CN109134233B - A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation - Google Patents
A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation Download PDFInfo
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- CN109134233B CN109134233B CN201811224192.9A CN201811224192A CN109134233B CN 109134233 B CN109134233 B CN 109134233B CN 201811224192 A CN201811224192 A CN 201811224192A CN 109134233 B CN109134233 B CN 109134233B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The invention discloses a kind of process units of synthesizing acetic acid by methanol low-voltage carbonylation and production methods, the present invention is arranged fluid stirring device and changes mechanical stirring axle envelope and transmission device situation easy to damage in the process of running, dynamic sealing point is eliminated, system safe and stable operation is greatly improved.It is matched simultaneously with CO distributor, is distributed the CO gas in reactor more uniform, improves gas-liquid two-phase mixed effect, promote reaction rate, optimization system reactiveness, device capbility is promoted to 600,000 tons/year by 300,000 tons/year.
Description
Technical field
The present invention relates to acetic synthesis fields, and in particular to a kind of process units of synthesizing acetic acid by methanol low-voltage carbonylation and
Production method.
Background technique
Acetic acid is important chemical intermediate and chemical reaction solvent, in the technique of the acetic synthesis to come into operation at present,
It is most common one is low-pressure methanol carbonylic synthesis technology, which is initiated by Monsanto Chemicals in the seventies, and process is several
Innovation development in 10 years, production technology have huge change, and device capbility, product quality, production cost achieve great prominent
It is broken.
In terms of technology and control, new scheme is constantly sought by each company, and Zehua Chemical Engineering Co., Ltd., Beijing is special
It is described in sharp CN 101665424, it is complete in a rectifying column to merging the existing function of being executed by lightness-removing column and dehydrating tower
At, the flow line of acetic acid preparation is simplified, the equipment investment of device is reduced, while also reducing the difficulty of operation control, it can
The energy consumption of device is effectively reduced, reduces production cost.It is retouched in the Hengsheng Hua Lu chemical inc patent CN 201525813
It states, by the way that iodomethane recycle column and evaporator are arranged before rectifier unit, recycle iodomethane in reaction system, reduce and be mixed into
The amount of iodomethane impurity in acetic acid, while having saved energy consumption required for purifying acetic acid.Currently, technological improvement is mostly in rectifying system
System, reaction system variation is less, especially reaction kettle unit, still stirs mould using conventional mechanical in gas-liquid agitation mixing
The mixing of liquid-liquid and solution-air can be effectively performed using churned mechanically consersion unit for formula, still, needed for machine driving
Axle envelope and bearing easily damaged in longtime running, cause maintenance shut-downs, it is difficult to realize and continue, stably and securely run.
In terms of control of product quality, the purification schemes of the companies such as external BP, Celanese Dichlorodiphenyl Acetate are studied, and are carried out
The improvement of purifying technique.BP company describes using the technology of single rectification zone in the patent CN93108283 of China and adapts to
The change of catalyst in reaction solution；And Celanese Int Corp produces second in a kind of improvement of patent CN 101808973 of China
The method of acid, including condense overhead vapours from light fraction tower and concentration vapor is isolated into light phase and heavy phase.Heavy phase is main
It is made of iodomethane, and the heavy phase that at least part is fallen off is back to light fraction tower.Light ends column overhead distillate
The water of acetic acid content and light fraction tower product stream is reduced containing rate, improves purification efficiency.The companies such as domestic Jiangsu Suo Pu are to production
Micro content of iodine control in product proposes new removing scheme, and a kind of ion exchange is invented in description in patent CN101396670
Resin iodine-removing adsorption agent and preparation method thereof, adsorbent are macro porous crosslinking type ion exchange resin by loading one or more gold
Belong to ion and be made, the Spectrophotometric Determination of Trace Iodide in Dichlorodiphenyl Acetate has preferable removal effect.
In recent years, control of product quality increasingly becomed an important ring of acetic acid synthesizer utilizing methanol carbonylation technological improvement
Section.
Summary of the invention
For above-mentioned the technical problems existing in the prior art, the object of the present invention is to provide a kind of low-pressure methanol carbonylations
The process units and production method of acetic acid are synthesized, fluid stirring device is arranged in reaction kettle and changes mechanical stirring axis by the present invention
Envelope and transmission device situation easy to damage in the process of running, dynamic sealing point is eliminated, system safety and stability is greatly improved
Operation.It is matched simultaneously with CO distributor, is distributed the CO gas in reactor more uniform, improve gas-liquid two-phase mixing effect
Fruit, promotes reaction rate, optimization system reactiveness, and device capbility is promoted to 600,000 tons/year by 300,000 tons/year.For yield
Full gear device and de- iodine device is arranged in distillation system in control of product quality after promotion, improves product reduction potassium permanganate and takes off
The color time reduces propionic acid, formic acid and content of iodine in product.
In order to solve problem above, the technical solution of the present invention is as follows:
A kind of process units of synthesizing acetic acid by methanol low-voltage carbonylation, including reaction kettle, transformation pot, evaporator, prewashing tower,
Lightness-removing column, dehydrating tower, finishing column and fluid stirring device, wherein the fluid stirring device include at least two spray heads, pump and
Heat exchanger, the input end of the pump are connected to the middle part of reaction kettle, and the outlet end of pump is connected to the input end of heat exchanger, spray head
Fixed -piping is fixed on the top of reaction kettle, and the end of the fixed -piping of the outlet end and spray head of heat exchanger is connected to, and spray head is close
The inner wall of reaction kettle is arranged, and spray head is set to reaction kettle liquid level or less 200-500mm, the folder of the diameter where two neighboring spray head
Angle is 45 ° -90 °.
Reaction solution in reaction kettle is flowed out from the middle part of reaction kettle, is delivered to heat exchanger under the power effect of pump and is dropped
Wen Hou is delivered at spray head and sprays, and reaction solution flows downward along the inner wall high speed of reaction kettle, drives the liquid on periphery that vector occurs
Change, and from the bottom of reaction kettle overturning and on, form the different Two-way Cycle flow regime of multiple main flow layers.
45 ° -90 ° are set by the angle of diameter where two neighboring spray head, is to ensure different Two-way Cycle flowing shapes
The generation of state, and then bigger disturbance is generated to the reaction solution in reaction kettle, it is ensured that reaction solution is uniformly mixed, without dead angle in kettle,
Reach better mixing effect.
Spray head is set to reaction kettle liquid level or less 200-500mm, is driven entire in order to ensure stronger fluid dynamic
Reaction solution flows in kettle, reaches better mixing effect.
Heat exchanger can cool down to the reaction solution in reaction kettle, the heat released in timely removal system reaction process
Amount, it is ensured that system response continuity and stability.
Pipeline where spray head is fixed on the top of reaction kettle, and the reaction solution after cooling is flowed down from eminence, can be provided higher
Speed, better mixing effect can be generated.
Preferably, the quantity of the pump is two, including the first pump and the second pump, the quantity of heat exchanger are two, including
First Heat Exchanger and the second heat exchanger, the first pump and the second pump are in parallel, and First Heat Exchanger and the second heat exchanger are in parallel.Two sets of setting
Pump and heat exchanger, can satisfy big volume reaction kettle gas-liquid two-phase and are sufficiently mixed requirement.
Preferably, the spout end of the spray head is undergauge structure.The jet velocity of circular response liquid can be significantly improved,
Improve the degree of gas-liquid mixed.
Preferably, it is additionally provided with CO distributor in the reaction kettle, is mounted on the bottom of reaction kettle, CO distributor is by 5 layers
Porous ring type tube body is interconnected and forms, and is followed successively by first layer ring type tube body, second layer ring type tube body, third layer ring from bottom to top
Formula tube body, the 4th layer of ring type tube body and layer 5 ring type tube body, this 5 layers of ring type tube bodies are concentric structure.
The porous ring type tube body of 5 layers of CO distributor is distributed at different height, and in distribution with one heart, can be by the CO same time-division
Cloth is distributed in the whole cross section of reaction kettle in different-diameter position convenient for CO.It is distributed at different height, ensure that Vertical Square
It is uniformly distributed to CO, especially in the case where fluid agitation reduction, guarantees that top reaction solution sufficiently reacts, it is mixed to improve gas-liquid two-phase
Close reaction effect.
Preferably, the 4th layer of ring type tube body, third layer ring type tube body, first layer ring type tube body, second layer ring type tube body and
The ring body radius of layer 5 ring type tube body is sequentially reduced.First layer ring type tube body be CO gas total score stringing, second and third, four layers of ring
Formula tube body is corresponding with hemispherical bottom plane space, and layer 5 ring type tube body is to preceding four layers of ring type tube body in plane and vertical
Supplement in CO distribution, 5 layers of porous ring type tube body do not stay dead angle in reaction kettle plane domain, and operation is integrally presented and rises
Gesture, along with the poly- of bubble and and separation, realize that the CO in entire reaction kettle space is uniformly distributed.
Preferably, the internal diameter of first layer ring type tube body is maximum, is CO gas total score stringing, is connected with bottom and central axis.
While distribution to CO gas, also acts as and play the role of bracing reinforcement to four layers of top ring type tube body.
Preferably, the distance between first layer ring type tube body and second layer ring type tube body, second layer ring type tube body and third
The distance between the distance between layer ring type tube body, third layer ring type tube body and the 4th layer of ring type tube body, the 4th layer of ring type tube body
The ratio of the distance between layer 5 ring type tube body is 1:1:3-5:2-3.
Preferably, the diameter of the stomata on the porous ring type tube body of CO distributor is 1-3mm, and stomata spacing is 3-6mm.
Preferably, the process units further includes quantizer, dealdehyder tower and decanter, the entrance of the quantizer and de- light
The top of tower is connected to, and the light phase export of quantizer is connected to the top entry of dealdehyder tower, and the top exit of dealdehyder tower passes through condensation
The connection of the entrance of device and decanter, the centre exit of decanter are connected to dealdehyder tower top, the lower part outlet of decanter and layering
Device connection, the upper outlet of decanter are connect with waste liquid recovery apparatus；
The outlet at bottom of dealdehyder tower is connect with lightness-removing column.
Lightness-removing column " light phase " pipeline is equipped with full gear device, process are as follows: " light phase " in quantizer flows back into lightness-removing column
Pump, pump discharge branch into dealdehyder tower.Into dealdehyder tower initial material after reboiler heats, dealdehyder tower from the bottom to top
Each layer filler in complete heat and Medium Exchange.The gaseous phase materials warp containing higher reducing impurity being concentrated at the top of dealdehyder tower
It is sent into decanter after condenser condensation and carries out extracting operation.Decanter at work, first passes around pretreated containing higher
The material of reducing impurity concentration, after mouth addition extractant is added by top material extractant, from top material tangential inlet
Into decanter cylinder inner funnel shape separator；Material rotates in separator generates centrifugal force, and heavy constituent is (mainly
Iodomethane) it is acted on by centrifugal force and throws to separator walls, and exported by helix downstream to separator bottom along wall, it is low
Stream.Light component impurity (mainly acetaldehyde, crotons aldehydes) then rises after being extracted agent extraction, by top material outlet overflows
Out.Decanter lower part is expansion chamber, and underflow, which falls into merge with extractant again after expansion chamber, carries out secondary settlement layering；Sedimentation layering
System participates in reaction before decanter bottom heavy phase is returned by bottoms material outlet afterwards, and middle part is mainly the mixing of acetic acid and soft water
System carries out multiple rectifying before material is returned by lower return material outlet, and top light component reducing impurity passes through top object
Material outlet, middle part material outlet discharge into spent acid storage tank.Product can be improved by the present apparatus and restore potassium permanganate fading time, and
Reduce the content of propionic acid in product.
A kind of production method of synthesizing acetic acid by methanol low-voltage carbonylation, includes the following steps:
1) the CO distributor in the reacted bottom portion of CO gas enters in reaction kettle, methanol mixed with diluted acid, iodomethane after from
Reactor bottom enters reaction kettle, is stirred using above-mentioned fluid stirring device to material, under the action of rhodium base catalyst
It reacts and generates acetic acid；
2) in reaction kettle after the reaction was completed, reaction solution enters in transformation pot that the reaction was continued；
3) reaction solution enters evaporator after flash valve depressurizes in transformation pot, and gas phase enters prewashing tower and washed, liquid phase
Reaction kettle is returned to continue to participate in reaction；
4) evaporator gas phase separates after the washing of prewashing tower into lightness-removing column rectifying, isolates light component at the top of lightness-removing column,
Main component is iodomethane, methyl acetate, water etc., returns to synthesis system and continues to participate in reaction；The thick vinegar of lightness-removing column bottom extraction
Acid is after dehydrating tower drying, finishing column purification, output essence acetic acid；
Lightness-removing column top gas phase is after heat exchanger condenses, and into quantizer, due to the difference of density, divides in quantizer
For light phase and heavy phase, light phase enters in dealdehyder tower, the gaseous phase materials warp containing higher reducing impurity being concentrated at the top of dealdehyder tower
Be sent into decanter after condenser condensation and extracted, be centrifuged, in the middle part of acetic acid and the mixed material of water return in dealdehyder tower,
The heavy phase of its bottom returns to quantizer.
Preferably, in step 1), the fluid flow that each pump of fluid stirring device provides is 350-420m3/h。
Preferably, in step 1), the fluid flow rate that each spray head sprays is 10-25m/s.
Preferably, in step 4), after the acetic acid produced from finishing column is cooled to 100 DEG C, into adsorption tower, in adsorption tower
Pressure is 0.2-0.5Mpa, and temperature is 40-138 DEG C, the formic acid in the absorption abjection acetic acid of silver-colored oxidant is overloaded, by adsorption tower
In the acetic acid that comes out enter ion exchange tower, the pressure of the ion exchange tower is 0.2-0.5Mpa, and temperature is 80-100 DEG C, is passed through
The absorption of sulfonic polystyrene type ion exchange resin removes the iodine in acetic acid, purification acetic acid is obtained, by what is come out in ion exchange tower
Acetic acid is cooled down by heat exchanger, and temperature is down to 30-50 DEG C, is stored subsequently into storage tank.Iodine device is taken off by this to take off
After removing, formic acid impurity content in acetic acid can be down to 30PPm hereinafter, content of iodine is down to 10PPb or less.
The invention has the benefit that
1) CO distributor and fluid stirring device of the invention improve CO gas using reaction kettle mother liquor repeats itself
And circulating mother liquor distribution, distributor aperture make CO air pocket be dispersed into minute bubbles and become more evenly, to realize gas-liquid in reaction kettle
Phase is sufficiently mixed, and reaction rate greatly improves, and ensure that CO is divided, and is improved conducive to the stability of catalyst, device
Production capacity is promoted to 600,000 tons/year by 300,000 tons/year.The application of the technology, which not only eliminates mechanical stirring, simultaneously may cause
Parking hidden danger, realize it is lasting, stables, be safely operated, and saved investment, operation, maintenance cost expenditure.
2) above-mentioned full gear device can effectively remove reducing impurity during acetic acid refining, and final product quality standard can be improved
In potassium permanganate recedence time, and reduce the content of most important impurity propionic acid in finished product.
3) present invention increases de- iodine device, formic acid impurity content in acetic acid can be down to 30PPm hereinafter, content of iodine is down to
10PPb or less.Acetate products are refined as made from this process for refining, are met the demand of downstream high-end product, be can be used for vinegar
The demand of the high-end customers such as the production of sour ethylene.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the attachment structure schematic diagram of the production system of improved synthesizing acetic acid by methanol low-voltage carbonylation of the invention；
Fig. 2 is fluid agitation system attachment structure schematic diagram of the invention；
Fig. 3 is the vertical view figure structure schematic representation of fluid agitation pipe of the invention；
The main view schematic diagram of Fig. 4 fluid agitation pipe；
Fig. 5 is CO distributor main view schematic diagram of the invention；
Fig. 6 is that CO distributor of the invention overlooks figure structure schematic representation；
Fig. 7 is that essence of the invention takes off iodine device flow chart；
Fig. 8 is full gear device flow chart of the invention.
Wherein: 1, high pressure absorber, 2, low-pressure absorption tower, 3, reaction kettle, 4, transformation pot, 5, evaporator, 6, prewashing tower, 7,
Lightness-removing column, 8, quantizer, 9, dehydrating tower, 10, finishing column, 11, de- iodine device, 12, stripping tower, 13, dealkylation tower, 14, dealdehyder tower,
15, first spray head, 16, second spray head, 17, First Heat Exchanger, the 18, second heat exchanger, 19, first pump, 20, second pump, 21, in
Heart fixing axle, 22, layer 5 ring type tube body, 23, the 4th layers of ring type tube body, 24, third layer ring type tube body, 25, second layer ring type
Tube body, 26, CO nozzle, 27, first layer ring type tube body, the 28, first cooler, 29, adsorption tower, 30, ion exchange tower, 31,
Two coolers, 32, decanter.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As shown in Figure 1, a kind of process units of synthesizing acetic acid by methanol low-voltage carbonylation, including high pressure absorber 1, low pressure are inhaled
Receive tower 2, reaction kettle 3, transformation pot 4, evaporator 5, prewashing tower 6, lightness-removing column 7, dehydrating tower 9, finishing column 10 and fluid stirring device.
Its process flow are as follows: reacted 3 bottom of kettle of the CO gas of gauge pressure 3.2MPa enters reaction kettle 3, is divided into CO greatly through CO distributor
Small uniform minute bubbles, methanol (comprising absorbing methanol) mixed with diluted acid, iodomethane from distillation system after from 3 bottom of reaction kettle
Portion enters reaction kettle 3, and each stock material reacts under the action of rhodium base catalyst generates acetic acid, and reaction solution is from reaction kettle 3
Portion enters in transformation pot 4 that the reaction was continued, improves conversion level, and 4 reaction solution of transformation pot enters evaporator 5 after pressure reducing valve depressurizes,
Gas phase in transformation pot 4 is passed through in high pressure absorber 1 iodomethane absorbed in tail gas using methanol as absorbent, acetic acid steams
Vapour etc., the gas phase in evaporator 5 enter prewashing tower 6 and are washed, and recycle the components such as HI and catalyst, the liquid phase in evaporator 5
Reaction kettle 3 is returned to continue to participate in reaction.The flash distillation gas phase of evaporator 5 carries out tentatively after the washing of prewashing tower 6 into lightness-removing column 7
Lock out operation, 7 top gas phase of lightness-removing column are condensed through heat exchanger, and condensate liquid is divided into " light phase " and " heavy phase " according to density difference, and
It is layered in quantizer 8, " light phase " is mainly methyl acetate and water, and " heavy phase " is mainly iodomethane, work of the two in kinetic pump
It is recycled under in reaction kettle 3 and continues to participate in reaction.Fixed gas enters in low-pressure absorption tower 2, using methanol as absorbent, inhales
Then iodomethane, acetic acid steam etc. in ending gas return to reaction kettle 3 and continue to participate in reaction.The thick vinegar of 7 bottom of lightness-removing column extraction
After acid is purified by the drying of dehydrating tower 9, finishing column 10, output content is up to 99.85% or more smart acetic acid.
As shown in Figure 2, Figure 3 and Figure 4, the fluid stirring device includes at least two spray heads, pump and heat exchanger, the pump
Input end be connected to the middle part of reaction kettle 3, the outlet end of pump is connected to the input end of heat exchanger, and the fixed -piping of spray head is fixed
At the top of reaction kettle 3, the end of the fixed -piping of the outlet end and spray head of heat exchanger is connected to, and spray head is in reaction kettle 3
Wall setting, spray head are set to reaction kettle liquid level or less 200-500mm, the angle of diameter where two neighboring spray head be set as 45 °-
90 °, preferably 90 °.
As a kind of specific embodiment, the quantity of the pump is two, including the first pump 19 and the second pump 20, heat exchange
The quantity of device is two, including First Heat Exchanger 17 and the second heat exchanger 18, and the first pump 19 and the second pump 20 are in parallel, the first heat exchange
Device 17 and the second heat exchanger 18 are in parallel.Two sets of pumps of setting and heat exchanger, it is sufficiently mixed to can satisfy big volume reaction kettle gas-liquid two-phase
It closes and requires.
As shown in figure 4, the spout end of spray head is set as undergauge structure.The injection speed of circular response liquid can be significantly improved
Degree, improves the degree of gas-liquid mixed.
As shown in Figure 5 and Figure 6, as a preferred embodiment, being additionally provided with CO distributor in reaction kettle 3, CO points
Orchestration is mounted on the bottom of reaction kettle 3 by central fixed shaft 21, CO distributor be interconnected by 5 layers of porous ring type tube body and
At being followed successively by 24, the 4th layers of first layer ring type tube body 27, second layer ring type tube body 25, third layer ring type tube body ring from bottom to top
Formula tube body 23 and layer 5 ring type tube body 22, this 5 layers of ring type tube bodies are concentric structure.
The porous ring type tube body of 5 layers of CO distributor is distributed at different height, and in distribution with one heart, can be by the CO same time-division
Cloth is distributed in the whole cross section of reaction kettle in different-diameter position convenient for CO.It is distributed at different height, ensure that Vertical Square
It is uniformly distributed to CO, especially in the case where fluid agitation reduction, guarantees that top reaction solution sufficiently reacts, it is mixed to improve gas-liquid two-phase
Close reaction effect.
As shown in figure 5, the 4th layer of ring type tube body 23, third layer ring type tube body 24, first layer ring type tube body 27, second layer ring
The ring body radius of formula tube body 25 and layer 5 ring type tube body 22 is sequentially reduced.4th layer of ring type tube body, third layer ring type tube body,
The ring body radius of one layer of ring type tube body, second layer ring type tube body and layer 5 ring type tube body is sequentially reduced.First layer ring type tube body
For CO gas total score stringing, second and third, four layers of ring type tube body it is corresponding with hemispherical bottom plane space, layer 5 ring type tube body
It is the supplement to preceding four layers of ring type tube body in plane and vertical CO distribution, 5 layers of porous ring type tube body are in reaction kettle plane domain
Do not stay dead angle, and integrally present operation ascendant trend, along with the poly- of bubble and and separation, realize the CO in entire reaction kettle space
It is uniformly distributed.The internal diameter of first layer ring type tube body 27 is maximum, is CO gas total score stringing, is connected with bottom and central axis, to CO
While gas is distributed, also acts as and play the role of bracing reinforcement to 4 layers of ring type tube body on top.First layer ring type tube body and second
The distance between the distance between layer ring type tube body, second layer ring type tube body and third layer ring type tube body, third layer ring type tube body
The ratio of the distance between the distance between 4th layer of ring type tube body, the 4th layer of ring type tube body and layer 5 ring type tube body is 1:1:
3-5:2-3。
The diameter of stomata on porous ring type tube body is 1-3mm, and stomata spacing is 3-6mm.
Fluid stirring device is set as two sets, and list covering device fluid flow controls 350-420m3/ h is anti-to meet big volume
Kettle gas-liquid two-phase is answered to be sufficiently mixed requirement, every covering device is made of kinetic pump, heat exchanger, fluid agitation pipe and spray head, process
Are as follows: reaction solution is flowed out by middle part, and two-way is divided to enter two covering device kinetic pumps, and power pump discharge connects heat exchanger, passes through heat exchange
After device cools down to reaction solution, reaction kettle is laterally entered from reaction kettle top and continues to participate in reaction, is equipped with and flows inside reaction kettle
Body stirring pipe, two covering device fluid agitation pipes and kettle central plane angle are 90 °, each fluid agitation pipe root variable diameter, control
Fluid flow rate 10-25m/s, in order to guarantee fluid agitation effect, fluid agitation pipe spray head should be at reaction kettle liquid level or less 200-
Between 500mm.When operation, reaction solution laterally enters reaction kettle at the top of reaction kettle, flows downward along kettle wall high speed, drives periphery
Liquid occur vector change, and from reaction kettle lower part overturning and on, form the different Two-way Cycle stream of multiple main flow layers
Dynamic state.
The CO distributor and fluid stirring device change mechanical stirring axle envelope and transmission device rapid wear in the process of running
Bad situation, dynamic sealing point is eliminated, and greatly improves system safe and stable operation, while the distribution of CO gas is more uniform,
Improve gas-liquid two-phase mixed effect, promote reaction rate, optimization system reactiveness, device capbility is promoted to by 300,000 tons/year
600000 tons/year.
As shown in figure 8, the process units further includes full gear process, full gear process includes quantizer 8, dealdehyder tower 14 and inclines
The entrance of parser 32, the quantizer 8 is connected to the top of lightness-removing column 7, the light phase export of quantizer 8 and the top of dealdehyder tower 14
The top exit of entrance connection, dealdehyder tower 14 is connect by condenser with the entrance of decanter 32, the centre exit of decanter 32
It is connected to 14 top of dealdehyder tower, the lower part outlet of decanter 32 is connect with quantizer 8, and the upper outlet and waste liquid of decanter 32 are returned
Receiving apparatus connection；The outlet at bottom of dealdehyder tower 14 is connect with lightness-removing column 7.
Its process are as follows: " light phase " in quantizer enters lightness-removing column reflux pump, and pump discharge branches into dealdehyder tower.Into de-
The initial material of aldehyde tower completes heat in each layer filler of dealdehyder tower from the bottom to top and medium is handed over after reboiler heats
It changes.The gaseous phase materials containing higher reducing impurity being concentrated at the top of dealdehyder tower are sent into decanter after condenser condenses to carry out
Extracting operation.Decanter at work, first passes around the pretreated material containing higher reducing impurity concentration, passes through top
After mouth addition extractant is added in materials abstraction agent, enter decanter cylinder inner funnel shape separator from top material tangential inlet；
Material rotates in separator generates centrifugal force, and heavy constituent (mainly iodomethane) throws to separator by centrifugal force effect
Wall, and exported by helix downstream to separator bottom along wall, it is low stream.Light component impurity (mainly acetaldehyde, crotonaldehyde
Class) be extracted agent extraction after then rise, gone out by top material outlet overflows.Decanter lower part is expansion chamber, and underflow falls into heavy
It is merged again with extractant behind drop room and carries out secondary settlement layering；Decanter bottom heavy phase is exported by bottoms material after sedimentation layering
System participates in reaction before returning, and middle part is mainly system before the mixed material of acetic acid and soft water is returned by lower return material outlet
System carries out multiple rectifying, and top light component reducing impurity discharges into spent acid storage tank by top material outlet, middle part material outlet.
Product can be improved by the present apparatus and restore potassium permanganate fading time, and reduce the content of propionic acid in product.
As shown in fig. 7, the finishing column is equipped with de- iodine device, including sequentially connected first cooling in finished product extraction pipeline
The acetic acid of device 28, adsorption tower 29, ion exchange tower 30 and the second cooler 31, the first cooler 28 and finishing column 10, which exports, to be connected
It connects.
Its process are as follows: the acetic acid produced from finishing column 10 is after the first cooler 28 is cooled to 100 DEG C, into adsorption tower
29, the pressure in adsorption tower 29 is 0.2-0.5Mpa, and temperature is 40-138 DEG C, and inside setting carries silver-colored oxidant adsorbent layer, warp
The formic acid in the absorption abjection acetic acid of silver-colored oxidant is overloaded, ion exchange tower 30 is entered by the acetic acid come out in adsorption tower 29, it should
The pressure of ion exchange tower 30 is 0.2-0.5Mpa, and temperature is 80-100 DEG C, inside setting sulfonic polystyrene type ion exchange resin
Layer, absorption of the acetic acid Jing Guo sulfonic polystyrene type ion exchange resin remove the iodine in acetic acid, obtain purification acetic acid, are handed over by ion
It changes the acetic acid come out in tower 30 to be cooled down by the second heat exchanger 31, temperature is down to 30-50 DEG C, is store subsequently into storage tank
It deposits, after this takes off the removing of iodine device, formic acid impurity content in acetic acid can be down to 30PPm hereinafter, content of iodine is down to 10PPb
Below.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (7)
1. a kind of process units of synthesizing acetic acid by methanol low-voltage carbonylation, it is characterised in that: including reaction kettle, transformation pot, evaporation
Device, prewashing tower, lightness-removing column, dehydrating tower, finishing column and fluid stirring device, wherein the fluid stirring device includes at least two
A spray head, pump and heat exchanger, the input end of the pump are connected to the middle part of reaction kettle, the outlet end of pump and the input end of heat exchanger
Connection, the fixed -piping of spray head are fixed on the top of reaction kettle, and the end of the fixed -piping of the outlet end and spray head of heat exchanger connects
Logical, spray head is arranged close to the inner wall of reaction kettle, and spray head is set to reaction kettle liquid level or less 200-500mm, two neighboring spray head institute
The angle of diameter be 45 ° -90 °, the spout end of spray head is undergauge structure, and when operation, reaction solution is from reaction kettle top side
To reaction kettle is entered, flows downward along kettle wall high speed, drive the liquid on periphery that the change of vector occurs, and turn over from reaction kettle lower part
On then, the different Two-way Cycle flow regime of multiple main flow layers is formd；
It is additionally provided with CO distributor in the reaction kettle, is mounted on the bottom of reaction kettle, CO distributor is by 5 layers of porous ring type tube body
It is interconnected and forms, be followed successively by first layer ring type tube body, second layer ring type tube body, third layer ring type tube body, the 4th from bottom to top
Layer ring type tube body and layer 5 ring type tube body, this 5 layers of ring type tube bodies are concentric structure；
4th layer of ring type tube body, third layer ring type tube body, first layer ring type tube body, second layer ring type tube body and layer 5 ring type pipe
The ring body radius of body is sequentially reduced；
The internal diameter of first layer ring type tube body is maximum, is CO gas total score stringing, is connected with bottom and central axis；
The distance between first layer ring type tube body and second layer ring type tube body, second layer ring type tube body and third layer ring type tube body it
Between the distance between distance, third layer ring type tube body and the 4th layer of ring type tube body, the 4th layer of ring type tube body and layer 5 ring type
The ratio of the distance between tube body is 1:1:3-5:2-3.
2. process units according to claim 1, it is characterised in that: the quantity of the pump be two, including first pump and
Second pump, the quantity of heat exchanger is two, including First Heat Exchanger and the second heat exchanger, and the first pump and the second pump are in parallel, first
Heat exchanger and the second heat exchanger are in parallel.
3. process units according to claim 1, it is characterised in that: stomata on the porous ring type tube body of CO distributor
Diameter is 1-3mm, and stomata spacing is 3-6mm.
4. process units according to claim 1, it is characterised in that: the process units further includes quantizer, dealdehyder tower
And decanter, the entrance of the quantizer are connected to the top of lightness-removing column, are entered at the top of the light phase export and dealdehyder tower of quantizer
The top exit of mouth connection, dealdehyder tower is connected by the entrance of condenser and decanter, the centre exit and dealdehyder tower of decanter
Top connection, the lower part outlet of decanter are connect with quantizer, and the upper outlet of decanter is connect with waste liquid recovery apparatus；
The outlet at bottom of dealdehyder tower is connect with lightness-removing column.
5. a kind of producer of the process units using the synthesizing acetic acid by methanol low-voltage carbonylation any in claim 1-4
Method, characterized by the following steps:
1) the CO distributor in the reacted bottom portion of CO gas enters in reaction kettle, from reacting after methanol and diluted acid, iodomethane mixing
Bottom portion enters reaction kettle, is stirred using fluid stirring device to material, is reacted under the action of rhodium base catalyst
Generate acetic acid；
2) in reaction kettle after the reaction was completed, reaction solution enters in transformation pot that the reaction was continued；
3) reaction solution enters evaporator after flash valve depressurizes in transformation pot, and gas phase enters prewashing tower and washed, and liquid phase returns
Reaction kettle continues to participate in reaction；
4) evaporator gas phase separates after the washing of prewashing tower into lightness-removing column rectifying, isolates light component at the top of lightness-removing column；It is de- light
The thick acetic acid of tower bottom extraction is after dehydrating tower drying, finishing column purification, output essence acetic acid；
Lightness-removing column top gas phase is after heat exchanger condenses, and into quantizer, due to the difference of density, is divided into quantizer light
Mutually enter in dealdehyder tower with heavy phase, light phase, the gaseous phase materials containing higher reducing impurity being concentrated at the top of dealdehyder tower are through condensing
Be sent into decanter after device condensation and extracted, be centrifuged, in the middle part of acetic acid and the mixed material of water return in dealdehyder tower, bottom
The heavy phase in portion returns to quantizer.
6. production method according to claim 5, it is characterised in that: in step 1), each pump of fluid stirring device is mentioned
The fluid flow of confession is 350-420m3/h；The fluid flow rate that each spray head sprays is 10-25m/s.
7. production method according to claim 5, it is characterised in that: in step 4), the acetic acid produced from finishing column is cooling
To after 100 DEG C, into adsorption tower, the pressure in adsorption tower is 0.2-0.5Mpa, and temperature is 40-138 DEG C, is overloaded silver-colored oxidant
Absorption abjection acetic acid in formic acid, by adsorption tower come out acetic acid enter ion exchange tower, the pressure of the ion exchange tower
For 0.2-0.5Mpa, temperature is 80-100 DEG C, by the absorption of sulfonic polystyrene type ion exchange resin, removes the iodine in acetic acid,
Purification acetic acid is obtained, is cooled down by the acetic acid come out in ion exchange tower by heat exchanger, temperature is down to 30-50 DEG C, then
It is stored into storage tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811224192.9A CN109134233B (en) | 2018-10-19 | 2018-10-19 | A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation |
| PCT/CN2019/112043 WO2020078476A1 (en) | 2018-10-19 | 2019-10-18 | Production device and production method for synthesizing acetic acid by low-pressure carbonylation of methanol |
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| CN201811224192.9A CN109134233B (en) | 2018-10-19 | 2018-10-19 | A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation |
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| CN109134233B (en) * | 2018-10-19 | 2019-08-30 | 兖矿鲁南化工有限公司 | A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation |
| CN112574021A (en) * | 2019-09-12 | 2021-03-30 | 南京延长反应技术研究院有限公司 | Enhanced carbonylation reaction system and process |
| CN114053961B (en) * | 2020-08-03 | 2023-01-03 | 中国石油化工股份有限公司 | Feeding distributor and reactor |
| CN112608232B (en) * | 2020-12-04 | 2023-01-20 | 兖矿鲁南化工有限公司 | System and method for recycling reaction heat in process of synthesizing acetic acid by methanol low-pressure carbonyl |
| CN112844251A (en) * | 2021-01-06 | 2021-05-28 | 上海华谊能源化工有限公司 | Reaction device and system and method for synthesizing acetic acid by carbonyl |
| CN115007099B (en) * | 2022-05-26 | 2023-06-20 | 浙江大学 | Oxo reactor and working method thereof |
| CN115650841B (en) * | 2022-10-26 | 2023-12-29 | 西南化工研究设计院有限公司 | Method for synthesizing acetic acid by methanol low-pressure carbonyl |
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| CN1257145C (en) * | 2004-02-18 | 2006-05-24 | 上海吴泾化工有限公司 | Carbonylation reactor for producing acetic acid, and application method |
| CN201280529Y (en) * | 2008-10-07 | 2009-07-29 | 兖矿国泰化工有限公司 | Methanol low-pressure carbonylation reaction device |
| CN101885678B (en) * | 2010-07-05 | 2013-03-13 | 兖矿国泰化工有限公司 | Reaction equipment for synthesizing ethylic acid by low-pressure methanol carbonylation of methanol |
| CN202238013U (en) * | 2011-09-15 | 2012-05-30 | 兖矿国泰乙酰化工有限公司 | Gas distributor of reactor for low-pressure carbonyl synthesized acetate |
| CN104623926B (en) * | 2015-02-10 | 2016-04-06 | 兖矿国泰化工有限公司 | Separating reducing impurity decanter in a kind of acetic acid refining process |
| CN107986953B (en) * | 2017-12-06 | 2021-07-23 | 江苏索普化工股份有限公司 | Production device and production process for synthesizing acetic acid by methanol low-pressure carbonyl |
| CN109134233B (en) * | 2018-10-19 | 2019-08-30 | 兖矿鲁南化工有限公司 | A kind of process units and production method of synthesizing acetic acid by methanol low-voltage carbonylation |
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