CN102659625B - Industrial production method of acrylonitrile - Google Patents
Industrial production method of acrylonitrile Download PDFInfo
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- CN102659625B CN102659625B CN201210118473.2A CN201210118473A CN102659625B CN 102659625 B CN102659625 B CN 102659625B CN 201210118473 A CN201210118473 A CN 201210118473A CN 102659625 B CN102659625 B CN 102659625B
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Abstract
The invention provides an industrial production method of acrylonitrile, which comprises that the air, propylene and ammonia are subjected to ammoxidation inside a reactor and generate a reaction gas containing the acrylonitrile; the reaction gas enters a first tower and shock cooling, neutralization and cooling are achieved; the reaction gas which is subjected to shock cooling, neutralization and cooling enters a second tower and the water absorbs organic materials contained in the reaction gas; the water absorbing liquid enters a third tower, the acrylonitrile, hydrocyanic acid and water vapor steamed out by the third tower are subjected to condensation, and then separation of an aqueous phase and an organic phase is achieved in a quantizer of the third tower; the water phase inside the quantizer of the third tower are delivered to the third tower; the water phase introduced from a last piece of tower plates of a tower kettle of the third tower is subjected to heat exchange and then serves as absorbing water of the second tower; a gas phase containing acetonitrile is extracted from the side lines of the third tower and sent into a fourth tower and a rough acetonitrile product is obtained; and the organic phase in the quantizer of the third tower enters a fifth tower and a sixth tower sequentially and hydrocyanic acid and a acrylonitrile product are respectively obtained. According to the method, the reliability of a device is improved and the energy utilization is high.
Description
Technical field
The present invention relates to a kind of industrialized preparing process of vinyl cyanide.
Background technology
Vinyl cyanide is mainly used in the productions such as acrylic fibers, paracril, adiponitrile, acrylamide, ABS resin, medicine, also can be used for the production of hexanolactam, polyhydric alcohol polymer, and it has broad application prospects in fields such as synthon, synthetic rubber, plastics.
For acrylonitrile process; the exploitation of its production technique, improvement, to improve what will pay close attention to especially be environment protection and occupational health; according to the regulation of < < Occupational Exposure harm of poison grading > >; the toxicity of the related substance that acrylonitrile process relates to mostly is extremely or highly harm; as unreasonablely in flow process probably there is problem of environmental pollution, and cause personal injury.Therefore, the principle of design of processing method is to improve as far as possible the reliability of device, reduces the outer row who even stops process stream.
For traditional process for production of acrylonitrile, its operating process is longer, and the waste water and gas of generation is more, and the comprehensive utilization aspect of device energy need further to improve and be perfect.Longer operating process needs more investment ability to complete on the one hand, has also increased the leakage point in device simultaneously, for the safety and stability of system, is disadvantageous; The pollutant treatment difficulty of acrylonitrile installation is large, special treatment unit need to be set and process, and the discharge that reduces waste water and gas contributes to reduce plant investment, can improve the competitive power of product; The comprehensive utilization of energy is a systematic engineering of business, and traditional technology relates to seldom in this respect, and in device, each grade thermal source does not make full use of, and has caused the waste of energy, has also improved the working cost of device.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of industrialized preparing process of vinyl cyanide, by the optimization to conventional process flow, can effectively reduce the outer row of device refuse, improve the stability of device operation, improve the yield of product, also by the comprehensive utilization of energy, save the consumption of steam simultaneously, finally can produce qualified vinyl cyanide product.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of industrialized preparing process of vinyl cyanide, comprise the steps: air, in reactor, there is oxidative ammonolysis generation and contain vinyl cyanide in propylene and ammonia, the reactant gases of prussic acid and acetonitrile, this reactant gases enters in a tower and completes quenching, neutralization and cooling, through quenching, neutralization, cooling reactant gases enters in No. two towers and absorbs contained organic materials with water, this water absorption liquid enters in No. three towers, the vinyl cyanide that No. three column overhead steam, prussic acid is realized the separated of water and organic phase after condensation in No. three tower quantizers with water vapour, water in No. three tower quantizers is sent back in No. three towers, the water of drawing from No. three last piece column plates of tower tower reactor circulates and does No. two towers and absorb water after heat exchange, the gas phase that contains acetonitrile is sent into tower No. four from the extraction of No. three tower side lines, obtains crude acetonitrile product, organic phase in No. three tower quantizers enters No. five towers and No. six towers successively, obtains respectively prussic acid and vinyl cyanide product.
Specifically, method of the present invention comprises the steps:
Reaction raw materials propylene liquid and liquefied ammonia are mixed in reactor after vaporizer and superheater.Another raw air of reaction enters air compressor after filtering, also enters after compression in reactor and participates in reacting.
In reactor, propylene, ammonia and air, under catalyst action, carry out oxidizing reaction and generate vinyl cyanide, also generate prussic acid, acetonitrile, carbon monoxide, carbonic acid gas, propenal, vinylformic acid and water etc. simultaneously.Reactant gases flows out in thing and also comprises the unreacted propylene of part, ammonia, oxygen and nitrogen etc.Reaction generates gas and enters the cyclonic separator in reactor, and the catalyzer that reactant gases is carried secretly returns to bed by cyclone dip-leg.Reactant gases enters reactant gases water cooler and delivers to tower No. one after cooling.
Preferably, a described tower is 3 segment structures, and hypomere chilling, stage casing neutralization and epimere are cooling; The reactant gases coming from reactor enters in a tower from hypomere tower reactor, and hypomere recycling waste water is sprayed reactant gases quenching to about 70-90 ℃ through nozzle by a tower hypomere recycle pump; Reactant gases rises to midsection No. one by riser after hypomere quenching, in reactant gases unreacted ammonia be added in the sulfuric acid of a tower epimere and generate sulphur ammonium; Process gas after overpickling enters tower epimere No. one, first gas get off the liquid phase separation of carrying secretly in gas phase by scum dredger, this liquid phase is collected on a valve tray, by flow by gravity, send in No. two towers, gaseous phase materials enters one section of water cooler, and gas temperature is also delivered to after being further cooled to 30-50 ℃ in No. two towers.
Preferably, the stage casing of a described tower and hypomere are respectively equipped with 1 stripping tower (i.e. the first stripping tower and the second stripping tower).Midsection still liquid and hypomere still liquid, except a part is as spray liquid circulation, are also sent into respectively the first stripping tower and the second stripping tower, and in stripping tower, a small amount of vinyl cyanide material of carrying secretly in liquid phase is out returned to tower No. one by stripping.
The ammonium sulfate solution of a midsection can send sulphur ammonium retrieving arrangement to produce ammonium sulfate products by stage casing still liquid pump, in hypomere still liquid, contains granules of catalyst, can deliver to catalyst sedimentation groove.
From tower top, reactant gases out enters tower bottom No. two, water counter-current absorption in tower, recover acrylonitrile and other organic reaction product.Tower reactor obtain containing vinyl cyanide, acetonitrile, prussic acid and other organic aqueous solution (Fu Shui), this solution is delivered to tower No. three.In No. two towers, the most of gas of carbon monoxide, carbonic acid gas, nitrogen and unreacted oxygen and hydro carbons is delivered to tower exhaust treatment system No. two by tower top.From the poor-water of No. six tower reboilers, enter No. two tops of tower and carry out spray-absorption.
No. two tower bottoms is delivered to tower No. three through still liquid pump.In No. three towers, water adopts the method for extracting rectifying that vinyl cyanide, prussic acid is separated with acetonitrile as solvent.The vinyl cyanide of No. three column overhead, prussic acid and water vapor, through No. three tower condensers, are divided into organic phase and water in No. three tower quantizers.Organic phase (being mainly crude acetonitrile) is delivered to tower No. five, and water is sent tower back to No. three by No. three tower water pumps.No. three tower bottomss are pumped to multiple-effect evaporation with No. three tower bottomss and process.
Less organic poor-water (aqueous solvent) is contained in the bottom of No. three towers, and this water temp is 100-130 ℃.Preferably, the water of drawing from No. three last piece column plates of tower tower reactor (poor-water) above, by series system successively as the thermal source of No. five towers and No. six tower reboilers.
The poor-water of No. three tower bottoms need to be returned to No. two towers and continue as solvent, reactant gases to be absorbed, but its temperature is higher, for meeting the cooling of assimilation effect needs, the present invention fully utilizes the poor-water heat of No. three tower bottoms, first this water enter tower reboiler No. five, and after heat exchange, series connection enters tower reboiler No. six again, for two towers provide heat, circulation water and steam has been saved in this measure, has good economic benefit.
Contain the gas phase of acetonitrile, water and a small amount of prussic acid by the extraction of No. three tower side lines, enter tower No. four.In No. four towers, acetonitrile, water and prussic acid, from overhead extraction, can be delivered to acetonitrile refining device and produce acetonitrile product.No. four tower tower reactor is mainly water, and this water pump is sent back in No. three towers.
Organic phase from No. three towers enters tower No. five.No. five tower is negative-pressure operation, and tower top obtains hydrogen cyanide product.Vinyl cyanide after tower reactor is dewatered, delivers to tower No. six.No. six tower also operates under negative pressure.Because vinyl cyanide and water form azeotrope, so this column overhead obtains is vinyl cyanide and water, so vinyl cyanide product is from the extraction of No. six tower side lines, send product storage tank after cooling.The overhead product of No. six towers is back to tower No. three.Tower reactor is vinyl cyanide and high boiling material, through No. six tower reactor liquid pumps, also returns to tower No. three.
The present invention rationally arranges the working pressure of No. five towers and No. six towers on the basis of negative-pressure operation, makes mode that the solvent poor-water of No. three towers can be by series connection successively as the thermal source of No. five towers and No. six tower reboilers.Preferably, No. five towers are negative-pressure operation, and tower top pressure is 60-90KPa (A), and tower reactor pressure is 80-110KPa (A), and No. six tower also operates under negative pressure, and tower top pressure is 20-60KPa (A), and tower reactor pressure is 50-90KPa (A).
Compare with traditional technology and related invention, the present invention has following advantage:
1, the present invention is designed to the structure of three sections by a tower, chilling, the neutralization and cooling of process gas in a tower, have been realized, the functions of the equipments of a tower have been strengthened, compare with traditional technology, relevant device is integrated, and the liquid under scum dredger enters tower No. two by flow by gravity, has saved the investment of pump, also reduced leakage point, improved the safety and reliability of system simultaneously.
2, the present invention respectively arranges a stripping tower at tower hypomere and stage casing, a small amount of material steam containing is put forward to the materials such as a small amount of vinyl cyanide of carrying secretly in recycle-water, acetonitrile, prussic acid in the still liquid of two sections.This technique has improved product yield; to produce vinyl cyanide product per ton; by two sections of recyclable vinyl cyanide of stripping, acetonitrile and the about 10.4kg of prussic acid; the about 8kg of vinyl cyanide wherein; can improve product, byproduct yield 1%; also reduced the content of vinyl cyanide material in waste water, played the effect of protection of the environment simultaneously.
3, because vinyl cyanide and prussic acid all have very strong toxicity, so vinyl cyanide and hydrogen cyanide product tower generally be negative-pressure operation, can effectively prevent the leakage of material, improves the safety and stability of device.The present invention rationally arranges the working pressure of two towers on the basis of negative-pressure operation, make No. three towers solvent poor-water can by series connection mode successively as the thermal source of No. five towers and No. six tower reboilers, saved the consumption of circulation water and steam; And No. five towers and No. six towers are to provide thermal source by steam in traditional technology, produce vinyl cyanide product needed per ton and consume 10.4t steam, also need to consume 49.2m simultaneously
3recirculated water (in 10 ℃ of temperature difference) is for cooling solvent poor-water.The method of the invention total energy approach degree is high, and pressure and the temperature of poor-water are more gentle simultaneously, has greatly extended the work-ing life of reboiler, has reduced the operational risk of reboiler, the security that has greatly improved system.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure:
1, reactor 2, tower 3, No. two towers
4, No. three towers 5, No. four towers 6, No. five towers
7, No. six towers 8, the first stripping tower 9, the second stripping tower
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
Reaction raw materials propylene liquid and liquefied ammonia are mixed in reactor 1 after vaporizer and superheater.Another raw air of reaction enters air compressor after filtering, also enters after compression the interior participation reaction of reactor 1.
In reactor 1, propylene, ammonia and air, under catalyst action, carry out oxidizing reaction and generate vinyl cyanide, also generate prussic acid, acetonitrile, carbon monoxide, carbonic acid gas, propenal, vinylformic acid and water etc. simultaneously.Reactant gases flows out in thing and also comprises the unreacted propylene of part, ammonia, oxygen and nitrogen etc.Reaction generates gas and enters the cyclonic separator in reactor 1, and the catalyzer that reactant gases is carried secretly returns to bed by cyclone dip-leg.Reactant gases enters reactant gases water cooler and delivers to tower 2 No. one after cooling.
No. one tower 2 is divided into three parts, and hypomere chilling, stage casing neutralization and epimere are cooling.The reactant gases coming from reactor 1 enters in a tower 2 from hypomere tower reactor, hypomere recycling waste water by tower 2 hypomere recycle pump through nozzle spray by reactant gases quenching to approximately 70 ℃.Reactant gases rises to tower 2 stage casings No. one by riser after hypomere quenching, in reactant gases unreacted ammonia be added in the sulfuric acid of tower 2 epimeres and generate sulphur ammonium.Process gas after overpickling enters tower 2 epimeres No. one, first gas get off the liquid phase separation of carrying secretly in gas phase by scum dredger, this liquid phase is collected on a valve tray, by flow by gravity, send in No. two towers 3 of distillation system, gaseous phase materials enters one section of water cooler, and gas temperature is further cooled in No. two towers 3 also delivering to distillation system after 30 ℃.Tower 2 stage casing still liquid and hypomere still liquid, except a part is as spray liquid circulation, are also sent into respectively the first stripping tower 8 and the second stripping tower 9, and in stripping tower, a small amount of vinyl cyanide material of carrying secretly in liquid phase is out returned to tower 2 No. one by stripping.
The ammonium sulfate solution in tower 2 stage casings can send sulphur ammonium retrieving arrangement to produce ammonium sulfate products by stage casing still liquid pump, in hypomere still liquid, contains granules of catalyst, can deliver to catalyst sedimentation groove.
From tower 2 top, reactant gases out enters tower 3 bottoms No. two, water counter-current absorption in tower, recover acrylonitrile and other organic reaction product.Tower reactor obtain containing vinyl cyanide, acetonitrile, prussic acid and other organic aqueous solution (Fu Shui), this solution is delivered to tower 4 No. three.In No. two towers 3, the most of gas of carbon monoxide, carbonic acid gas, nitrogen and unreacted oxygen and hydro carbons is delivered to tower 3 exhaust treatment systems No. two by tower top.From the poor-water of No. six tower reboilers, enter No. two tower 3 tops and carry out spray-absorption.
No. two tower 3 still liquid are delivered to tower 4 No. three through still liquid pump.In No. three towers 4, water adopts the method for extracting rectifying that vinyl cyanide, prussic acid is separated with acetonitrile as solvent.Vinyl cyanide, prussic acid and the water vapor on No. three tower 4 tops, through No. three tower 4 condensers, are divided into organic phase and water in No. three tower quantizers.Organic phase (being mainly crude acetonitrile) is delivered to tower 6 No. five, and water is sent tower 4 back to No. three by No. three tower 4 water pumps.No. three tower 4 still liquid are delivered to multiple-effect evaporation with No. three tower 4 still liquid pumps and are processed.Less organism is contained in the bottom of No. three towers 4, poor-water (aqueous solvent) is drawn and is entered a surge tank from No. three last piece column plates of tower 4 tower reactors, and this water temp is 100 ℃, first enters tower 6 reboilers No. five, after heat exchange, series connection enters tower reboiler No. six again, for two towers provide heat.
Contain the gas phase of acetonitrile, water and a small amount of prussic acid by No. three tower 4 side line extraction, enter tower 5 No. four.In No. four towers 5, acetonitrile, water and prussic acid, from overhead extraction, can be delivered to acetonitrile refining device and produce acetonitrile product.No. four tower 5 tower reactors are mainly water, and this water pump is sent back in No. three towers 4.
Organic phase from No. three towers 4 enters tower 6 No. five.No. five tower 6 is negative-pressure operation, and tower top pressure is 60KPa (A), and tower reactor pressure is 80KPa (A), and tower top obtains hydrogen cyanide product.Vinyl cyanide after tower reactor is dewatered, delivers to tower 7 No. six.
No. six tower 7 also operates under negative pressure, and tower top pressure is 20KPa (A), and tower reactor pressure is 50KPa (A).What this column overhead obtained is vinyl cyanide and water, and vinyl cyanide product, from No. six tower 7 side line extraction, send product storage tank after cooling.The overhead product of No. six towers 7 is back to tower 4 No. three.Tower reactor is vinyl cyanide and high boiling material, through No. six tower 7 still liquid pumps, also returns to tower 4 No. three.
Embodiment 2
Reaction raw materials propylene liquid and liquefied ammonia are mixed in reactor 1 after vaporizer and superheater.Another raw air of reaction enters air compressor after filtering, also enters after compression the interior participation reaction of reactor 1.
In reactor 1, propylene, ammonia and air, under catalyst action, carry out oxidizing reaction and generate vinyl cyanide, also generate prussic acid, acetonitrile, carbon monoxide, carbonic acid gas, propenal, vinylformic acid and water etc. simultaneously.Reactant gases flows out in thing and also comprises the unreacted propylene of part, ammonia, oxygen and nitrogen etc.Reaction generates gas and enters the cyclonic separator in reactor 1, and the catalyzer that reactant gases is carried secretly returns to bed by cyclone dip-leg.Reactant gases enters reactant gases water cooler and delivers to tower 2 No. one after cooling.
No. one tower 2 is divided into three parts, and hypomere chilling, stage casing neutralization and epimere are cooling.The reactant gases coming from reactor 1 enters in a tower 2 from hypomere tower reactor, hypomere recycling waste water by tower 2 hypomere recycle pump through nozzle spray by reactant gases quenching to approximately 83 ℃.Reactant gases rises to tower 2 stage casings No. one by riser after hypomere quenching, in reactant gases unreacted ammonia be added in the sulfuric acid of tower 2 epimeres and generate sulphur ammonium.Process gas after overpickling enters tower 2 epimeres No. one, first gas get off the liquid phase separation of carrying secretly in gas phase by scum dredger, this liquid phase is collected on a valve tray, by flow by gravity, send in No. two towers 3 of distillation system, gaseous phase materials enters one section of water cooler, and gas temperature is further cooled in No. two towers 3 also delivering to distillation system after 40 ℃.Tower 2 stage casing still liquid and hypomere still liquid, except a part is as spray liquid circulation, are also sent into respectively the first stripping tower 8 and the second stripping tower 9, and in stripping tower, a small amount of vinyl cyanide material of carrying secretly in liquid phase is out returned to tower 2 No. one by stripping.
The ammonium sulfate solution in tower 2 stage casings can send sulphur ammonium retrieving arrangement to produce ammonium sulfate products by stage casing still liquid pump, in hypomere still liquid, contains granules of catalyst, can deliver to catalyst sedimentation groove.
From tower 2 top, reactant gases out enters tower 3 bottoms No. two, water counter-current absorption in tower, recover acrylonitrile and other organic reaction product.Tower reactor obtain containing vinyl cyanide, acetonitrile, prussic acid and other organic aqueous solution (Fu Shui), this solution is delivered to tower 4 No. three.In No. two towers 3, the most of gas of carbon monoxide, carbonic acid gas, nitrogen and unreacted oxygen and hydro carbons is delivered to tower 3 exhaust treatment systems No. two by tower top.From the poor-water of No. six tower reboilers, enter No. two tower 3 tops and carry out spray-absorption.
No. two tower 3 still liquid are delivered to tower 4 No. three through still liquid pump.In No. three towers 4, water adopts the method for extracting rectifying that vinyl cyanide, prussic acid is separated with acetonitrile as solvent.Vinyl cyanide, prussic acid and the water vapor of No. three tower 4 tower tops, through No. three tower 4 condensers, is divided into organic phase and water in No. three tower quantizers.Organic phase (being mainly crude acetonitrile) is delivered to tower 6 No. five, and water is sent tower 4 back to No. three by No. three tower 4 water pumps.No. three tower 4 tower bottomss are pumped to multiple-effect evaporation with No. three tower 4 tower bottomss and process.Less organism is contained in the bottom of No. three towers 4, poor-water (aqueous solvent) is drawn and is entered a surge tank from No. three last piece column plates of tower 4 tower reactors, and this water temp is 115 ℃, first enters tower reboiler No. five, after heat exchange, series connection enters tower reboiler No. six again, for two towers provide heat.
Contain the gas phase of acetonitrile, water and a small amount of prussic acid by No. three tower 4 side line extraction, enter tower 5 No. four.In No. four towers 5, acetonitrile, water and prussic acid, from overhead extraction, can be delivered to acetonitrile refining device and produce acetonitrile product.No. four tower 5 tower reactors are mainly water, and this water pump is sent back in No. three towers 4.
Organic phase from No. three towers 4 enters tower 6 No. five.No. five tower 6 is negative-pressure operation, and tower top pressure is 75KPa (A), and tower reactor pressure is 95KPa (A), and tower top obtains hydrogen cyanide product.Vinyl cyanide after tower reactor is dewatered, delivers to tower 7 No. six.
No. six tower 7 also operates under negative pressure, and tower top pressure is 40KPa (A), and tower reactor pressure is 70KPa (A).What this column overhead obtained is vinyl cyanide and water, and vinyl cyanide product, from No. six tower 7 side line extraction, send product storage tank after cooling.The overhead product of No. six towers 7 is back to tower 4 No. three.Tower reactor is vinyl cyanide and high boiling material, through No. six tower 7 still liquid pumps, also returns to tower 4 No. three.
Embodiment 3
Reaction raw materials propylene liquid and liquefied ammonia are mixed in reactor 1 after vaporizer and superheater.Another raw air of reaction enters air compressor after filtering, also enters after compression the interior participation reaction of reactor 1.
In reactor 1, propylene, ammonia and air, under catalyst action, carry out oxidizing reaction and generate vinyl cyanide, also generate prussic acid, acetonitrile, carbon monoxide, carbonic acid gas, propenal, vinylformic acid and water etc. simultaneously.Reactant gases flows out in thing and also comprises the unreacted propylene of part, ammonia, oxygen and nitrogen etc.Reaction generates gas and enters the cyclonic separator in reactor 1, and the catalyzer that reactant gases is carried secretly returns to bed by cyclone dip-leg.Reactant gases enters reactant gases water cooler and delivers to tower 2 No. one after cooling.
No. one tower 2 is divided into three parts, and hypomere chilling, stage casing neutralization and epimere are cooling.The reactant gases coming from reactor 1 enters in a tower 2 from hypomere tower reactor, hypomere recycling waste water by tower 2 hypomere recycle pump through nozzle spray by reactant gases quenching to approximately 90 ℃.Reactant gases rises to tower 2 stage casings No. one by riser after hypomere quenching, in reactant gases unreacted ammonia be added in the sulfuric acid of tower 2 epimeres and generate sulphur ammonium.Process gas after overpickling enters tower 2 epimeres No. one, first gas get off the liquid phase separation of carrying secretly in gas phase by scum dredger, this liquid phase is collected on a valve tray, by flow by gravity, send in No. two towers 3 of distillation system, gaseous phase materials enters one section of water cooler, and gas temperature is further cooled in No. two towers 3 also delivering to distillation system after 50 ℃.Tower 2 stage casing still liquid and hypomere still liquid, except a part is as spray liquid circulation, are also sent into respectively the first stripping tower 8 and the second stripping tower 9, and in stripping tower, a small amount of vinyl cyanide material of carrying secretly in liquid phase is out returned to tower 2 No. one by stripping.
The ammonium sulfate solution in tower 2 stage casings can send sulphur ammonium retrieving arrangement to produce ammonium sulfate products by stage casing still liquid pump, in hypomere still liquid, contains granules of catalyst, can deliver to catalyst sedimentation groove.
From tower 2 top, reactant gases out enters tower 3 bottoms No. two, water counter-current absorption in tower, recover acrylonitrile and other organic reaction product.Tower reactor obtain containing vinyl cyanide, acetonitrile, prussic acid and other organic aqueous solution (Fu Shui), this solution is delivered to tower 4 No. three.In No. two towers 3, the most of gas of carbon monoxide, carbonic acid gas, nitrogen and unreacted oxygen and hydro carbons is delivered to tower 3 exhaust treatment systems No. two by tower top.From the poor-water of No. six tower reboilers, enter No. two tower 3 tops and carry out spray-absorption.
No. two tower 3 still liquid are delivered to tower 4 No. three through still liquid pump.In No. three towers 4, water adopts the method for extracting rectifying that vinyl cyanide, prussic acid is separated with acetonitrile as solvent.Vinyl cyanide, prussic acid and the water vapor of No. three tower 4 tower tops, through No. three tower 4 condensers, is divided into organic phase and water in No. three tower quantizers.Organic phase (being mainly crude acetonitrile) is delivered to tower 6 No. five, and water is sent tower 4 back to No. three by No. three tower 4 water pumps.No. three tower 4 tower bottomss are pumped to multiple-effect evaporation with No. three tower 4 tower bottomss and process.Less organism is contained in the bottom of No. three towers 4, poor-water (aqueous solvent) is drawn and is entered a surge tank from No. three last piece column plates of tower 4 tower reactors, and this water temp is 130 ℃, first enters tower reboiler No. five, after heat exchange, series connection enters tower reboiler No. six again, for two towers provide heat.
Contain the gas phase of acetonitrile, water and a small amount of prussic acid by No. three tower 4 side line extraction, enter tower 5 No. four.In No. four towers 5, acetonitrile, water and prussic acid, from overhead extraction, can be delivered to acetonitrile refining device and produce acetonitrile product.No. four tower 5 tower reactors are mainly water, and this water pump is sent back in No. three towers 4.
Organic phase from No. three towers 4 enters tower 6 No. five.No. five tower 6 is negative-pressure operation, and tower top pressure is 90KPa (A), and tower reactor pressure is 110KPa (A), and tower top obtains hydrogen cyanide product.Vinyl cyanide after tower reactor is dewatered, delivers to tower 7 No. six.
No. six tower 7 also operates under negative pressure, and tower top pressure is 60KPa (A), and tower reactor pressure is 90KPa (A).What this column overhead obtained is vinyl cyanide and water, and vinyl cyanide product, from No. six tower 7 side line extraction, send product storage tank after cooling.The overhead product of No. six towers 7 is back to tower 4 No. three.Tower reactor is vinyl cyanide and high boiling material, through No. six tower 7 still liquid pumps, also returns to tower 4 No. three.
Above preferred embodiment of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the present patent application scope and improvement etc., within all should still belonging to patent covering scope of the present invention.
Claims (1)
1. the industrialized preparing process of a vinyl cyanide, it is characterized in that: comprise the steps: air, in reactor, there is oxidative ammonolysis generation and contain vinyl cyanide in propylene and ammonia, the reactant gases of prussic acid and acetonitrile, this reactant gases enters in a tower and completes quenching, neutralization and cooling, through quenching, neutralization, cooling reactant gases enters in No. two towers and absorbs contained organic materials with water, this water absorption liquid enters in No. three towers, the vinyl cyanide that No. three column overhead steam, prussic acid is realized the separated of water and organic phase after condensation in No. three tower quantizers with water vapour, water in No. three tower quantizers is sent back in No. three towers, the water of drawing from No. three last piece column plates of tower tower reactor circulates and does No. two towers and absorb water after heat exchange, the gas phase that contains acetonitrile is sent into tower No. four from the extraction of No. three tower side lines, obtains crude acetonitrile product, organic phase in No. three tower quantizers enters No. five towers and No. six towers successively, obtains respectively prussic acid and vinyl cyanide product,
A described tower is 3 segment structures, and hypomere chilling, stage casing neutralization and epimere are cooling; The reactant gases coming from reactor enters in a tower from hypomere tower reactor, and hypomere recycling waste water is sprayed reactant gases quenching to 70-90 ℃ through nozzle by a tower hypomere recycle pump; Reactant gases rises to midsection No. one by riser after hypomere quenching, in reactant gases unreacted ammonia be added in the sulfuric acid of a tower epimere and generate sulphur ammonium; Process gas after overpickling enters tower epimere No. one, first gas get off the liquid phase separation of carrying secretly in gas phase by scum dredger, this liquid phase is collected on a valve tray, by flow by gravity, send in No. two towers, gaseous phase materials enters one section of water cooler, and gas temperature is also delivered to after being further cooled to 30-50 ℃ in No. two towers;
The stage casing of a described tower and hypomere are respectively equipped with 1 stripping tower;
The water of drawing from No. three last piece column plates of tower tower reactor, by series system successively as the thermal source of No. five towers and No. six tower reboilers;
The absolute pressure of top of the tower of No. five towers is 60-90KPa, and tower reactor absolute pressure is 80-110KPa; No. six towers are also negative-pressure operation, and absolute pressure of top of the tower is 20-60KPa, and tower reactor absolute pressure is 50-90KPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210118473.2A CN102659625B (en) | 2012-04-20 | 2012-04-20 | Industrial production method of acrylonitrile |
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| CN104941380A (en) * | 2014-03-31 | 2015-09-30 | 英尼奥斯欧洲股份公司 | Improved smog eliminator operation for quenching effluent |
| CN105521616A (en) * | 2014-09-29 | 2016-04-27 | 英尼奥斯欧洲股份公司 | Evaporation system used for process stream |
| CN104672106A (en) * | 2015-03-06 | 2015-06-03 | 英尼奥斯欧洲股份公司 | Improved acrylonitrile manufacture process |
| CN104693068B (en) * | 2015-03-06 | 2017-10-20 | 英尼奥斯欧洲股份公司 | Improved acrylonitrile manufacture |
| CN105985262A (en) * | 2015-03-06 | 2016-10-05 | 英尼奥斯欧洲股份公司 | Improved acrylonitrile preparation |
| CN104693069A (en) * | 2015-03-06 | 2015-06-10 | 英尼奥斯欧洲股份公司 | Improved acrylonitrile production |
| CN106474900A (en) * | 2015-08-26 | 2017-03-08 | 中国石油化工股份有限公司 | Improve recovery of acrylonitrile the chilling tower apparatus of reduces cost and quick cooling method |
| CN108164436B (en) * | 2018-02-23 | 2023-12-19 | 上海晟兰石化工程技术有限公司 | Process and system for preparing acrylonitrile and propylene by ammoxidation of crude propylene |
| CN112439220A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Recovery tower kettle liquid treatment system |
| CN112441948A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Comprehensive utilization method and system for energy of water recovered by dehydrocyanation tower |
| CN112439302A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Tail gas treatment method in acrylonitrile production system |
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