CN101798265B - Novel method for preparing vinyl acetate from bioethanol - Google Patents
Novel method for preparing vinyl acetate from bioethanol Download PDFInfo
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Abstract
The invention relates to a novel method for preparing vinyl acetate from bioethanol. Ethanol is fermented into finished yeast mash used as the raw material, and three cells, i.e. bio-ethylene preparation, vinyl acetate synthetic reaction, vinyl acetate refinement, are used for producing the vinyl acetate product satisfying the requirements. The method is realized in a way that: the mass concentration of the ethanol water solution from an ethanol distillation tower is 40-60%, and the raw material ethanol used for preparing ethylene through dehydration does not need to be diluted by adding water, and is directly vaporized by heating and conveyed into an ethylene reactor; after cooling to condense the ethylene reaction gas from an ethylene reactor, gas is separated from liquid in a gas/liquid separating tank, and the gas mainly containing the ethylene is conveyed to a vinyl acetate reaction unit to synthesize the vinyl acetate after being compressed by using an ethylene compressor, thereby realizing zero consumption of process water in the ethylene production process. Thus, the invention simplifies and shortens the production process and reduces the energy consumption and material consumption in the vinyl acetate production process. By using the method, renewable biomass materials in the vinyl acetate production process can partially replace unrenewable fossil materials.
Description
Technical field
The present invention relates to a kind of novel method of preparing vinyl acetate from bioethanol, the method is according to the characteristics of bio-ethanol raw material and the preparation of biological ethane intermediate product, the technical optimizations such as bio-ethanol raw material, ethene intermediate product and the preparation of vinyl acetate product is integrated, thereby shorten the production process of having simplified preparing vinyl acetate from bioethanol, reduced energy consumption and material consumption that vinyl acetate is produced, improved take bio-ethanol as the raw material production vinyl acetate competitiveness of product in market.
Background technology
Vinyl acetate (VAc) is a kind of important Organic Chemicals, by self-polymerization or with other monomer copolymerization, can generate the derivatives such as polyvinyl alcohol (PVA), vinyl acetate ethylene (EVA), polyvinyl acetate (PVAC), vinyl acetate-vinyl chloride copolymer (EVC).The purposes of these derivatives is very extensive, generally can be used for caking agent, the aspects such as the cementing agent of paper or fabric, paint, ink, leather processing, emulsifying agent, water-solubility membrane, soil improvement agent.Vinyl acetate is as intermediate, and the expansion along with the non-fiber art of polyvinyl alcohol is used increases and improves so that the demand of vinyl acetate is continuous.
The vinyl acetate production process route has two kinds of ethylene process and acetylene methods.Acetylene method was the main production method of vinyl acetate in the past in the sixties in 20th century.Since 20 century 70s, along with the development of Global Oil chemical industry, ethene is cheap and easy to get, and ethylene process has occupied the dominant position that vinyl acetate is produced thus, and at present, the throughput of ethylene process device accounts for 77.48% of total capacity.
Ethylene process is divided into again ethene liquid phase method and ethene vapor phase process.The ethene liquid phase method is not eliminated owing to etching problem and Technological Economy pass a test, and the ethene vapor phase process is occupied an leading position owing to manufacturability and good economy performance.But because producing vinyl acetate, ethylene process relies on petroleum resources, along with World Oil Market imbalance between supply and demand serious unbalance, and ballooning oil prices, economic competitiveness descends.Therefore, adopt the production technology of the alternative ethylene production vinyl acetates take oil as raw material of renewable resources such as bio-ethanol, become the focus that industry is paid close attention to.
Bio-ethanol is take starchiness, saccharic or biomass as raw material, makes through operations such as liquefaction, fermentation, distillations, and be a kind of reproducible important foundation raw material and product.Beginning in 2008, the external interdependency of CNPC surpasses 50%.Therefore, the renewable resourcess such as popularization bio-ethanol substitute take oil as raw material production basic chemical raw materials and product, to guaranteeing the energy security of China, improve the ecological environment, and promote that the agricultural development meaning is very great.
The present invention relates to a kind of novel method of preparing vinyl acetate from bioethanol, will adopt the ripe wine with dregs of ethanol fermentation is raw material, produces the vinyl acetate product by refining three unit of biological ethane preparation, vinyl acetate building-up reactions and vinyl acetate.The method adopts the alternative ethylene raw take oil as raw material of bio-ethanol renewable raw materials, and according to the preparation characteristic of bio-ethanol raw material and biological ethane intermediate product, the technology such as employing thermal coupling precise distillation prepare the bio-ethanol raw material, the process optimizations such as ethene intermediate product and vinyl acetate production are integrated, thereby simplify the production process that has shortened preparing vinyl acetate from bioethanol, energy consumption and material consumption that vinyl acetate is produced have been reduced, improved take bio-ethanol as the raw material production vinyl acetate competitiveness of product in market, realized the circulation low-carbon (LC) production model of vinyl acetate product
Summary of the invention
The present invention relates to a kind of novel method of preparing vinyl acetate from bioethanol, it is raw material that the method will adopt the ripe wine with dregs of ethanol fermentation, meets the requirements of the vinyl acetate product by refining three the unit productions of biological ethane preparation, vinyl acetate building-up reactions and vinyl acetate.Thereby realize the preparing vinyl acetate from bioethanol process, the recyclable organism raw material substitutes the part of non-renewable fossil feedstock, simplifies and shortens production process, reduces energy consumption and material consumption that vinyl acetate is produced.
Technical scheme of the present invention:
The present invention relates to a kind of novel method of preparing vinyl acetate from bioethanol, it is characterized in that take from the ripe wine with dregs of the ethanol fermentation of ethanol fermentation unit as raw material production vinyl acetate product, the ripe wine with dregs ethanol of ethanol fermentation volumetric concentration is 5-20%, production process comprises that biological ethane prepares unit, vinyl acetate building-up reactions unit and vinyl acetate product purification unit
Feature of the present invention is to prepare the unit at biological ethane, it is 40～60% aqueous ethanolic solution from the ethanol mass concentration of ethanol distillation tower 2, ethanol raw material as the standby ethene of Dehydration operates without thin up, send into ethylene reaction device 12 after the direct boiling heating, realize that the process water consumption in the ethylene production is zero.
Feature of the present invention is to prepare the unit at biological ethane, after the ethylene reaction gas cooling condensation from ethylene reaction device 12, in vapor-liquid separation tank, carry out vapor-liquid separation, mainly contain the gas material of ethene without further separating-purifying, directly by after the ethylene compressor compression, send into vinyl acetate reaction member synthesis of acetic acid ethene.
Feature of the present invention is that overhead condenser and the Second distillation column reboiler 51 of the 6th rectifying tower 46 is same equipment, and Second distillation column reboiler 51 heating mediums are the overhead vapours of the 6th rectifying tower 46, and Second distillation column 42 operations do not consume live steam.
Feature of the present invention is in vinyl acetate product purification unit, the overhead condenser of the 5th rectifying tower 45 and the 7th rectifying tower reboiler 58 are same equipment, the 7th rectifying tower reboiler 58 heating mediums are the overhead vapours of the 5th rectifying tower 45, and 47 operations of the 7th rectifying tower do not consume live steam.
The concrete Production Flow Chart of the novel method of preparing vinyl acetate from bioethanol is described as follows:
The production process that the ripe wine with dregs of employing ethanol fermentation is the raw material production vinyl acetate mainly comprises three unit: biological ethane prepares unit, vinyl acetate building-up reactions unit and vinyl acetate product purification unit.
1. biological ethane prepares the unit
Biological ethane prepares production process and prepares the unit schema referring to Fig. 1-biological ethane.Prepare the unit by ethanol distillation and dehydration operation from the ripe wine with dregs of the ethanol fermentation of fermentation unit at biological ethane, obtain the biological ethane raw material that vinyl acetate is produced.Biological ethane prepares the unit and mainly is made of ethanol distillation tower 2, ethanol evaporation tank 9, ethylene reaction device 12, vapor-liquid separation tank 15 and ethylene compressor 16 etc.
From the ripe wine with dregs of the ethanol fermentation of zymamsis unit at first after the heat-eliminating medium preheating as ethanol distillation column overhead condenser 4, after further heating up by tower bottoms water cooler 1 again, enter ethanol distillation tower 2 as charging at last and carry out distillation operation, the ripe wine with dregs ethanol of ethanol fermentation volumetric concentration is 5-20%, ethanol distillation tower 2 working pressures (absolute pressure) are 0.02～0.5MPa, the ripe wine with dregs of ethanol fermentation removes water in the ethanol distillation tower, organic acid and heavy component impurity etc., it is 40～60% aqueous ethanolic solution that overhead vapours obtains the ethanol mass concentration through overhead condenser 4 and cat head aftercooler 5, aqueous ethanolic solution enters return tank 6, the ethanol content of cat head aqueous ethanolic solution is adjusted control by parameters such as control feeding temperature and quantity of reflux, cat head aftercooler 5 heat-eliminating mediums are recirculated cooling water, alcohol concn in the return tank 6 is that the aqueous ethanolic solution of 40-60% is sent into three grades of water coolers of ethene 13 and reacted the heat exchange of generation gas to the ethanol evaporation temperature, enter into ethanol evaporation tank 9, ethanol distillation tower 2 stills are adopted after 1 cooling of still liquid water cooler and are expelled to Waste Water Treatment outside the device.
Aqueous ethanolic solution after the preheating carries out the carburation by evaporation operation in evaporating pot 9, vaporizer heats by steam heater 7 and ethene secondary coolers 8, alcohol steam after the vaporization generates the further heat exchange of gas at ethene one-level water cooler 10 and ethylene reaction from the ethylene reaction device and heats up, deliver at last raw material electric heater 11 and be heated to temperature of reaction and enter ethylene reaction device 12, it is 350 ℃～500 ℃ that reaction generates the gas Heating temperature.Ethanol carries out adiabatic dehydration reaction in the ethylene reaction device, obtains ethene and water, and the catalyzer in the ethylene reaction device is molecular sieve or AlO
3The temperature of reaction of ethylene reaction device outlet is down to 250 ℃～350 ℃, ethylene reaction gas is successively by ethene one-level water cooler 10, ethene secondary coolers 8, three grades of water coolers 13 of ethene and ethene level Four level water cooler 14, cool the temperature to 40 ℃～80 ℃, then enter and carry out vapor-liquid separation in the vapor-liquid separation tank 15, the liquid phase discharger that contains water and a small amount of ethanol, acetaldehyde, ether etc. is delivered to Waste Water Treatment, contains CO
2, H
2, CH
4, the impurity such as acetaldehyde and ethane the crude ethylene gas phase enter ethylene compressor 16, send into vinyl acetate building-up reactions unit, in vinyl acetate product purification process in the lump separation removal, simplified technical process, reduce process cost, suppressed the generation of side reaction in the vinyl acetate reaction process.
Ethanol volumetric concentration from ethanol distillation tower 2 is the aqueous ethanolic solution of 40-50%, directly send into ethylene reaction device 12 without further dehydration, with traditional technology adopt the aqueous ethanolic solution of volumetric concentration about 95% be raw material ratio, omitted the operation that adds certain water gaging in the raw material, to realize improving the yield of ethene, solve the purpose of the carbon distribution of reactor, reduced process water consumption and the processing wastewater quantity discharged in the production process.
2. vinyl acetate building-up reactions unit
Vinyl acetate building-up reactions unit production process is referring to Fig. 2-vinyl acetate building-up reactions unit schema.At this unit acetic acid and the two kinds of raw materials of ethene that prepare the unit from biological ethane, chemical reaction occurs in the vinyl acetate synthesis reactor generate vinyl acetate.The vinyl acetate synthesis unit is mainly by vinyl acetate synthesis reactor 18, acetic acid vaporizer 17, gas delivery tower 25, water wash column 31, absorption tower 32, desorption tower 33 formations such as grade.
After fresh ethylene and cyclic ethylene mix, after carrying out heat exchange and heat up by reaction gas the second water cooler 23 and reaction gas, enter acetic acid vaporizer 17 from the bottom, in vaporizer ethylene raw saturated acetic acid gas from the vaporizer Base top contact, by reaction gas the first water cooler 21 and again heat exchange intensification of reaction gas, then be heated to 130～200 ℃ through feed gas heater 22 usefulness live steams again.This gas is sent into oxygen mixer 19 again and is mixed with oxygen feed, makes oxygen account for 4.5-6.0% in whole reaction mixture, sends into vinyl acetate synthesis reactor 18 from oxygen mixer material out by the top.
Vinyl acetate synthesis reactor 18 is calandria type fixed bed reactor, pass into hot water between the shell side pipe of calandria type fixed bed reactor 18, liberated heat in the vinyl acetate synthetic reaction process, shift out reaction heat by hot water intensification between the pipe of calandria type fixed bed reactor 18, hot water after the intensification leaves calandria type fixed bed reactor 18, enter 20 vapour liquid separator step-downs and produce steam, for other productive unit, the hot water Returning reactor recycle after the cooling.Load the palladium catalyst series in vinyl acetate synthesis reactor 18 tubulations, temperature of reaction is that 130～200 ℃, reaction pressure are 0.4～1.2MPa.The reacting synthesis gas body that vinyl acetate synthesis reactor 18 bottoms are got rid of carries out the heat exchange cooling by the first water cooler 21 and the second water cooler 23 with unstripped gas successively, then enter again reaction gas condenser 24, with recirculated cooling water reaction gas is further sent into gas delivery tower 25 after the cooling.The hypomere of gas delivery tower 25 and the circulating absorption solution in stage casing adopt respectively gas delivery tower the first water cooler 27,28 coolings of gas delivery tower the second water cooler, heat-eliminating medium is respectively chilled brine and water coolant, gas delivery tower 25 gets off the high boiling point material condensations such as contained acetic acid, vinyl acetate in the reaction gas, send into degassing vessel 25, gas delivery tower 25 epimeres acetic acid drip washing gas.From gas delivery tower 25 tops reaction gas out, after recycle gas compressor 26 compressions, vinyl acetate synthesis reactor 18 is returned in most of circulation, small part is delivered to water wash column 31, gas delivery tower 25 tower reactor materials are also delivered to degassing vessel 29 degassed processing, and the reaction solution of degassing vessel 29 bottom extraction is delivered to the first rectifying tower 41 chargings of vinyl acetate building-up reactions unit.
The partial tail gas that water wash column 31 cats head the are got rid of gas processing system that truncates, remainder enters absorption tower 32, and water wash column 31 tower reactor materials enter degassing vessel 29.Absorption tower 32 overhead gas return synthesis reactor 18 after recycle compressor 26 compressions, absorption tower tower reactor liquid is delivered to desorption tower 33.The desorption tower 33 overhead gas gas processing system that truncates, desorption tower tower bottoms return absorption tower 32 recyclings.
3. vinyl acetate product purification unit
Vinyl acetate product purification unit production process is referring to Fig. 3-vinyl acetate product purification unit schema.Reaction solution from the vinyl acetate synthesis unit obtains qualified vinyl acetate finished product and acetaldehyde byproduct in vinyl acetate product purification unit by distillation operation.Vinyl acetate product purification unit is mainly by the first rectifying tower 41, the formations such as Second distillation column 42, the three rectifying tower, 43, the four rectifying tower 44, the five rectifying tower, 45, the six rectifying tower 46 and the 7th rectifying tower 47.
The reaction solution that 41 chargings of the first rectifying tower just go out from degassing vessel 29 bottoms, vinyl acetate building-up reactions unit, the recovery acetic acid of the first tower bottom of rectifying tower extraction is delivered to 17 chargings of vinyl acetate building-up reactions unit, overhead vapours is after 50 condensations of the first rectifying tower cat head condenser, enter 34 layerings of the first separator, upper organic phase is that crude ethylene acetic acid is delivered to Second distillation column 42 chargings, and lower floor's water is delivered to 45 chargings of the 5th rectifying tower.
Second distillation column 42 chargings are from the thick vinyl acetate on the first separator 34 upper stratas, the Second distillation column tower bottoms is not for containing the vinyl acetate of low-boiling-point substance, deliver to the 3rd rectifying tower 43, overhead vapours is after 52 condensations of Second distillation column overhead condenser, enter 36 layerings of the second separator, upper organic phase is vinyl acetate and low boiling component mixture, deliver to the 4th rectifying tower 44, lower floor's water is delivered to the 5th rectifying tower 45, Second distillation column reboiler 51 is the overhead condenser of the 6th rectifying tower 46 simultaneously, and heating medium is the overhead vapours of the 6th rectifying tower 46.
43 chargings of the 3rd rectifying tower are from the tower bottoms of Second distillation column 41, the 3rd rectifying tower cat head steam obtains the product of vinyl acetate after 56 condensations of the 3rd rectifying tower cat head condenser, tower bottoms is high boiling component and part vinyl acetate mixture, returns 41 chargings of the first rectifying tower.
44 chargings of the 4th rectifying tower are from the second separator 36 upper organic phase, the 4th rectifying tower cat head steams take acetaldehyde as main low boiling component and deliver to 47 chargings of the 7th rectifying tower after 54 condensation of the 4th rectifying tower cat head condenser, tower bottoms mainly comprises vinyl acetate, is back to Second distillation column 42 and refluxes.
47 chargings of the 7th rectifying tower are from the overhead extraction of the 4th rectifying tower 44, the 7th rectifying tower cat head steam through 59 condensations of the 7th rectifying tower cat head condenser after, lime set to 40 the 7th rectifying column top return tank, the 7th rectifying column top return tank extraction acetaldehyde finished product, bottom product is delivered to liquid waste treatment system.
46 chargings of the 6th rectifying tower are from the still liquid of vinyl acetate synthesizing section acetic acid vaporizer 17, after the 6th rectifying tower cat head steam and Second distillation column reboiler 51 carry out the heat exchange condensation, lime set to 35 the 6th rectifying column top return tank, lime set partial reflux in the 6th rectifying column top return tank, part is delivered to 41 chargings of the first rectifying tower, the overhead condenser of the 6th rectifying tower 46 and Second distillation column reboiler 51 are same equipment, heating medium is the overhead vapours of the 6th rectifying tower 46, and the bottom product of the 6th rectifying tower 46 is delivered to the waste residue treatment system.
45 chargings of the 5th rectifying tower are from lower floor's water of the first separator 34 and the second separator 36, after the 5th rectifying tower cat head steam and the 7th rectifying tower reboiler 58 carry out the heat exchange condensation, partial reflux, overhead condenser and the 7th rectifying tower reboiler 58 that part is delivered to the second separator 36, the five rectifying tower 45 are same equipment.The still water of the 5th rectifying tower 45 is delivered to Waste Water Treatment.
48,49,53,55,57 be respectively the 6th rectifying tower reboiler, the first rectifying tower reboiler, the 4th rectifying tower reboiler, the 3rd rectifying tower reboiler, the 5th rectifying tower reboiler, adopt rectifying tower corresponding to live steam heating
Description of drawings
Fig. 1: biological ethane prepares the unit schema;
Fig. 2: vinyl acetate building-up reactions unit schema;
Fig. 3: vinyl acetate product purification unit schema.
Embodiment
Embodiment:
Take the ripe wine with dregs of cassava ethanol fermentation as raw material, adopt the novel method of Fig. 1, Fig. 2, a kind of preparing vinyl acetate from bioethanol shown in Figure 3 to operate, produce the vinyl acetate product.
1. biological ethane prepares the unit
From the ripe wine with dregs of the ethanol fermentation of zymamsis unit, at first after the heat-eliminating medium preheating as ethanol distillation column overhead condenser 4, after further heating up by tower bottoms water cooler 1 again, enter ethanol distillation tower 2 as charging at last and carry out distillation operation, the ripe wine with dregs ethanol of ethanol fermentation volumetric concentration is 12%, ethanol distillation tower 2 working pressures (absolute pressure) are 0.1MPa, the ripe wine with dregs of ethanol fermentation removes water in the ethanol distillation tower, organic acid and heavy component impurity etc., it is 50% aqueous ethanolic solution that overhead vapours obtains the ethanol mass concentration through overhead condenser 4 and cat head aftercooler 5, the ethanol content of cat head aqueous ethanolic solution is adjusted control by parameters such as control feeding temperature and quantity of reflux, cat head aftercooler 5 heat-eliminating mediums are recirculated cooling water, alcohol concn is that 50% aqueous ethanolic solution is sent into three grades of water coolers of ethene 13 and generated the gas heat exchange to the ethanol evaporation temperature with reaction, enter into ethanol evaporation tank 9, ethanol distillation tower 2 stills are adopted after still liquid water cooler 1 cooling discharger to Waste Water Treatment.
Aqueous ethanolic solution after the preheating carries out the carburation by evaporation operation in evaporating pot 9, vaporizer heats by steam heater 7 and ethene secondary coolers 8, alcohol steam after the vaporization generates the further heat exchange of gas at ethene one-level water cooler 10 and ethylene reaction from the ethylene reaction device and heats up, deliver at last raw material electric heater 11 and be heated to temperature of reaction, be heated to 450 ℃ and enter ethylene reaction device 12.Ethanol carries out adiabatic dehydration reaction in reactor, obtains ethene and water, and the catalyzer in the reactor is molecular sieve or AlO
3The gas reaction temperature of reactor outlet is down to 340 ℃, ethylene reaction gas is successively by ethene one-level water cooler 10, ethene secondary coolers 8, three grades of water coolers 13 of ethene and ethene level Four level water cooler 14, cool the temperature to 45 ℃, then enter and carry out vapor-liquid separation in the vapor-liquid separation tank 15, the liquid phase discharger that contains water and a small amount of ethanol, acetaldehyde, ether etc. is delivered to Waste Water Treatment, contains CO
2, H
2, CH
4, the impurity such as acetaldehyde and ethane the crude ethylene gas phase enter ethylene compressor 16, send into the vinyl acetate reaction member.
2. vinyl acetate building-up reactions unit
Prepare the fresh ethylene raw material and cyclic ethylene mixing of unit from biological ethane after, after carrying out heat exchange and heat up by reaction gas the second water cooler 23 and reaction gas, enter acetic acid vaporizer 17 from the bottom, in vaporizer ethylene raw saturated acetic acid gas from the vaporizer Base top contact, by reaction gas the first water cooler 21 and reaction gas again heat exchange heat up, then again through feed gas heater 22 usefulness steam heating to 150 ℃.This gas is sent into oxygen mixer 19 again and is mixed with oxygen feed, makes oxygen account for 4.5-6.0% in whole reaction mixture, sends into vinyl acetate synthesis reactor 18 from oxygen mixer material out by the top.
Vinyl acetate synthesis reactor 18 is calandria type fixed bed reactor, pass into hot water between the shell side pipe of calandria type fixed bed reactor 18, liberated heat in the vinyl acetate synthetic reaction process, shift out reaction heat by hot water intensification between the pipe of calandria type fixed bed reactor 18, the temperature that hot water after the intensification leaves calandria type fixed bed reactor 18 is 135 ℃, enter the steam that 0.3MPa is produced in 20 vapour liquid separator step-downs, for other productive unit, the hot water after the cooling returns the recycle of vinyl acetate synthesis reactor.Load palladium catalyst in vinyl acetate synthesis reactor 18 tubulations, temperature of reaction is that 150 ℃, reaction pressure are 0.8MPa.The reacting synthesis gas body that vinyl acetate synthesis reactor 18 bottoms are got rid of carries out the heat exchange cooling by the first water cooler 21 and the second water cooler 23 with unstripped gas successively, then enter again reaction gas condenser 24, with water coolant reaction gas is further sent into gas delivery tower 25 after the cooling.The hypomere of gas delivery tower 25 and the circulating absorption solution in stage casing adopt respectively recirculated cooling water and chilled brine cooling, and gas delivery tower 25 gets off the high boiling point material condensations such as contained acetic acid, vinyl acetate in the reaction gas; Gas delivery tower 25 epimeres acetic acid drip washing gas.From gas delivery tower 25 tops reaction gas out, after recycle gas compressor 26 compressions, vinyl acetate synthesis reactor 18 is returned in most of circulation, small part is delivered to water wash column 31, gas delivery tower 25 tower reactor materials are also delivered to degassing vessel 29 degassed processing, and the reaction solution of degassing vessel 29 bottom extraction is delivered to the first rectifying tower 41 chargings of vinyl acetate building-up reactions unit.
The partial tail gas that water wash column 31 cats head the are got rid of gas processing system that truncates, remainder enters absorption tower 32, and water wash column 31 tower reactor materials enter degassing vessel 29.Absorption tower 32 overhead gas return synthesis reactor 18 after recycle compressor 26 compression, absorption tower tower reactor liquid is delivered to desorption tower 33, the desorption tower 33 overhead gas gas processing system that truncates, and the desorption tower tower bottoms returns absorption tower 32 recyclings.
3. vinyl acetate product purification unit
41 chargings of the first rectifying tower are from the reaction solution of vinyl acetate building-up reactions unit degassing vessel 29, the recovery acetic acid of the first tower bottom of rectifying tower extraction is delivered to vinyl acetate building-up reactions unit, overhead vapours is after 50 condensations of the first rectifying tower cat head condenser, enter 34 layerings of the first separator, upper organic phase is that crude ethylene acetic acid is delivered to Second distillation column 42, and lower floor's water is delivered to 45 chargings of the 5th rectifying tower.
Second distillation column 42 chargings are from the thick vinyl acetate on the first separator 34 upper stratas, the Second distillation column tower bottoms is not for containing the vinyl acetate of low-boiling-point substance, deliver to the 3rd rectifying tower 43, overhead vapours is after 52 condensations of Second distillation column overhead condenser, enter 36 layerings of the second separator, upper organic phase is vinyl acetate and low boiling component mixture, deliver to 44 chargings of the 4th rectifying tower, lower floor's water is delivered to 45 chargings of the 5th rectifying tower, Second distillation column reboiler 51 is the overhead condenser of the 6th rectifying tower 46 simultaneously, and heating medium is the overhead vapours of the 6th rectifying tower 46.
43 chargings of the 3rd rectifying tower are from the tower bottoms of Second distillation column 41, and the 3rd rectifying tower cat head steam obtains the product of vinyl acetate after 56 condensations of the 3rd rectifying tower cat head condenser.Tower bottoms is high boiling component and part vinyl acetate mixture, returns the first rectifying tower charging.
44 chargings of the 4th rectifying tower are from the second separator 36 upper organic phase, the 4th rectifying tower cat head steams take acetaldehyde as main low boiling component and deliver to 47 chargings of the 7th rectifying tower after 54 condensation of the 4th rectifying tower cat head condenser, tower bottoms mainly comprises vinyl acetate, is back to Second distillation column 42 and refluxes.
47 chargings of the 7th rectifying tower are from the overhead extraction of the 4th rectifying tower 44, the 7th rectifying tower cat head steam through 59 condensations of the 7th rectifying tower cat head condenser after, extraction acetaldehyde finished product, bottom product are delivered to the outer liquid waste treatment system of device.
46 chargings of the 6th rectifying tower are from the still liquid of vinyl acetate synthesizing section acetic acid vaporizer 17, after the 6th rectifying tower cat head steam and Second distillation column reboiler 51 carry out the heat exchange condensation, partial reflux, part is delivered to 41 chargings of the first rectifying tower, the overhead condenser of the 6th rectifying tower 46 and Second distillation column reboiler 51 are same equipment, heating medium is the overhead vapours of the 6th rectifying tower 46, and the bottom product of the 6th rectifying tower 46 is delivered to the outer waste residue treatment system of device.
45 chargings of the 5th rectifying tower are from lower floor's water of the first separator 34 and the second separator 36, after the 5th rectifying tower cat head steam and the 7th rectifying tower reboiler 58 carry out the heat exchange condensation, partial reflux, overhead condenser and the 7th rectifying tower reboiler 58 that part is delivered to the second separator 36, the five rectifying tower 45 are same equipment.The still water of the 5th rectifying tower 45 is delivered to the outer Waste Water Treatment of device.
48,49,53,55,57 be respectively the 6th rectifying tower reboiler, the first rectifying tower reboiler, the 4th rectifying tower reboiler, the 3rd rectifying tower reboiler, the 5th rectifying tower reboiler adopt rectifying tower corresponding to live steam heating.
Claims (3)
1. the method for a preparing vinyl acetate from bioethanol, it is characterized in that take from the ripe wine with dregs of the ethanol fermentation of ethanol fermentation unit as raw material production vinyl acetate product, the ripe wine with dregs ethanol of ethanol fermentation volumetric concentration is 5-20%, and production process comprises that biological ethane prepares unit, vinyl acetate reaction synthesis unit and vinyl acetate product purification unit; Prepare the unit at biological ethane, the ripe wine with dregs of ethanol fermentation removes water, organic acid and heavy component impurity in ethanol distillation tower (2), it is 40～60% aqueous ethanolic solution that overhead vapours obtains the ethanol mass concentration through overhead condenser (4) and cat head aftercooler (5), aqueous ethanolic solution enters return tank (6), and the ethanol content of cat head aqueous ethanolic solution is adjusted control by control feeding temperature and quantity of reflux parameter; Prepare the unit at biological ethane, it is 40～60% aqueous ethanolic solution from the ethanol mass concentration of ethanol distillation tower (2), ethanol raw material as the standby ethene of Dehydration operates without thin up, send into ethylene reaction device (12) after the direct boiling heating, realize that the process water consumption in the ethylene production is zero.
2. the method for a kind of preparing vinyl acetate from bioethanol as claimed in claim 1, it is characterized in that in vinyl acetate product purification unit, the overhead condenser of the 6th rectifying tower (46) and Second distillation column reboiler (51) are same equipment, Second distillation column reboiler (51) heating medium is the overhead vapours of the 6th rectifying tower (46), and Second distillation column (42) operation does not consume live steam.
3. the method for a kind of preparing vinyl acetate from bioethanol as claimed in claim 1, it is characterized in that in vinyl acetate product purification unit, the overhead condenser of the 5th rectifying tower (45) and the 7th rectifying tower reboiler (58) are same equipment, the 7th rectifying tower reboiler (58) heating medium is the overhead vapours of the 5th rectifying tower (46), and the 7th rectifying tower (47) operation does not consume live steam.
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| DE102011085165A1 (en) | 2011-10-25 | 2013-04-25 | Wacker Chemie Ag | Process for the preparation of vinyl acetate |
| CN102936198B (en) * | 2012-10-12 | 2016-05-25 | 天津大学 | Produce the method for vinyl acetate |
| CN106608787B (en) * | 2015-10-22 | 2019-04-12 | 中国石油化工股份有限公司 | The method that heat integration utilizes in producing ethylene from dehydration of ethanol technique |
| CN105964008B (en) * | 2016-07-14 | 2018-05-04 | 中国石化长城能源化工（宁夏）有限公司 | A kind of high-purity vinyl acetate piece-rate system |
| BR112022018132A2 (en) * | 2020-10-15 | 2023-04-25 | Kuraray Co | POLYVINYL ALCOHOL RESIN FILM, METHOD FOR DISTINGUISHING POLYVINYL ALCOHOL RESIN FILM, AND METHOD FOR MAKING POLYVINYL ALCOHOL RESIN FILM |
| CN115055132B (en) * | 2022-06-15 | 2022-12-16 | 天津大学 | Production process and device for preparing ethylene by ethanol dehydration |
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| US4423270A (en) * | 1981-09-28 | 1983-12-27 | Pearson Donald E | Process for catalytic dehydration of ethanol vapor to ethylene |
| CN1699326A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for refining vinyl acetate crude products |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
| CN101153257A (en) * | 2007-09-27 | 2008-04-02 | 广州保捷机电有限公司 | Five-tower two-grade difference pressure distillation equipment for senior edible ethanol and technique thereof |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423270A (en) * | 1981-09-28 | 1983-12-27 | Pearson Donald E | Process for catalytic dehydration of ethanol vapor to ethylene |
| CN1699326A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for refining vinyl acetate crude products |
| CN101153257A (en) * | 2007-09-27 | 2008-04-02 | 广州保捷机电有限公司 | Five-tower two-grade difference pressure distillation equipment for senior edible ethanol and technique thereof |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
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