710066673A CN 106831527 A CN106831527 A CN 106831527A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
A kind of pyrroles and preparation method thereof, is related to chemical preparation field.A kind of preparation method of pyrroles, including：Under conditions of vapor presence, furans is set to be reacted with ammonia by catalyst of solid super-strong acid.The method make use of price relatively low and wide material sources furans prepare pyrroles with ammonia reaction under conditions of solid super-strong acid is as catalyst, and technological process is simple, reduces reaction temperature, improves yield, can be mass.A kind of pyrroles, is prepared from by above-mentioned preparation method, and product purity is high.
Description
Technical field
The present invention relates to chemical preparation field, and more particularly to a kind of pyrroles and preparation method thereof.
Background technology
Pyrroles is a kind of important organic preparation and medicine intermediate.Many important medicines can be prepared from pyrroles.
Pyrroles is the fine solvent of many organic compounds, can solvent plurality of inorganic salt class, such as copper chloride, zinc chloride.Meanwhile, pyrroles
It is very wide as new material application field.Pyrroles can be used to prepare conducting polymer, as the electrode material of high-energy rechargeable battery,
Microwave absorbing material and solid electrolyte.Pyrroles can be used to prepare biomaterial, coating material.Pyrroles makes extensively in food
With.Therefore, pyrroles is in great demand.
But at present, China falls behind relatively to the production technology of pyrroles, and production cost is high, causes the price of pyrroles costly,
But also can not mass produce, so limit the application and further development of pyrroles.Therefore, a kind of efficient, letter is sought
The preparation method of single production pyrroles, with highly important economic implications and social effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of pyrroles, the method is in solid super-strong acid as catalyst
Under the conditions of, make use of price relatively low and wide material sources furans prepare pyrroles with ammonia reaction, technological process is simple, reduces reaction
Temperature, improves yield, can be mass.
Another object of the present invention is to provide one kind pyrroles as obtained in above-mentioned preparation method, product purity is high.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of pyrroles's preparation method, including：Under conditions of vapor presence, with solid super-strong acid to urge
Agent makes furans be reacted with ammonia.
The present invention proposes a kind of pyrroles, is prepared from by above-mentioned preparation method.
The beneficial effect of the pyrroles of the embodiment of the present invention and preparation method thereof is：With furans, ammonia as reactant, solid super strong
Acid prepares pyrroles for catalyst carries out reaction, and technological process is simple.The preparation method is using the metal oxygen for loading sulfate ion
Compound is catalyst, can with relatively low reaction temperature such as 360 DEG C reacted, the reaction of more other pyrroles's preparation methods
Temperature is low, reduces production difficulty.The molar yield of obtained pyrroles is that 98.5%, G/C content is 99.8%, improves yield,
Can be mass.The preparation method uses wide material sources and low-cost furans is used as raw material, with very big economic benefit.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the gas chromatogram of the pyrroles of the embodiment of the present invention 4.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional product that can be obtained by commercially available purchase
Product.
Pyrroles of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of pyrroles provided in an embodiment of the present invention, including：Under conditions of vapor presence, with solid
Super acids make furans be reacted with ammonia for catalyst.
Pyrroles also known as pyrrole, are five member ring heterocyclic compound, are the basic structure of many important biochemical substances.The system of pyrroles
Preparation Method is a lot, industrially prepares more use pyrrolidines dehydriding, and production cost is high, result in the costliness of pyrroles's price, mesh
Preceding market price is about 30~350,000 yuan/ton, but also can not mass produce, and limits the application of pyrroles and further sends out
Exhibition.
In the embodiment of the present invention, with furans and ammonia as raw material, in the presence of a catalyst, reaction generation pyrroles.Furans comes
Source is extensive and price is low, and price is about 30,000 yuan/ton, therefore prepares pyrroles with very big economic benefit by furans.Reactional equation
Formula such as (1)：
From formula (1), furans is oxygen atom displacement reaction with ammonia reaction generation pyrroles, and knowable to structural formula, furans is
Five member ring heterocyclic compound, with big π keys, Stability Analysis of Structures.Generally need to be completed in the presence of the catalyst of high temperature and high selectivity
Reaction.
The problem of activation of catalyst time is typically due to, the life-span of catalyst is shorter, it is impossible to meet actual industrial needs.And
Vapor is added in the reaction, the soak time of catalyst is greatly extended so that the reaction time extends.
Solid super-strong acid is a kind of new catalytic material, the characteristics of overcome liquid acid, with easily with reactants separate,
It is reusable, not etching reactor, reduce catalyst public hazards advantage.Through inventor research find, solid super-strong acid because
Its superpower acidity, in the reaction that furans prepares pyrroles, shows activity higher.Solid super-strong acid mainly has support type to consolidate
Body super acids, are that liquid superacid is carried on the class of metal oxide etc.；Mixed inorganic class, is formed by inorganic salts compounding；
Flurosulphonic acid ion exchange resin；Sulfate ion acidic metal oxide；Metal oxide-loaded solid super-strong acid.Sulphur
Acid ion acidic metal oxide does not pollute the environment because not containing halogen atom, can reuse at high temperature.
Further, in present pre-ferred embodiments, solid super-strong acid includes being loaded with the metal oxygen of sulfate ion
Compound, the metal oxide for loading sulfate ion includes TiO2、SnO2、Al2O3In one or more, such as SO4 2-/ZrO2-
Al2O3、SO4 2-/ZrO2-TiO2、SO4 2-/ZrO2-SnO2-Al2O3、SO4 2-/ZrO2-Fe2O3-Cr2O3Deng.In implementation of the invention
In example, solid super-strong acid is SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid, it has catalysis activity high, easily and reactant
The characteristics of system separates, conveniently reclaims and reuse, do not produce pollution.In the present invention, compared to the acid of other sulfate ions
Property metal oxide, SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid repeat performance is good, more conducively industrial applications.
The SO4 2-/TiO2-SnO2-Al2O3The active carrier of type solid super acid catalyst is carried on carrier is carrier surface, active carrier
Containing with SO4 2-Combine to form the oxide of active catalytic layer.Wherein, carrier is carrier is Al2O3, active carrier is TiO2-SnO2。
Pyrroles is gas phase reaction with the reaction of ammonia, and preferably fixed bed is used as consersion unit.Fixed bed has that back-mixing is small, fluid
The characteristics of effectively contact, simple structure, small mechanical loss being carried out with catalyst.Solid super-strong acid is attached to fixed bed, with
Air speed is passed through inert gas such as nitrogen deoxygenation for 0.0625~0.0875g/min, then fixed bed is heated up be heated to 300~
At 320 DEG C, to ammonia, 10~15min of vapor is passed through in fixed bed, now temperature is 300~400 DEG C in fixed bed, to fixation
Furans is passed through in bed.Reactant is passed through in two steps, in order in optimal conditions, furans fully reacts with ammonia.Preferably, temperature is reacted
Spend is 330~370 DEG C.Found by the lot of experiments of inventor, with SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid
Used as catalyst, furans is 360 DEG C with the optimum temperature of ammonia, and the reaction temperature of more other pyrroles's preparation methods is low, reduces
Production difficulty.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:6~10:9~11, furans, ammonia, the water steaming being passed through
Total air speed of gas is preferably 0.4~1.2g/min.At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 5
~10min, it is ensured that it is more complete, thorough that reaction is carried out.
After the completion of reaction, the pyrroles in product can also be purified, the pyrroles higher to obtain purity.Purification
Method can have multiple choices, for example, in the embodiment of the present invention purify method be by mixed reaction product be passed through condensation dress
In putting, reactant mixture is cooled down under conditions of -20~0 DEG C, make the which part gaseous matter be by condensation liquefaction
Liquid, adds highly basic and adjusts pH value to 10~12, it is preferred that highly basic is NaOH or potassium hydroxide.Stratification, obtains
Layer mixture and lower floor's alkali lye.
The boiling point of known furans is 31 DEG C, and the boiling point of pyrroles is 131 DEG C.Under conditions of 40~80 DEG C, upper strata is mixed
Thing is distilled, and obtains crude product pyrroles.Preferably, the furans in the mixture of upper strata, utilization is circulated by distillation is recyclable.
Further, rectifying is carried out to crude product pyrroles and obtains pyrroles.
In the industrial production, after lower floor's alkali lye is concentrated, recycle, can economize on resources, reduce cost.
The method under conditions of solid super-strong acid is as catalyst, make use of price relatively low and wide material sources furans with
Ammonia reaction prepares pyrroles, and technological process is simple, reduces reaction temperature, improves yield, can be mass.
A kind of pyrroles provided in an embodiment of the present invention, is prepared from by above-mentioned preparation method, and pyrroles's purity is high.
Feature of the invention and performance are described in further detail with reference to embodiments.
Embodiment 1
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.0625g/min of air speed
Nitrogen deoxygenation；
Fixed bed is heated up again when being heated to 300 DEG C, to being passed through ammonia, vapor 10min in fixed bed, now in fixed bed
Temperature is 320 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are 1:6:9, it is passed through
Furans, ammonia, vapor total air speed be 0.4g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 5min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is 0 DEG C；
Mix products are mixed liquor by condensation liquefaction, add NaOH to adjust pH value to 10；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 40 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 2
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.075g/min of air speed
Nitrogen deoxygenation；
Fixed bed is heated up again when being heated to 310 DEG C, to being passed through ammonia, vapor 12min in fixed bed, now in fixed bed
Temperature is 360 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:8:10, lead to
The furans that enters, ammonia, total air speed of vapor are 0.8g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 8min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is -10 DEG C；
Mix products are mixed liquor by condensation liquefaction, add potassium hydroxide to adjust pH value to 11；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 60 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 3
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.0875g/min of air speed
Nitrogen deoxygenation；
Fixed bed is heated up again when being heated to 320 DEG C, to being passed through ammonia, vapor 15min in fixed bed, now in fixed bed
Temperature is 400 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:10:11, lead to
The furans that enters, ammonia, total air speed of vapor are 1.2g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 10min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is -20 DEG C；
Mix products are mixed liquor by condensation liquefaction, add NaOH to adjust pH value to 12；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 80 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 4
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.075g/min of air speed
Nitrogen deoxygenation；
Fixed bed is heated up again when being heated to 320 DEG C, to being passed through ammonia, vapor 10min in fixed bed, now in fixed bed
Temperature is 360 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:8:11, lead to
The furans that enters, ammonia, total air speed of vapor are 1g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 10min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is -20 DEG C；
Mix products are mixed liquor by condensation liquefaction, add NaOH to adjust pH value to 12；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 80 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 5
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed；
Fixed bed is heated up again when being heated to 300 DEG C, to being passed through ammonia, vapor 15min in fixed bed, now in fixed bed
Temperature is 400 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:6:9, it is passed through
Furans, ammonia, vapor total air speed be 0.4g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 5min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is 0 DEG C；
Mix products are mixed liquor by condensation liquefaction, add potassium hydroxide to adjust pH value to 10；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 60 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 6
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.0875g/min of air speed
Helium deoxygenation；
Fixed bed is heated up again when being heated to 320 DEG C, to being passed through ammonia, vapor, furans in fixed bed.Wherein, it is passed through
Furans, ammonia, the mol ratio of vapor are：1:8:11, the furans that is passed through, ammonia, total air speed of vapor are 0.8g/min；
Be passed through mixed reaction product in condensing unit after terminating by reaction, and the temperature of condensing unit is -15 DEG C；
Mix products are mixed liquor by condensation liquefaction, add potassium hydroxide to adjust pH value to 11；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 80 DEG C, upper strata mixture is distilled, the furans for reclaiming distillation is circulated utilization, obtain thick
Product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 7
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/ZrO2-Al2O3Type solid super-strong acid is attached to fixed bed, and nitrogen is passed through by 0.0875g/min of air speed
Deoxygenation；
Fixed bed is heated up again when being heated to 320 DEG C, to being passed through ammonia, vapor 10min in fixed bed, now in fixed bed
Temperature is 380 DEG C, to being passed through furans in fixed bed.Wherein, the furans that is passed through, ammonia, the mol ratio of vapor are：1:10:11, lead to
The furans that enters, ammonia, total air speed of vapor are 1.1g/min；
At the end of reaction, first stop being passed through furans, be further continued for being passed through ammonia, vapor 8min；
Mixed reaction product is passed through in condensing unit, the temperature of condensing unit is -10 DEG C；
Mix products are mixed liquor by condensation liquefaction, add potassium hydroxide to adjust pH value to 11；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 70 DEG C, upper strata mixture is distilled, the furans for reclaiming distillation is circulated utilization, obtain thick
Product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Embodiment 8
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
By SO4 2-/ZrO2-SnO2-Al2O3Type solid super-strong acid is attached to fixed bed, is passed through by 0.0875g/min of air speed
Nitrogen deoxygenation；
Fixed bed is heated up again when being heated to 400 DEG C, to being passed through ammonia, vapor, furans in fixed bed.Wherein, it is passed through
Furans, ammonia, the mol ratio of vapor are：1:10:11, the furans that is passed through, ammonia, total air speed of vapor are 1.1g/min；
Be passed through mixed reaction product in condensing unit after terminating by reaction, and the temperature of condensing unit is 0 DEG C；
Mix products are mixed liquor by condensation liquefaction, add potassium hydroxide to adjust pH value to 11；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 70 DEG C, upper strata mixture is distilled, the furans for reclaiming distillation is circulated utilization, obtain thick
Product pyrroles；After lower floor's alkali lye is concentrated, recycle；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Comparative example 1
The pyrroles that the present embodiment is provided is prepared from by following preparation method, and it includes：
Alumina silicate catalyst is attached to fixed bed；
Fixed bed is heated up again when being heated to 360 DEG C, to being passed through furans, ammonia, water in fixed bed.The furans that wherein, is passed through,
Ammonia, the mol ratio of vapor are：1:6:9, the furans that is passed through, ammonia, total air speed of vapor are 1g/min；
After reaction terminates, mixed reaction product is passed through in condensing unit, the temperature of condensing unit is -20 DEG C；
Mix products are mixed liquor by condensation liquefaction, add NaOH to adjust pH value to 12；
Stratification, obtains upper strata mixture and lower floor's alkali lye；
Under conditions of 80 DEG C, upper strata mixture is distilled, the furans that recovery is distilled off is circulated utilization, obtains
To crude product pyrroles；
Rectifying is carried out to crude product pyrroles and obtains pyrroles.
Comparative example 2
After being passed through nitrogen, add catalyst alumina silicate to be heated to 380 DEG C, ammonia is passed through with the air speed of 0.9ml/min
After 30min, furans is passed through with the air speed of 0.2ml/min.After reaction terminates, product is collected.
Gas chromatographic analysis test is carried out to the product in the product in embodiment 1~8 and comparative example 1,2, pyrroles is calculated
Molar yield and G/C content, the results are shown in Table 1.
The test result of table 1
As shown in Table 1, the molar yield of the pyrroles of embodiment 1~6 is high compared with comparative example 1, comparative example 2, more than 95%,
And the G/C content of embodiment 1~6 is high compared with comparative example 1, comparative example 2, more than 99.5%, the preparation side of embodiment 1~6 is illustrated
Method is more excellent compared with the preparation method of comparative example 1, comparative example 2.Embodiment 7 and embodiment 8 use different catalyst, and its pyrroles's rubs
Your yield, G/C content are low compared with embodiment 1~6, and based on embodiment 1~8, in the present invention, three constituent element solid super-strong acids are urged
Change excellent catalytic effect of the effect compared with two constituent element solid super-strong acids, in three constituent element solid super-strong acids, what embodiment 1~6 was used
SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is more beneficial for the carrying out of reaction, and preparation method is more excellent.Wherein, embodiment 4
The molar yield and G/C content highest of pyrroles, respectively 98.5%, 99.8%.It follows that optimal reaction condition is：With
SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is catalyst, and furans, ammonia, the reaction temperature of vapor are 360 DEG C, moles
Than being 1:8:11st, the furans that is passed through, ammonia, total air speed of vapor are 1g/min, and condensation temperature is -20 DEG C, adds highly basic regulation
PH value is to 12.
Fig. 1 is the gas chromatogram of the pyrroles of embodiment 4, and gas-chromatography shown in analysis chart 1 understands that retention time is
The peak area of 3.415min is maximum, and its content is maximum, it is possible to determine that, the product of synthesis is purity pyrroles high.
In sum, it is reaction with furans, ammonia in the preferred embodiment of pyrroles of the embodiment of the present invention and preparation method thereof
Thing, SO4 2-/TiO2-SnO2-Al2O3Type solid super-strong acid is catalyst, carries out reaction under conditions of letting nitrogen in and deoxidizing and prepare pyrrole
Cough up, technological process is simple.Optimal reaction temperature is 360 DEG C, and the preparation method reaction temperature of more other pyrroles is low, reduces
Production difficulty.The molar yield of obtained pyrroles is that 98.5%, G/C content is 99.8%, improves yield, be can be mass.Should
Preparation method uses wide material sources and low-cost furans is used as raw material, with very big economic benefit.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of pyrroles, it is characterised in that including：Under conditions of vapor presence, it is with solid super-strong acid
Catalyst makes furans be reacted with ammonia.
2. the preparation method of pyrroles according to claim 1, it is characterised in that the solid super-strong acid includes being loaded with sulphur
The metal oxide of acid ion, the metal oxide for being loaded with sulfate ion includes TiO2、SnO2、Al2O3In one
Plant or various.
3. the preparation method of pyrroles according to claim 1, it is characterised in that the reaction temperature of the furans and the ammonia
It is 300~400 DEG C.
4. the preparation method of pyrroles according to claim 1, it is characterised in that the reaction temperature of the furans and the ammonia
It is 330~370 DEG C.
5. the preparation method of pyrroles according to claim 1, it is characterised in that under conditions of vapor presence,
It is that the catalyst includes the method that the furans reacts with the ammonia with the solid super-strong acid：By the ammonia, the water
Steam, the furans are passed through the fixed bed for being attached with the solid super-strong acid with total air speed of 0.4~1.2g/min.
6. the preparation method of pyrroles according to claim 5, it is characterised in that by the ammonia, vapor, described
Furans is passed through before being attached with the fixed bed of the solid super-strong acid also to be included：With the sky of 0.0625~0.0875g/min
Speed in the fixed bed to being passed through inert gas.
7. the preparation method of the pyrroles according to any one of claim 1 to 6, it is characterised in that the furans, the ammonia,
The mol ratio of the vapor is：1:6~10:9~11.
8. the preparation method of the pyrroles according to any one of claim 1 to 6, it is characterised in that also including being adjusted with alkali lye
The pH value of product separates to obtain upper strata mixture to 10~12.
9. the preparation method of pyrroles according to claim 8, it is characterised in that also including being carried out to the upper strata mixture
Distillation, vapo(u)rizing temperature is 40~80 DEG C.
10. a kind of pyrroles, it is characterised in that the preparation method of the pyrroles described in any one of claim 1 to 9 is prepared from.
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| WO2022197944A1 (en) * | 2021-03-16 | 2022-09-22 | Chevron Phillips Chemical Company Lp | Two-step synthesis of pyrrole compounds from furan compounds |
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