CN107011163B - The method that acetylene method gas phase produces vinylacetate - Google Patents
The method that acetylene method gas phase produces vinylacetate Download PDFInfo
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- CN107011163B CN107011163B CN201710277632.6A CN201710277632A CN107011163B CN 107011163 B CN107011163 B CN 107011163B CN 201710277632 A CN201710277632 A CN 201710277632A CN 107011163 B CN107011163 B CN 107011163B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The present invention relates to a kind of method of acetylene in gas phase production vinylacetate, including acetylene and acetic acid reaction synthesizing vinyl acetate ester units, acetylene and acetic acid, vinylacetate separative element；Fresh acetylene from acetylene cleaning process is mixed with the acetylene gas circulated, enter recyclegas air blower after being heated by steam, acetate evaporator is sent into after supercharging heats up, fresh acetic acid and rectifying acetic acid add to acetate evaporator respectively, discharged by the acetylene gas of acetic acid saturation from the top of acetate evaporator, reacted after heated into synthesis reactor, reaction product is sent to gas knockout tower tower reactor after cooling, gas knockout tower tower reactor is equipped with cooling cycle, acetylene and acetic acid in gas knockout tower, vinylacetate is separated, tower top obtains circulation acetylene, send to recyclegas blower inlet and boost, form gas circulation, tower reactor obtains acetic acid and is sent with vinylacetate reaction solution to rectification section.High selectivity that the present invention reacts, catalyst life length, process simplification, reduces energy consumption.
Description
Technical field
The present invention relates to a kind of method for producing vinylacetate, in particular to a kind of technological process is succinct, energy consumption is low
Acetylene method gas phase production vinylacetate method.
Background technology
Vinylacetate is a kind of important Organic Chemicals, is widely used in production polyvinyl acetate, polyvinyl alcohol, painting
A series of chemical products such as material, adhesive, can make the vehicle seat of bicycle, the filler of agricultural film and refrigerator and as polychlorostyrene second
The modifying agent of alkene and synthetic rubber.Vinyl acetate is as intermediate, the expansion applied with polyvinyl alcohol non-fiber field so that
The demand of vinyl acetate constantly increases.
At present, producing the technique of vinylacetate mainly has two kinds of ethylene process and acetylene method；Acetylene method and ethylene process all divide
For vapor phase method and liquid phase method；Wherein liquid phase method has been eliminated in succession due to corroding with cost problem.Provided in calcium carbide, coal or natural gas
The area that source is enriched, acetylene method have more the market competitiveness than ethylene process.It is divided into electricity again according to raw material sources are different in acetylene method
Stone acetylene method and gas acetylene method.
The existing most Introduced from Japan of producing vinyl acetate by acetylene method ester technology in China and the technology of France.Wherein, it is Japanese
Electrochemically company uses fluidized bed reactor technology.French Synthesizing Vinyl Acetate from Acetylene in Natural Gas technology is anti-using fixed bed
Answer device technology.Reaction process is：Acetylene and acetic acid are under the action of Zinc Acetate/activated Carbon Catalyst, at 160~220 DEG C, normal pressure
Under carry out the reaction generation accessory substance such as vinyl acetate and acetaldehyde, crotonaldehyde, gas after reaction is separated through multistage cooling, point
The acetylene gas separated out continues cycling through use, and the acetic acid and vinyl acetate liquid isolated send to rectification working process and carries out vinyl acetate
It is refined.
Compared with fluid bed, fixed bed has its own advantage.The space time yield of fixed bed is high, can rub in high acetylene/acetic acid
You can inhibit the generation of the accessory substances such as acetaldehyde, improve the selectivity and production capacity of reaction than lower progress；Catalysis in fixed bed
Agent is substantially without abrasion, catalyst life length；The pressure drop of fixed bed is low, material is evenly distributed, and is conducive to control the temperature of reactor.
The reaction of acetylene and acetic acid is exothermic reaction, and fixed bed reactors use shell and tube reactor more, and catalyst is placed in
In pipe, circulated between conventional art middle pipe by conduction oil to withdraw from reaction heat, but reaction heat is not utilized further,
Cause thermal loss.
For the hot synthesis gas of vinyl acetate production device reaction device outlet, conventional art is used to carry out with circulating air
Level-one exchanges heat, and synthesis gas enters gas knockout tower after being cooled to 120 DEG C, also needs using cooling water and follows in gas knockout tower
Ring water continues to cool down, and adds public work consumption.
In acetic acid evaporation process, the operation temperature of acetate evaporator is high, requires height to equipment material, while easily block up
The problem of plug.
The method for developing the producing vinyl acetate by acetylene method ester that a kind of technological process is succinct, energy consumption is low is very favorable.
The content of the invention
It is an object of the present invention to provide a kind of method of producing vinyl acetate by acetylene method ester, this method passes through optimization
Technological process, reduces the consumption of public work, and the energy consumption of vinylacetate production is greatly lowered.
The present invention relates to a kind of production method of vinylacetate, and acetic acid second is produced in particular to a kind of acetylene method gas phase
The method of enester.
Technical scheme is as follows：
A kind of method of acetylene method gas phase production vinylacetate；Including acetylene and acetic acid reaction synthesizing vinyl acetate ester list
Member, acetylene and acetic acid, vinylacetate separative element；Fresh acetylene from acetylene cleaning process is mixed with the acetylene gas circulated
Close, recyclegas air blower is entered after being heated by steam, acetate evaporator, fresh acetic acid and rectifying vinegar are sent into after supercharging heats up
Acid adds to acetate evaporator respectively, is discharged by the acetylene gas of acetic acid saturation from the top of acetate evaporator, enters synthesis after heated
Reactor is reacted, and reaction product is sent to gas knockout tower tower reactor, gas knockout tower tower reactor and is equipped with cooling cycle after cooling,
Acetylene is separated with acetic acid, vinylacetate in gas knockout tower, and tower top obtains circulation acetylene, send to recyclegas air blast
Machine entrance boosts, and forms gas circulation, and tower reactor obtains acetic acid and sent with vinylacetate reaction solution to rectification section.
Synthesis reactor of the present invention connects acetate evaporator and gas knockout tower by First Heat Exchanger；In First Heat Exchanger
Reactor feed preheater is provided between connection synthesis reactor；Reaction is equipped between First Heat Exchanger and gas knockout tower
The second heat exchanger of gas；Recyclegas superheater is equipped between gas knockout tower and recyclegas air blower；Recyclegas air blower
Connected by the second heat exchanger with acetate evaporator.
The acetylene gas of acetic acid saturation of the present invention is discharged from acetate evaporator tower top, by reaction gas First Heat Exchanger shell
Journey, reactor feed preheater send the tube-side inlet to synthesis reactor to be reacted, and the synthesis gas generated after reaction synthesizes certainly
After the tube side outlet discharge of reactor, by reaction gas First Heat Exchanger tube side, the second heat exchanger tube pass of reaction gas, into gas
Knockout tower tower reactor, circulation acetylene are discharged from the tower top of gas knockout tower, and into recyclegas superheater, circulating air is entered after heating
Body air blower, enters the second heat exchanger shell pass of reaction gas after boosting, acetate evaporator tower reactor feed inlet is entered after heating, forms one
A circulatory system.
The compression ratio of the recyclegas air blower is 0.2~2.
The tower reactor of acetate evaporator of the present invention is equipped with a circulatory system：Acetic acid is arranged from the tower reactor discharge port of acetate evaporator
After going out, enter circulation acetic acid heater through acetate evaporator circulating pump, acetate evaporator tower reactor feed inlet is back to after heating；It is logical
The heating quantity of steam for overregulating circulation acetic acid heater controls the tower top temperature of acetate evaporator, further control acetylene and vinegar
The molar ratio of acid.The tower top temperature of acetate evaporator is 40~100 DEG C, and the molar ratio of acetylene and acetic acid is 4~10.
The reaction temperature of synthesis reactor of the present invention is 150~250 DEG C, and pressure is 20~100KPa.
Catalyst atomization device is set on preferred reactor entrance pipe.
Vinyl acetate synthesis reactor of the present invention is calandria type fixed bed reactor, and catalyst, acetylene and vinegar are housed in pipe
Acid is reacted in pipe, is pressure (hydraulic) water between pipe, synthesis reactor coupled reaction device drum, forms one with reactor drum and follow
Loop system：Liquid phase water in reactor drum enters synthesis reactor shell side inlet, liquid phase water in synthesis reactor by hot gas
Gas-liquid two-phase is turned to, is discharged from synthesis reactor shell-side outlet, enters back into the mixed vapor liquid phase entrance of reactor drum 1；Drum
In pressure (hydraulic) water rely on the heated vaporization in synthesis reactor and hot rainbow that the vapor-liquid separation in reactor drum is formed
Inhale Natural Circulation and remove reaction heat；145~245 DEG C of the temperature of reactor drum, pressure are 0.6~2MPa.
Gas knockout tower cooler uses plate heat exchanger or shell-and-tube heat exchanger；It is water at low temperature or freezing to cool down medium
Water；Cryogenic media walks shell side；1~5 cooler is set in tower；The tower top temperature of gas knockout tower is 10~50 DEG C, gas
Knockout tower intercooler material outlet temperature is 10~50 DEG C.
Chilled water circulating slot is set outside gas knockout tower, and chilled water is added into circulating slot, the chilled water one in circulating slot
The chilled water pump in part is squeezed into the shell side of gas knockout tower intercooler, through the gas converting heat with rising in gas knockout tower
Afterwards, return again into freezing water circulating slot；Another part chilled water flowed out from circulating slot is sent to chilled water return pipe manifold.
It is described as follows：
One of the method for the equipment synthesizing vinyl acetate ester connected using the present invention, raw material of use are acetylene, the acetylene
Can be carbide acetylene or gas acetylene.
In the vinylacetate building-up process of the present invention, acetylene conversion per pass is relatively low, and a large amount of unconverted acetylene must
It must recycle.Acetylene is added from the bottom of acetate evaporator, and fresh acetic acid is added from the top of acetate evaporator, and rectification section comes
Distillation acetic acid from acetate evaporator middle and upper part add.Acetylene gas and acetic acid counter current contacting in acetate evaporator, by acetic acid
The acetylene gas of saturation is discharged from top, by reaction gas First Heat Exchanger shell side, reactor feed preheater, is sent to synthetic reaction
The tube-side inlet of device is reacted, and the synthesis gas generated after reaction is from after the tube side outlet discharge of synthesis reactor, by reaction
Gas First Heat Exchanger tube side, the second heat exchanger tube pass of reaction gas, into gas knockout tower tower reactor, circulate acetylene from gas knockout tower
Tower top discharge, into recyclegas superheater, recyclegas air blower is entered after heating, is changed after boosting into reaction gas second
Hot device shell side, enters acetate evaporator tower reactor feed inlet after heating, form a circulatory system.
The tower reactor of acetate evaporator is equipped with a circulatory system：Acetic acid from after the discharge of the tower reactor discharge port of acetate evaporator,
Enter circulation acetic acid heater through acetate evaporator circulating pump, acetate evaporator tower reactor feed inlet is back to after heating.Pass through tune
The heating quantity of steam for saving acetic acid heater controls the tower top temperature of acetate evaporator, further mole of control acetylene and acetic acid
Than.
The acetylene of discharge and the gaseous mixture of acetic acid initially enter reaction gas First Heat Exchanger at the top of from acetate evaporator, then
Reacted gas feed preheater is preheating to reaction temperature, and reaction gas feed preheater is heated using steam.Reaction gas is by reactor
Top is sent into catalyst bed and carries out catalytic reaction.According to an embodiment, the reactor is calandria type fixed bed anti-
Answer device.Acetylene and acetic acid react under the action of catalyst in the reactor.As described above, catalyst used can use this
The zinc acetate catalyst of the known load for acetylene in gas phase production vinyl acetate on the activated carbon in field.On catalyst
Detailed description, reference can be made to《Polyvinyl alcohol production technology》, chapter 2, Section four, in January, 1988, it is fully incorporated herein work
For reference.
The reaction temperature of the synthesis reactor is 150~250 DEG C, and pressure is 20~100KPa (gauge pressure).This area
Technical staff understands that method of the invention does not have particular/special requirement to used catalyst, carrier, temperature and pressure, as long as can be real
Vinylacetate is now obtained by acetylene and acetic acid with vapor phase method.
In one embodiment, to prevent the loss of zinc acetate in catalyst, present invention employs one it is continuous or
Have a rest and add the spare measure of zinc acetate：Catalyst atomization device is set on reactor inlet pipeline.The acetum of zinc acetate exists
It is atomized in catalyst atomization device, then is sent in the lump to synthesis reactor with reaction gas.In the reactor, the zinc acetate quilt with people
It is adsorbed on activated carbon, so that supplemented with the zinc acetate being lost in during the reaction, extends the service life of catalyst.
In one embodiment, vinyl acetate synthesis reactor is calandria type fixed bed reactor, equipped with catalysis in pipe
Agent, acetylene are reacted with acetic acid in pipe, are pressure (hydraulic) water between pipe, by its heated vaporization in synthesis reactor and anti-
The thermal siphon Natural Circulation that the vapor-liquid separation in device drum is formed is answered to remove reaction heat.This method heat transfer efficiency is high, is conducive to
The control of reaction bed temperature, ensure that the high selectivity of reaction and the long-life of catalyst.Two produced by reactor drum
Secondary steam, into respective level steam pipe network, can effectively reduce the overall steam consumption of process units；Pressure (hydraulic) water circulation is using heat
Siphon self-circulation mode, eliminates pressurization water-circulating pump, reduces power consumption.
In synthesis gas after reaction in addition to containing purpose product vinyl acetate, also containing unconverted acetic acid, acetylene, and
The accessory substances such as other a small amount of acetaldehyde, crotonaldehydes and nitrogen, carbon dioxide etc..Only by means of the method cooled down indirectly, it is difficult to by vinegar
Acid and vinyl acetate total condensation are got off.Further direct condensation by contact must carry out reacting gas using gas knockout tower.
Synthesis pneumatic transmission after reaction is to the bottom of gas knockout tower, and the partial reaction liquid of gas knockout tower tower reactor is by gas point
After being pumped into gas knockout tower cooler by low temperature water cooling from tower circulation, gas separation midsection is back to, with uprising gas
Counter current contacting, acetic acid contained therein, vinyl acetate are condensed out, and the acetic acid come from exhaust gas recovery workshop section enters gas knockout tower
Epimere elutes gas, the vinyl acetate in further gas recovery.
A favourable embodiment according to the present invention, the gas knockout tower cooler use plate heat exchanger or pipe
Shell heat exchanger.
In the gas come out from gas separation column, it is mainly formed as acetylene, acetaldehyde, nitrogen and carbon dioxide etc.,
Most of and fresh acetylene enters recyclegas air blower after converging, and synthesis reactor is returned after compression；In addition an extraction part
Effluent pneumatic transmission is to inert components such as exhaust gas recovery workshop section carbon dioxide removals, to ensure concentration of acetylene not because of inert component accumulation
Reduce, make synthetic reaction smooth.The reaction solution of gas knockout tower tower reactor, which is sent to rectification section, to be separated.
In one embodiment, the fresh acetylene to come from peace and quiet workshop section can add to gas knockout tower feed entrance,
The acetic acid leacheate counter current contacting added in gas knockout tower with tower top, so that the water contained in fresh acetylene gas be taken off
Remove, when fresh acetylene is back to reactor after compression and is reacted with circulation acetylene, because of the reduction of water content, it is possible to reduce secondary
The generation of product acetaldehyde.
In order to which acetic acid, vinyl acetate are farthest condensed out in gas knockout tower, only tower cooler is separated by gas
The shifting heat of device water at low temperature, is not met by requiring.In an effective embodiment, shell-and-plate is set in gas knockout tower
Or tubular heat exchanger is cooled down, preferred tubular heat exchanger, cooling medium is water at low temperature or chilled water.Process stream walks pipe
Journey, cryogenic media walk shell side.1~5 cooler, preferably 3 coolers are set in tower.Compound built-in cooler in tower,
Heat exchange area is big, simple in structure, and maintenance is convenient.
The present invention uses to ensure the heat transfer efficiency of material and cooling medium in the built-in cooler of gas knockout tower
The mode of medium foundation circulation will be cooled down, by reducing the temperature difference of cooling medium and storeroom, increase cools down the flow of medium, comes
The flow velocity of cooling medium is improved, so as to ensure heat transfer efficiency.Concrete scheme is：One freezing water circulating slot is set, it is a certain amount of new
Fresh chilled water is added into circulating slot, and a part of chilled water pump of the chilled water in circulating slot is squeezed into cooling down in gas knockout tower
The shell side of device, after the gas converting heat with rising in gas knockout tower, returns again into freezing water circulating slot.Flowed from circulating slot
Another part chilled water gone out is sent to chilled water return pipe manifold.
Usually, a certain amount of reaction solution (acetic acid and vinylacetate mixing are continuously produced from gas knockout tower tower reactor
Liquid), send to rectification section and further purified.
The quality group of the reaction solution becomes vinyl acetate 20~50%, acetic acid 50~80%.
The operating method of gas knockout tower using the present invention, heavy constituent content has obtained effective reduction in tower overhead gas：Vinegar
Vinyl acetate<900ppm, acetaldehyde<2.2%, crotonaldehyde<20ppm.
High selectivity that the present invention reacts, catalyst life length, ensure that gas separation system is continuous, stablizes, Effec-tive Function,
Process simplification, reduces energy consumption.
Brief description of the drawings
Fig. 1：The flow diagram of vinylacetate synthesizing section.
Acetate evaporator -101, circulation acetic acid heater -102, acetate evaporator circulating pump -103, reaction gas second exchange heat
Device -104, reaction gas First Heat Exchanger 105, reactor feed preheater 106, synthesis reactor 107, reactor drum 108, gas
Body knockout tower 109, gas knockout tower cooler 110, gas knockout tower circulating pump -111, gas knockout tower intercooler 112~
114th, water circulating slot -115, chilled water pump -116, recyclegas superheater -117, recyclegas air blower -118, acetic acid are freezed
Zinc atomizer -119.
Embodiment
The method of the acetylene in gas phase production vinyl acetate of the present invention mainly includes the building-up process of vinyl acetate and separated
Journey, is described below in conjunction with attached drawing.
Fresh acetylene and the acetylene gas of circulation from acetylene production process are mixed into recyclegas superheater 117, quilt
Enter recyclegas air blower 118 after steam heating, enter the second heat exchanger of reaction gas after the supercharging of recyclegas air blower 118
104, the lower part of acetate evaporator 101 is sent into after reacted gas preheating, fresh acetic acid is added from the top of acetate evaporator 101,
The distillation acetic acid that rectification section comes is added from 101 middle and upper part of acetate evaporator.Acetylene gas is with acetic acid in acetate evaporator 101
Counter current contacting, is discharged by the acetylene gas of acetic acid saturation from top, by adjust the heating quantity of steam of circulation acetic acid heater 102 come
The tower top temperature of acetate evaporator 101 is controlled, further controls the molar ratio of acetylene and acetic acid.It is outer that kettle liquid mainly flows stock-traders' know-how pressure
Acetate evaporator 101 is back to after circulating-heating, fraction stream stock is sent to 109 tower reactor of gas knockout tower.
The gaseous mixture of acetylene and acetic acid from the discharge of the top of acetate evaporator 101 enters reaction gas First Heat Exchanger 105, and
Reaction temperature is preheating to by reaction gas feed preheater 106, reaction gas feed preheater 106 is heated using steam.Reaction gas
Catalyst bed is sent into by the top of synthesis reactor 107 and carries out catalytic reaction.The synthesis reactor 107 can be shell and tube
Fixed bed reactors.Acetylene and acetic acid react in synthesis reactor 107 under the action of catalyst.Reaction temperature for 150~
250 DEG C, pressure is 20~100KPa (gauge pressure).Vinyl acetate synthesis reactor 107 is calandria type fixed bed reactor, is between pipe
Pressure (hydraulic) water, is formed by its heated vaporization in synthesis reactor 107 and the vapor-liquid separation in reactor drum 108
Thermal siphon Natural Circulation removes reaction heat.Indirect steam produced by reactor drum 108, into respective level steam pipe network.
Catalyst atomization device 119 is equipped with the entrance pipe of synthesis reactor 107.The acetum of zinc acetate is being catalyzed
It is atomized in agent atomizer 119, then is sent in the lump to synthesis reactor 107 with reaction gas.In the reactor, the zinc acetate with people
It is adsorbed on activated carbon, so that supplemented with the zinc acetate being lost in during the reaction, extends the service life of catalyst.
The forming gas of synthesis reactor 107 is left by reaction gas First Heat Exchanger 105, the second heat exchanger of reaction gas
Sent after 104 to the bottom of gas knockout tower 109, the partial reaction liquid of 109 tower reactor of gas knockout tower is by gas knockout tower circulating pump
After 111 are sent into gas knockout tower cooler 110 by low temperature water cooling, 109 stage casing of gas knockout tower is back to, it is inverse with uprising gas
Stream contact, acetic acid contained therein, vinyl acetate are condensed out.The acetic acid come from exhaust gas recovery workshop section enters gas knockout tower
109 epimeres elute gas, the vinylacetate in further gas recovery.The gas knockout tower cooler 110 is using board-like
Heat exchanger or shell-and-tube heat exchanger.
From the gas of the top of gas knockout tower 109 out, it is mainly formed as acetylene, acetaldehyde, nitrogen and carbon dioxide
Deng, it is most of converge with fresh acetylene after enter recyclegas air blower 118, return synthesis reactor 107 after compression；In addition adopt
Go out a part of effluent pneumatic transmission to inert components such as exhaust gas recovery workshop section carbon dioxide removals.The reaction of 109 tower reactor of gas knockout tower
Liquid send to rectification section and is separated.
The fresh acetylene to come from peace and quiet workshop section can add to 109 entrance of gas knockout tower, in gas knockout tower with tower
The acetic acid leacheate counter current contacting added is pushed up, so as to the water contained in fresh acetylene gas be removed, fresh acetylene and circulation
When acetylene is back to reactor 107 and is reacted after compression, because of the reduction of water content, it is possible to reduce the life of acetaldehyde byproduct
Into.
In order to which acetic acid, vinyl acetate are farthest condensed out in gas knockout tower 109, tower top temperature need to be cooled to 10
~50 DEG C, only the shifting heat by 110 water at low temperature of gas knockout tower cooler, are not met by requiring.Set in gas knockout tower
Shell-and-plate or tubular heat exchanger are cooled down, preferably tubular heat exchanger 112~114, and cooling medium is water at low temperature or freezing
Water.Process stream walks tube side, and cryogenic media walks shell side.1~5 cooler, preferably 3 coolers are set in tower.
In order to ensure the heat transfer efficiency of material and cooling medium in tower, by the way of cooling medium is established circulation, lead to
Cross the temperature difference for reducing cooling medium and storeroom, the flow of increase cooling medium, to improve the flow velocity of cooling medium, so as to ensure
Heat transfer efficiency.Concrete scheme is：One freezing water circulating slot 115 is set, and a certain amount of fresh food frozen water is added to circulating slot 115
In, a part of chilled water pump 116 of chilled water in circulating slot 115 is squeezed into the shell of gas knockout tower intercooler 112~114
Journey, after the gas converting heat with rising in gas knockout tower 109, returns again into freezing water circulating slot 115.From circulating slot 115
Another part chilled water of middle outflow is sent to chilled water return pipe manifold.
A certain amount of reaction solution (acetic acid and vinylacetate mixed liquor) is continuously produced from 109 tower reactor of gas knockout tower, is sent
Further purified to rectification section.
Claims (9)
- A kind of 1. method of acetylene method gas phase production vinylacetate；Including acetylene and acetic acid reaction synthesizing vinyl acetate ester list Member, acetylene and acetic acid, vinylacetate separative element；It is characterized in that fresh acetylene and the second of circulation from acetylene cleaning process Alkynes gas mixes, and recyclegas air blower is entered after being heated by steam, and acetate evaporator is sent into after supercharging heats up, fresh acetic acid with Rectifying acetic acid adds to the top of acetate evaporator respectively, is discharged by the acetylene gas of acetic acid saturation from the top of acetate evaporator, through adding Reacted after heat into synthesis reactor, reaction product is sent to gas knockout tower tower reactor, gas knockout tower tower reactor after cooling Equipped with cooling cycle, acetylene is separated with acetic acid, vinylacetate in gas knockout tower, and tower top obtains circulation acetylene, send Boost to recyclegas blower inlet, form gas circulation, tower reactor obtains acetic acid and sent with vinylacetate reaction solution to rectifying Workshop section；The acetylene gas of acetic acid saturation from acetate evaporator tower top discharge, by reaction gas First Heat Exchanger shell side, reactor into Material preheater send the tube-side inlet to synthesis reactor to be reacted, tube side of the synthesis gas generated after reaction from synthesis reactor After outlet discharge, by reaction gas First Heat Exchanger tube side, the second heat exchanger tube pass of reaction gas, into gas knockout tower tower reactor, Circulate acetylene to discharge from the tower top of gas knockout tower, recyclegas superheater is entered after being mixed with fresh acetylene, is entered after heating Recyclegas air blower, enters the second heat exchanger shell pass of reaction gas after boosting, acetate evaporator tower reactor feed inlet is entered after heating, Form a circulatory system.
- 2. the method as described in claim 1, steams it is characterized in that synthesis reactor connects acetic acid by reaction gas First Heat Exchanger Send out device and gas knockout tower；Reactor feed preheater is provided between reaction gas First Heat Exchanger connects synthesis reactor； The second heat exchanger of reaction gas is equipped between reaction gas First Heat Exchanger and gas knockout tower；Gas knockout tower and recyclegas drum Recyclegas superheater is equipped between wind turbine；Recyclegas air blower connects by the second heat exchanger of reaction gas and acetate evaporator Connect.
- 3. the method as described in claim 1, it is characterized in that the compression ratio of the recyclegas air blower is 0.2~2.
- 4. the method as described in claim 1, it is characterized in that the tower reactor of acetate evaporator is equipped with a circulatory system：Acetic acid is from vinegar After the tower reactor discharge port discharge of sour evaporator, enter circulation acetic acid heater through acetate evaporator circulating pump, be back to after heating Acetate evaporator tower reactor feed inlet；The tower top of acetate evaporator is controlled by adjusting the heating quantity of steam of circulation acetic acid heater Temperature, further controls the molar ratio of acetylene and acetic acid.The tower top temperature of acetate evaporator is 40~100 DEG C, acetylene and acetic acid Molar ratio be 4~10.
- 5. the method as described in claim 1, it is characterized in that the reaction temperature of synthesis reactor is 150~250 DEG C, pressure 20 ~100KPa.
- 6. the method as described in claim 1, it is characterized in that setting catalyst atomization device on reactor inlet pipeline.
- 7. method as claimed in claim 2, it is characterized in that vinyl acetate synthesis reactor is calandria type fixed bed reactor, pipe Interior that catalyst is housed, acetylene is reacted with acetic acid in pipe, is pressure (hydraulic) water between pipe, synthesis reactor coupled reaction device drum, A circulatory system is formed with reactor drum：Liquid phase water in reactor drum enters synthesis reactor shell side inlet, liquid phase Water in synthesis reactor by it is thermal evaporation be gas-liquid two-phase, from synthesis reactor shell-side outlet discharge, enter back into reactor drum 1 Mixed vapor liquid phase entrance；Pressure (hydraulic) water in drum relies on heated vaporization in synthesis reactor and in reactor drum The thermal siphon Natural Circulation that is formed of vapor-liquid separation remove reaction heat；145~245 DEG C of the temperature of reactor drum, pressure are 0.6~2MPa.
- 8. the method as described in claim 1, it is characterized in that gas knockout tower intercooler uses plate heat exchanger or shell-and-tube Heat exchanger；It is water at low temperature or chilled water to cool down medium；Cryogenic media walks shell side；1~5 cooler is set in tower；Gas point Tower top temperature from tower is 10~50 DEG C, and gas knockout tower intercooler material outlet temperature is 10~50 DEG C.
- 9. the method as described in claim 1, it is characterized in that set chilled water circulating slot outside gas knockout tower, chilled water add to In circulating slot, a part of chilled water pump of chilled water in circulating slot is squeezed into the shell side of gas knockout tower intercooler, through with After the gas converting heat risen in gas knockout tower, return again into freezing water circulating slot；The another part flowed out from circulating slot Chilled water is sent to chilled water return pipe manifold.
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| CN104177254A (en) * | 2013-05-28 | 2014-12-03 | 上海浦景化工技术有限公司 | Treatment process for acetylene method vinyl acetate synthetic reaction gas |
| CN104177258A (en) * | 2013-05-27 | 2014-12-03 | 中国石油化工集团公司 | Method for preparing vinyl acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104177258A (en) * | 2013-05-27 | 2014-12-03 | 中国石油化工集团公司 | Method for preparing vinyl acetate |
| CN104177254A (en) * | 2013-05-28 | 2014-12-03 | 上海浦景化工技术有限公司 | Treatment process for acetylene method vinyl acetate synthetic reaction gas |
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