CN109988082A - A kind of method that continuous oxide hydrogenation prepares acrylonitrile - Google Patents
A kind of method that continuous oxide hydrogenation prepares acrylonitrile Download PDFInfo
- Publication number
- CN109988082A CN109988082A CN201910366911.9A CN201910366911A CN109988082A CN 109988082 A CN109988082 A CN 109988082A CN 201910366911 A CN201910366911 A CN 201910366911A CN 109988082 A CN109988082 A CN 109988082A
- Authority
- CN
- China
- Prior art keywords
- propionitrile
- acrylonitrile
- reaction
- water
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of methods that continuous oxide hydrogenation prepares acrylonitrile, comprising the following steps: using propionitrile as raw material, under the catalytic action of nickel catalyst, oxidative dehydrogenation occurs, obtains acrylonitrile；The nickel catalyst is made of Ni, Co, Mo and Zr.The method that above-mentioned continuous oxide hydrogenation provided by the invention prepares acrylonitrile, only the complete propionitrile of unreacted, product acrylonitrile and water, reaction product obtain propionitrile and acrylonitrile after separation in product, and propionitrile is reusable.The process route is simple, cleanliness without any pollution, and later separation process is short, corrosion-free to equipment, and yield is high, has biggish industrial application value.In addition, propionitrile is generally only used as solvent or medicine intermediate, purposes is less, and market capacity is small, and acrylonitrile is widely used, after converting acrylonitrile for propionitrile, considerably increases the market capacity of propionitrile.
Description
Technical field
The present invention relates to a kind of methods that technical field of organic synthesis more particularly to continuous oxide hydrogenation prepare acrylonitrile.
Background technique
Acrylonitrile is the important monomer of synthetic fibers, synthetic rubber and synthetic resin.The polyacrylonitrile as made from acrylonitrile
Synthetic wool is also like wool in fiber, that is, acrylic fibers, performance pole.Nitrile rubber can be made in acrylonitrile and butadiene copolymer,
With good oil resistivity, cold resistance, wearability and electrical insulation capability, and in most of chemical solvents, sunlight and heat effect
Under, performance is more stable.Acrylonitrile and butadiene, styrene copolymerized ABS resin obtained, have light, cold-resistant, impact resistance
Can be preferable the advantages that.Acrylamide and acrylicacidandesters class can be made in acrylonitrile hydrolysis, they are important organic chemical industry's original
Material.Acrylonitrile can also electrolytic hydrogenation be coupled be made adiponitrile, hexamethylene diamine can be made by adipic dinitrile hydrogenation again, hexamethylene diamine is nylon66 fiber
Raw material can manufacture water repellent agent and adhesive etc., be also used in other organic syntheses and medical industry, and be used as cereal fumigant
Deng.In addition, the product are also a kind of non-protonic polar solvent, as php slurry auxiliary agent PAC142 raw material.Acrylonitrile is still made
Standby insecticide worm expires the intermediate of nitrile.
There are mainly three types of the industrial processes of acrylonitrile, respectively cyanoethanol method, acetylene method, propylene ammmoxidation process.
Wherein, cyanoethanol method is reacted in the presence of water and trimethylamine mainly using ethylene oxide and hydrogen cyanide as raw material
Cyanoethanol is obtained, then using magnesium carbonate as catalyst, is dehydrated in 200-280 DEG C and acrylonitrile, yield about 75% is made.The production of this method
Acrylonitrile purity it is higher, but hydrogen cyanide toxicity is big, higher cost.
Acetylene method is to urge using acetylene and hydrogen cyanide as main material in stannous chloride-potassium chloride-sodium chloride dilute hydrochloric acid solution
Under change effect, acrylonitrile is reacted to obtain at 80-90 DEG C.This method production process is simple, and yield is good, up to 97% in terms of hydrogen cyanide.
But side reaction is more, and product purification is more difficult, and toxicity is also big, and raw material acetylene price is higher than propylene, lags behind technically and economically
Propylene ammmoxidation process.
Propylene ammmoxidation process is to enter ebullated bed using propylene, ammonia, air and water as raw material according to a certain ratio or fixed bed is anti-
Device is answered, it is raw at 400-500 DEG C of temperature and normal pressure under the phosphorus molybdenum bismuth system for making carrier with silica gel or the effect of antimony Fe-series catalyst
At acrylonitrile.Then neutralized tower dilute sulfuric acid removes unreacted ammonia, then absorbs the gases such as acrylonitrile, shape through absorption tower water
At aqueous solution, make the aqueous solution through extraction tower separating acetonitrile, removes hydrogen cyanide in dehydrogenation cyanic acid tower, third is obtained through dehydration, rectifying
Alkene nitrile product, byproduct have acetonitrile, hydrogen cyanide and ammonium sulfate.This method energy consumption is larger, and pollution is big.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing the side that a kind of continuous oxide hydrogenation prepares acrylonitrile
Method prepares acrylonitrile using the new method of oxidative dehydrogenation using propionitrile as raw material, and process route is simple, while receipts with higher
Rate and purity.
In order to solve the above technical problems, the present invention provides a kind of methods that continuous oxide hydrogenation prepares acrylonitrile, including
Following steps:
Using propionitrile as raw material, under the catalytic action of nickel catalyst, oxidative dehydrogenation occurs, obtains acrylonitrile；
The nickel catalyst is made of the oxide of Ni, Co, Mo and Zr.
For the present invention using propionitrile as raw material, the present invention is to the source of the propionitrile and is not particularly limited, can be general commercially available,
Such as general industrial raw material, in some embodiments of the invention, the mass content of the propionitrile is 99.5%.
The nickel catalyst is made of the oxide of Ni, Co, Mo and Zr.
Currently preferred, the Ni, Co, the molar ratio of Mo and Zr are 10~12:3~4:5:2~3.
It is further preferred that the molar ratio of the Ni, Co, Mo and Zr are 11~12:3~3.5:5:2~2.5.In this hair
In bright some specific embodiments, the Ni, Co, the molar ratio of Mo and Zr are 12:3:5:2.
Currently preferred, the catalyst is prepared in accordance with the following methods:
By nickeliferous water-soluble inorganic salt, water-soluble inorganic salt containing cobalt, water-soluble inorganic salt containing molybdenum, water-soluble inorganic salt containing zirconium
It mixes, dissolve in water, obtain mixed solution；
Mixed solution is heated and is reacted, cooling is dried to obtain catalyst.
The present invention is first by nickeliferous water-soluble inorganic salt, water-soluble inorganic salt containing cobalt, water-soluble inorganic salt containing molybdenum, water containing zirconium
Soluble inorganic salt mixes in water, stirring and dissolving, more preferably first by nickeliferous water-soluble inorganic salt, water-soluble inorganic salt containing cobalt,
The mixing of water-soluble inorganic salt containing molybdenum, adjusting pH value to 7, then mixed with water-soluble inorganic salt containing zirconium, it stirs.The present invention is for described
The mode of stirring is well known to those skilled in the art without limiting；The time of the stirring is preferably 20~30min；
The mixing time for adding zirconium hydroxide is preferably 40~60min.
According to the present invention, the nickeliferous water-soluble inorganic salt includes but is not limited to Nickelous nitrate hexahydrate；The nickel is water-soluble
Inorganic salt is preferably >=99%.
The water-soluble inorganic salt containing cobalt includes but is not limited to cabaltous nitrate hexahydrate；The water-soluble inorganic salt containing cobalt it is dense
Degree is preferably 0.50~0.75mol/L；The water-soluble inorganic salt containing molybdenum includes but is not limited to ammonium molybdate；The molybdenum water solubility nothing
The mass concentration of machine salt is preferably >=98%.
The water-soluble inorganic salt containing zirconium includes but is not limited to zirconium hydroxide.The quality of the water-soluble inorganic salt containing zirconium is dense
Degree preferably >=99.9%.
Mixed solution is heated and is reacted, cooling is dried to obtain catalyst.
Mixed solution is preferably transferred in ptfe autoclave by the present invention；Reaction kettle is preferably put by the present invention
Perseverance 12h in 160 DEG C of air dry oven.
The present invention is for the cooling without restriction, cooled to room temperature.
After cooling, using vacuum pump, bottle,suction and filter paper vacuumize suction filtration, wash organic solvent repeatedly using dehydrated alcohol
After reuse distillation water washing, be dried to obtain catalyst；The drying temperature is 70~80 DEG C；The drying time be 10~
12h。
Then by shaping of catalyst machine, fixed bed catalyst is prepared.
In propionitrile oxidative dehydrogenation process, since three key of carbon nitrogen is highly polar covalent bond, it will lead in reaction process separate
The carbon-carbon bond of cyano is easily broken off, and generates acetonitrile and methyl, methyl, which be combined with each other, generates ethane.The present invention selects above-mentioned specific urge
Agent, by four kinds of Precious metals ratios in allotment catalyst, control catalytic dehydrogenation ability is strong and weak, to make the carbon far from cyano
Carbon key is oxidized dehydrogenation, and then inhibits the fracture of carbon-carbon bond, and under the catalytic action of catalyst, the carbon-carbon bond far from cyano is by oxygen
Fluidized dehydrogenation generates acrylonitrile.
The reaction equation of above-mentioned reaction is as follows:
Currently preferred, above-mentioned reaction can carry out in the serializations chemical production device such as fixed bed reactors.
Preferably, the process flow chart of the reaction is as shown in Figure 1.
Specifically, the reaction system of reaction of the present invention includes sequentially connected premixed device, fixed bed reactors, gas-liquid
Separator, continuous extraction separator and continuous rectification apparatus.
Wherein, blended absorbent of the premixed device for gas-liquid early period of propionitrile liquid and oxygen, keeps gas-liquid emulsifying effectiveness, has
Conducive to quickening extent of reaction.
The present invention is to above-mentioned fixed bed reactors and is not particularly limited, and can be well known to those skilled in the art general solid
Fixed bed reactor, present invention preferably employs the fixed bed reactors of metal material.
Above-mentioned nickel catalyst is loaded in fixed bed reactors by the present invention.
Filling process is preferably as follows:
Quartz sand is loaded in fixed bed reactors bottom, middle part loads catalyst, and top refills quartz sand.
Currently preferred, the nickel catalyst accounts for the 0.01%~0.50% of propionitrile quality.
It is currently preferred, reaction system is purged using nitrogen before reactions, nitrogen enters reaction system by premixed device,
Purging speed and the time can be set as needed, can starvation, that is, avoid oxygen or air from entering reaction system, this
Invention is to this and is not particularly limited.Preferably, the purging speed of the nitrogen is 10~40mL/min, and the time is 5~20min.
In some embodiments of the invention, purging speed is 20mL/min, time 10min.
Using nitrogen to purge reaction system in advance can guarantee anti-with starvation, when no propionitrile is passed through
Answer system in temperature-rise period, catalyst is in anaerobic state, prevents catalyst coking, guarantees catalyst activity.
Meanwhile fixed bed reactors temperature is risen to 200~220 DEG C by room temperature, to the catalyst in fixed bed reactors
It is activated.
The speed of the heating can be according to experimental conditions self-setting, preferably 10~30 DEG C/min.Of the invention
In some specific embodiments, the speed of the heating is 20 DEG C/min.Slowly heating is conducive to the slow activation of catalyst.
In the present invention, the reaction is using air or oxygen as oxidant.
When reaction temperature reaches predetermined temperature, start to be passed through air or oxygen from premixed device to reaction system.Preferably,
The air or oxygen flow is slowly increased to 1500mL/min by 0mL/min.The present invention is to the air or oxygen flow
Advance the speed and be not particularly limited, can as needed or response situation self-setting, can steady air flow, and make reacting balance into
Row.Preferably, the air or oxygen flow is increased speed as 50~200mL/min.Of the invention some specific
In embodiment, the air or oxygen flow is increased speed as 100mL/min.
While being passed through air, nitrogen flow rate is slowly dropped to 0mL/min.Reduction of the present invention to the nitrogen flow
Rate is simultaneously not particularly limited, can as needed or response situation self-setting, can steady air flow, and make reacting balance i.e.
It can.Preferably, the reduction speed of the nitrogen flow is 5~20 mL/min.In some embodiments of the invention, institute
The reduction speed for stating nitrogen flow is 10mL/min.
Currently preferred, by reducing the aperture of outlet, in fixed bed reactors end, slow back pressure to reaction is suitble to
Pressure, it is preferred that back pressure to 1.0~7.0MPa.In some embodiments of the invention, back pressure is to 2.0MPa.
After pressure is stablized, started to be passed through liquid phase propionitrile to reaction system from premixed device, the liquid phase propionitrile and air exist
Premixed device carries out the blended absorbent of gas-liquid early period, and steadily enters reaction system.
The flow velocity of the propionitrile is preferably 2~7mL/min, in some embodiments of the invention, the propionitrile
Flow velocity is 5mL/min.
After the mixture of propionitrile and air enters fixed bed reactors, under the action of nickel catalyst, aoxidized
Dehydrogenation reaction obtains acrylonitrile.
The residence time of the reaction is preferably≤5min.
The temperature of the reaction is preferably 200~450 DEG C, and the pressure of reaction is preferably 1.0~7.0MPa.
Oxygen concentration is higher under such pressure condition, and oxidation is more abundant, and yield is higher.
The molar ratio of the propionitrile and air is preferably 1:(5~15)；The molar ratio of the propionitrile and oxygen is preferably 1:
(1~3).
After reaction, reaction solution enters gas-liquid separation device, and the gas of recycling can be with reuse.
Liquid phase material enters continuous extraction separator, wherein and water phase stores for future use, and oil mutually enters continuous rectification apparatus,
After continuous rectification is handled, acrylonitrile is obtained, a small amount of by-product propionitrile can reuse.
The method that above-mentioned continuous oxide hydrogenation provided by the invention prepares acrylonitrile, only unreacted complete third in product
Nitrile, product acrylonitrile and water, reaction product obtain propionitrile and acrylonitrile after separation, and propionitrile is reusable.The process route
Simply, cleanliness without any pollution, later separation process is short, corrosion-free to equipment, and yield is high, has biggish industrial application valence
Value.In addition, propionitrile is generally only used as solvent or medicine intermediate, purposes is less, and market capacity is small, and acrylonitrile purposes is wide
It is general, after converting acrylonitrile for propionitrile, considerably increase the market capacity of propionitrile.
Detailed description of the invention
Fig. 1 is acrylonitrile standard mass spectrogram；
The reaction of Fig. 2 embodiment of the present invention 2 obtains sample mass spectrum；
Fig. 3 is the process flow chart that continuous oxide hydrogenation provided by the invention prepares acrylonitrile reactor.
Specific embodiment
In order to further illustrate the present invention, prepared by propylene to continuous oxide hydrogenation provided by the invention below with reference to embodiment
The method of nitrile is described in detail.
In following embodiment, reactor uses tubular fixed-bed reactor.
Wherein, gas reuse takes gas compressor to compress, and squeezes into reaction system.Propionitrile is obtained pure by rectifying
Product squeeze into reaction system using feed pump.Gas-liquid separation is separated using knockout drum.
Embodiment 1
It weighs 30.00g Nickelous nitrate hexahydrate to add in the cabaltous nitrate hexahydrate solution that 80mL concentration is 0.5mol/L, stirring
It makes it dissolve, then weighs 10.00g ammonium molybdate, be dissolved in above-mentioned solution, then the NaOH solution of 2. 5mol/L is added to above-mentioned
In solution, pH to 7 is adjusted, stirs 30min, 7.5g zirconium hydroxide is then added, continues to stir 1.0h.Then mixed liquor is transferred to
Into ptfe autoclave, and reaction kettle is put into perseverance 12h in 160 DEG C of air dry oven.Reaction kettle is taken out, it is cooling
To room temperature, vacuum pump is used；Bottle,suction and filter paper vacuumize suction filtration, reuse after washing organic solvent repeatedly using dehydrated alcohol
Water washing is distilled, the drying 12 hours of 80 DEG C of baking oven is put into, obtains catalyst sample, then by shaping of catalyst machine, preparation is solid
Fixed bed catalyst.
Embodiment 2
It weighs 48.40g Nickelous nitrate hexahydrate to add in the cabaltous nitrate hexahydrate solution that 80mL concentration is 0.5mol/L, stirring
It makes it dissolve, then weighs 14.85g ammonium molybdate, be dissolved in above-mentioned solution, then the NaOH solution of 2. 5mol/L is added to above-mentioned
In solution, pH to 7 is adjusted, stirs 30min, 11.38g zirconium hydroxide is then added, continues to stir 1.0h.Then mixed liquor is turned
Enter into ptfe autoclave, and reaction kettle is put into perseverance 12h in 160 DEG C of air dry oven.Reaction kettle is taken out, it is cold
But to room temperature, vacuum pump is used；Bottle,suction and filter paper vacuumize suction filtration, make again after washing organic solvent repeatedly using dehydrated alcohol
It is washed with distilled water, is put into the drying 12 hours of 80 DEG C of baking oven, obtains catalyst sample, then pass through shaping of catalyst machine, preparation
Fixed bed catalyst.
Embodiment 3
It weighs 52.87 Nickelous nitrate hexahydrates to add in the cabaltous nitrate hexahydrate solution that 80mL concentration is 0.5mol/L, stirring
It makes it dissolve, then weighs 14.85 and be dissolved in above-mentioned solution, then the NaOH solution of 2.5mol/L is added in above-mentioned solution, adjust
PH to 7 is saved, 30min is stirred, 7.58 zirconium hydroxides is then added, continues to stir 1.0h.Then mixed liquor is transferred to polytetrafluoro
In ethylene reaction kettle, and reaction kettle is put intoAir dry oven in perseverance 12h.Reaction kettle is taken out, room is cooled to
Temperature uses vacuum pump；Bottle,suction and filter paper vacuumize suction filtration, reuse distillation after washing organic solvent repeatedly using dehydrated alcohol
Water washing is put into the drying 12 hours of 80 DEG C of baking oven, obtains catalyst sample, then by shaping of catalyst machine, prepares fixed bed
Use catalyst.
Embodiment 4
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 10mL embodiment 1 is loaded in fixed bed reactors
For 10:3:5:3), process is loaded are as follows: load quartz sand in fixed bed bottom, middle part loads catalyst, and top refills quartz
Sand.Nitrogen is connect with premixed device, is entered from premixed device, and reaction system is purged, and purging speed is 20mL/min, and purge time is
10min, and slowly by reaction temperature by room temperature to 200 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, be passed through air to reaction system since premixed device, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
20mL/min is slowly dropped to 0mL/min, and reduction rate is 10mL/min.By reducing the aperture of outlet, in fixed bed reactors
The slow back pressure in end is to 2.0MPa, after pressure is stablized, since premixed device be passed through liquid phase propionitrile, propionitrile flow velocity is 5mL/
Min, reaction time≤5min after stablizing discharging, collect reaction solution, after extraction and separation, oily phase gas chromatographic analysis are taken to examine
Analysis is surveyed, wherein propionitrile content 38.6%, acrylonitrile content 60.7%.Reaction yield 56.9%.
Reaction product structure is characterized using mass spectrum (Mass).Fig. 1 is acrylonitrile standard mass spectrogram, Fig. 2 present invention
The reaction of embodiment 2 obtains sample mass spectrum.By Fig. 1 and Fig. 2 it was determined that the embodiment of the present invention 2 was prepared is third
Alkene nitrile.
Embodiment 5
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 10mL embodiment 1 is loaded in fixed bed reactors
For 10:3:5:3), process is loaded with embodiment 2, nitrogen purges reaction system, purge time 15min with 20mL/min, and delays
Slowly by reaction temperature by room temperature to 300 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, start to be passed through air from premixed device to reaction system, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
Slowly near 0mL/min, reduction rate are 10mL/min to 20mL/min.In fixed bed reactors end, slow back pressure is extremely
2.0MPa starts to be passed through liquid phase propionitrile after pressure is stablized, and propionitrile flow velocity is 5mL/min, reaction time≤5min, surely
After making material, reaction solution is collected, after extraction and separation, takes oily phase gas chromatographic analysis to test and analyze, wherein propionitrile content 28.4%,
Acrylonitrile content 70.5%.Reaction yield 66.9%.
Embodiment 6
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 20mL embodiment 1 is loaded in fixed bed reactors
For 10.0:3:5:3), process is loaded with embodiment 2, nitrogen purges reaction system with 20mL/min, purge time 20min,
And slowly by reaction temperature by room temperature to 300 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, start to be passed through air from premixed device to reaction system, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
Slowly near 0mL/min, reduction rate are 10mL/min to 20mL/min.In fixed bed reactors end, slow back pressure is extremely
2.0MPa starts to be passed through liquid phase propionitrile after pressure is stablized, and propionitrile flow velocity is 5mL/min, reaction time≤5min, surely
After making material, reaction solution is collected, after extraction and separation, takes oily phase gas chromatographic analysis to test and analyze, wherein propionitrile content 15.1%,
Acrylonitrile content 83.8%.Reaction yield 78.5%.
Embodiment 7
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 25mL embodiment 1 is loaded in fixed bed reactors
For 10:3:5:3), process is loaded with embodiment 2, nitrogen purges reaction system, purge time 20min with 20mL/min, and delays
Slowly by reaction temperature by room temperature to 300 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, start to be passed through air from premixed device to reaction system, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
Slowly near 0mL/min, reduction rate are 10mL/min to 20mL/min.In fixed bed reactors end, slow back pressure is extremely
2.0MPa starts to be passed through liquid phase propionitrile after pressure is stablized, and propionitrile flow velocity is 5mL/min, reaction time≤5min, surely
After making material, reaction solution is collected, after extraction and separation, takes oily phase gas chromatographic analysis to test and analyze, wherein propionitrile content 8.1%,
Acrylonitrile content 90.8%.Reaction yield 86.7%.
Embodiment 8
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 20mL embodiment 2 is loaded in fixed bed reactors
For 12:3:5:2), process is loaded with embodiment 2, nitrogen purges reaction system, purge time 20min with 20mL/min, and delays
Slowly by reaction temperature by room temperature to 400 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, start to be passed through air from premixed device to reaction system, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
Slowly near 0mL/min, reduction rate are 10mL/min to 20mL/min.In fixed bed reactors end, slow back pressure is extremely
2.0MPa starts to be passed through liquid phase propionitrile after pressure is stablized, and propionitrile flow velocity is 5mL/min, reaction time≤5min, surely
After making material, reaction solution is collected, after extraction and separation, takes oily phase gas chromatographic analysis to test and analyze, wherein propionitrile content 8.1%,
Acrylonitrile content 90.8%.Reaction yield 86.0%.
Embodiment 9
Nickel catalyst (the molar ratio of Ni, Co, Mo and Zr prepared by 20mL embodiment 3 is loaded in fixed bed reactors
For 12:4:5:2), process is loaded with embodiment 2, nitrogen purges reaction system, purge time 20min with 20mL/min, and delays
Slowly by reaction temperature by room temperature to 400 DEG C, heating rate is 20 DEG C/min.
When reaction temperature reaches predetermined temperature, start to be passed through air from premixed device to reaction system, air mass flow by
0mL/min is slowly increased to 1500mL/min, and the increased rate of air mass flow is 100mL/min, meanwhile, by nitrogen flow rate by
Slowly near 0mL/min, reduction rate are 10mL/min to 20mL/min.In fixed bed reactors end, slow back pressure is extremely
2.0MPa starts to be passed through liquid phase propionitrile after pressure is stablized, and propionitrile flow velocity is 5mL/min, reaction time≤5min, surely
After making material, reaction solution is collected, after extraction and separation, takes oily phase gas chromatographic analysis to test and analyze, wherein propionitrile content 8.1%,
Acrylonitrile content 90.8%.Reaction yield 83.5%.
As can be seen from the above embodiments, acrylonitrile, and process route letter has been prepared in the above method provided by the invention
It is single, while yield with higher and purity.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of method that continuous oxide hydrogenation prepares acrylonitrile, comprising the following steps:
Using propionitrile as raw material, under the catalytic action of nickel catalyst, oxidative dehydrogenation occurs, obtains acrylonitrile；
The nickel catalyst is made of the oxide of Ni, Co, Mo and Zr.
2. the method according to claim 1, wherein the molar ratio of the Ni, Co, Mo and Zr be 10~12:3~
4:5:2~3.
3. according to the method described in claim 2, it is characterized in that, the molar ratio of the Ni, Co, Mo and Zr be 11~12:3~
3.5:5:2~2.5.
4. according to the method described in claim 3, it is characterized in that, the molar ratio of the Ni, Co, Mo and Zr are 12:3:5:2.
5. the method according to claim 1, wherein the reaction carries out in fixed bed reactors.
6. according to the method described in claim 5, it is characterized in that, the continuous oxide hydrogenation prepares acrylonitrile preparation method tool
Body are as follows:
A) catalyst is loaded in fixed bed reactors；
B) inert gas purge reactor is used；
C) it is passed through oxidant, propionitrile is passed through from premixer, oxidative dehydrogenation occurs, obtains acrylonitrile；The oxidant is
Air or oxygen.
7. the method according to claim 1, wherein the temperature of the reaction be 200~450 DEG C, the pressure of reaction
It is by force 1.0~7.0MPa.
8. the method according to the description of claim 7 is characterized in that the molar ratio of the propionitrile and air is 1:(5~15)；Institute
The molar ratio for stating propionitrile and oxygen is 1:(1~3).
9. the method according to claim 1, wherein the nickel catalyst account for propionitrile quality 0.01%~
0.50%.
10. the method according to claim 1, wherein the catalyst is prepared in accordance with the following methods:
By nickeliferous water-soluble inorganic salt, water-soluble inorganic salt containing cobalt, water-soluble inorganic salt containing molybdenum, water-soluble inorganic salt containing zirconium in water
Middle mixing, dissolution, obtain mixed solution；
Mixed solution is heated and is reacted, cooling is dried to obtain catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910366911.9A CN109988082B (en) | 2019-05-05 | 2019-05-05 | Method for preparing acrylonitrile by continuous oxidative dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910366911.9A CN109988082B (en) | 2019-05-05 | 2019-05-05 | Method for preparing acrylonitrile by continuous oxidative dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109988082A true CN109988082A (en) | 2019-07-09 |
| CN109988082B CN109988082B (en) | 2022-04-19 |
Family
ID=67135826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910366911.9A Active CN109988082B (en) | 2019-05-05 | 2019-05-05 | Method for preparing acrylonitrile by continuous oxidative dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109988082B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821278A (en) * | 1970-02-09 | 1974-06-28 | Mobil Oil | Oxidative dehydrogenation of propionitrile to aerylonitrile |
| JPS5350119A (en) * | 1976-10-15 | 1978-05-08 | Monsanto Co | Method of oxidative dehydration of propionitrile |
| US4178305A (en) * | 1976-10-15 | 1979-12-11 | Monsanto Company | Oxidative dehydrogenation of propionitrile to acrylonitrile |
| CN1037282A (en) * | 1988-04-29 | 1989-11-22 | 国际壳牌研究有限公司 | Catalyst for dehydrogenating organic compounds and its production and application |
-
2019
- 2019-05-05 CN CN201910366911.9A patent/CN109988082B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821278A (en) * | 1970-02-09 | 1974-06-28 | Mobil Oil | Oxidative dehydrogenation of propionitrile to aerylonitrile |
| JPS5350119A (en) * | 1976-10-15 | 1978-05-08 | Monsanto Co | Method of oxidative dehydration of propionitrile |
| US4178305A (en) * | 1976-10-15 | 1979-12-11 | Monsanto Company | Oxidative dehydrogenation of propionitrile to acrylonitrile |
| CN1037282A (en) * | 1988-04-29 | 1989-11-22 | 国际壳牌研究有限公司 | Catalyst for dehydrogenating organic compounds and its production and application |
Non-Patent Citations (1)
| Title |
|---|
| 廖鹏: "丙烯腈生产用催化剂研究进展", 《江西化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109988082B (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105032428B (en) | A kind of preparation method of microwave heating synthetic catalyst and the method that catalyst one-step synthesis method cyclohexylamine is made based on the preparation method | |
| CN104028283B (en) | The method of magnetic carbon material load metallic catalyst and the dechlorination of catalysis chlorophenol thereof | |
| CN103121987B (en) | Method for preparing alkylene carbonate | |
| CN101264453A (en) | Titanium-silicon molecular sieve/tripolite composite catalyst and preparation | |
| CN113563201B (en) | Method for continuously and efficiently synthesizing 3, 4-dichloroaniline based on fixed bed microreactor | |
| CN106607091B (en) | Microporous polymer-nanometer metal particle catalyst and its preparation method and application | |
| CN101069847A (en) | Mesoporous-structure metal nickel catalyst and its preparing method and use | |
| CN105148990B (en) | A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst | |
| CN102658125B (en) | Catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and preparation method thereof | |
| CN108069831A (en) | A kind of method for synthesizing 2,3- dimethyl -4- fluorophenols | |
| CN106588758A (en) | Synthetic process for 2-hydrazinylpyridine derivative | |
| CN104028289A (en) | Nanocrystalline metal-loaded titanium carbide catalyst and method for preparing chloro aniline with nanocrystalline metal-loaded titanium carbide catalyst in reduction mode | |
| CN104387340B (en) | A kind of method for preparing N methyl piperazines and its catalyst | |
| CN103586049B (en) | A kind of bimetallic magnetic catalyst, preparation and react for Heck | |
| CN104689832B (en) | Preparation method for modified palladium-carbon catalyst for Suzuki coupling reaction | |
| CN109988082A (en) | A kind of method that continuous oxide hydrogenation prepares acrylonitrile | |
| CN105251488A (en) | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst | |
| CN105749954B (en) | A kind of no catalytic hydrogenation and its application for being catalyzed 1,5- dinitronaphthalene hydrogenation reactions | |
| CN111302981B (en) | Method for preparing taurine | |
| CN102836711B (en) | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof | |
| CN109174120A (en) | Loading type Pd-Ni duplex metal nano granule catalyst and its preparation method and application | |
| CN109529833A (en) | A kind of graphene oxide-loaded copper catalyst and its preparation method and application | |
| CN113943943A (en) | Gas diffusion electrode for preparing p-aminophenol by nitrobenzene electrolytic reduction method and preparation and application thereof | |
| CN104109095B (en) | The method that oxalate hydrogenation produces ethyl glycolate | |
| CN105777577B (en) | A kind of application of no catalytic hydrogenation in nitrocyclohexane hydrogenation reaction is catalyzed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |