CN108929436A - A kind of preparation method of copolymer nylon - Google Patents
A kind of preparation method of copolymer nylon Download PDFInfo
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- CN108929436A CN108929436A CN201810599410.0A CN201810599410A CN108929436A CN 108929436 A CN108929436 A CN 108929436A CN 201810599410 A CN201810599410 A CN 201810599410A CN 108929436 A CN108929436 A CN 108929436A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
The present invention provides a kind of preparation method of copolymer nylon, includes the following steps：1）Caprolactam melt and storage；2）Dissolution, storage, the concentration of salt；3）Auxiliary agent is prepared；4）Three-step approach continuous polymerization；5）Cast Strip pelletizing；6）Extraction；7）It is dry.The present invention has the beneficial effect that：1）It is simple process, safe and reliable；2）Properties of product are excellent；3）Water resource realization in preparation process recycles, non-wastewater discharge, energy-saving and emission-reduction；4）The caprolactam of fusing and the solid caprolactam entered in melting tank, which are mixed together, can accelerate it in the melting of tank, and melting efficiency is high；5）66 salt dissolved and 66 salt of solid entered in dissolving tank, which are mixed together, can accelerate its dissolving in tank, dissolve high-efficient.
Description
Technical field
The present invention relates to nylon field, in particular to a kind of preparation method of copolymer nylon.
Background technique
For polyamide due to highly polar feature, hygroscopicity is strong, poor dimensional stability, and the polyamide of one-component is far from full
The demand applied enough.In order to expand the application range of polyamide, by carrying out modification by copolymerization to existing polyamide, it is new to assign it
Properity and use field, be a kind of widely used chemical modification method and a very promising job.
Summary of the invention
It is an object of the invention to propose a kind of preparation method of copolymer nylon, the simple, properties of product with preparation process
The advantages that excellent, energy-saving.
To achieve the goals above, the present invention provides a kind of preparation method of copolymer nylon, includes the following steps：
1）Caprolactam melt and storage
Solid caprolactam in packaging bag is transported in pulverizer, and pulverizer will squeeze broken under filtering ventilation protection
Caprolactam is through screw rod transmission into the melting tank with nitrogen protection, and the caprolactam of melting tank fusing is after filtering by pumping section
Divide and deliver into storage tank and then be subsequent technique use, another part example in mass ratio is adjusted, and is entered after heated with just crushing
Solid caprolactam in melting tank is mixed together to accelerate it in the melting of tank.（The caprolactam of fusing：Solid caprolactam
=1：4-4：1）
The pipeline of all melting zones melts and holding vessel uses hot water heating, and the caprolactam in storage tank is defeated by pumping after filtration
It is sent to subsequent technique area.
Further, the caprolactam of the fusing is first sent by tank car to independent pans, is conveyed again after sampling is qualified
Storage tank.
2）Dissolution, storage, the concentration of salt
Synthesize 66 salt techniques：It is mixed using 20% methanol solution of adipic acid and 50% methanol solution of hexamethylene diamine, reaction temperature 60-
70 DEG C, pH control is in 6.7-7.0, and methanol eddy product separates through crystallisation by cooling, cleaning, dry 66 salt.
66 salt of solid is transported in pulverizer, and it is defeated by screw rod that pulverizer will squeeze 66 broken salt under filtering ventilation protection
It is sent in the dissolving tank with nitrogen protection, storage tank is delivered by pump portion after filtering in 66 saline solutions that dissolving tank dissolves
And then used for subsequent concentration technique, another part example in mass ratio, which is adjusted after heat exchanger heats and just crushed, enters dissolving tank
In 66 salt of solid be mixed together to accelerate it in the dissolution of tank.（66 saline solutions dissolved：66 salt=1 of solid：2-6：1）
The pipeline and holding vessel of all dissolution zones use 90 degree or more hot water heatings, according to setting yield needs, in storage tank 66
Salt is transported to concentration tank by pump after filtration.
Further, the water of the concentration tank concentration and evaporation and fresh water mixing circulation are used as dissolution water.
3）Auxiliary agent is prepared
The configuration of 3.1 auxiliary agent A D21
AD21 is automatically controlled by the pressure of the second polymer reactor, its liquid with other auxiliary agents and from tank area is fresh in oneself
Amide is continuously introduced into the mixing channel before the second polymerizer by process requirement flow and enters back into reactor after mixing.
3.2 auxiliary agent A D26 configuration
Stabilizer AD26 and desalted water by setting volume ratio it is agitated be uniformly mixed, filtered after sampling confirmation, be continuously introduced into the
Mixing channel before dimerization clutch.
The configuration of 3.3 high effective and modified doses 28 (HPA28)
A certain amount of liquid CPL is made into aqueous solution and is transported to preparing tank, is added given HPA28 amount under stiring, while by giving
Heating of fixing time dissolves by heating high effective and modified dose 28 (HPA28), is pressed into storage tank with nitrogen after sampling is qualified, and HPA28 solution is from storage
Through filtering the mixing channel before being continuously introduced into the second polymer reactor in tank.
4）Three-step approach continuous polymerization
4.1 first step high pressure prepolymerizations
Caprolactam in storage tank and 66 salting liquids from concentration tank convey through pump and add via high temperature heating agent such as biphenyl
The pipeline and special heater of heat are transported in mixer and enter back into the first polymer reactor, 66 salting liquids being concentrated herein and
Caprolactam in storage tank after forcing turbulent condition to be sufficiently mixed by pump by being conveyed into high pressure pre-polymerizer, by the stop of setting
After time aggregation reaction, discharge vapor is purified from overhead reflux, reaction pre-polymer melt delivers into second step polymerization together
The mixing such as reactor and fresh caprolactam, auxiliary agent A D26, HPA28 continue polymerization reaction.Pressure can when first step high pressure polymerisation
Reach 36-40 Bar.
The polymerization of 4.2 second steps
It is compared with the high pressure of the first polymer reactor and overhead reflux draining, the second polymer reactor is closed and pressure does not surpass
Cross 8 bar, the dynamic mixing channel mixing of fresh caprolactam and auxiliary agent before the reactor inlet, subsequently into the second polymerization reaction
Special Mixed device in device and the mixing of the prepolymer from the first polymer reactor continue polymerization reaction, are entering the
Most water are detached from by the fractionating column at the top of the first polymer reactor before dimerization reactor, thus guarantee polymerization reaction after
The continuous pressure for quickly pushing ahead the second polymer reactor is 6-8 bar.
The polymerization of 4.3 third steps
The prepolymer come out from the second polymer reactor is conveyed by gear pump, through melt drier into post-polymerization device,
In melt drier, because the excessive water of pressure change in prepolymer melt from separating and by the bubble at the top of post polymerizer
It mixes, cool down with protection nitrogen in cover tower, then feed liquor sealing groove condenses together.The low molecule raw material of moisture entrainment is in bubble column
It condenses and passes back into post polymerizer.
Further, the three-step approach continuous polymerization technique section all by liquid biphenyl or biphenyl steam jacket heating or it is cold
But.
5）Cast Strip pelletizing
Melt cools down after pattern hole extrusion again through pump conveying, is then delivered to cutter pelletizing, transport platform has water circulation system cold
But, slice is delivered directly to dewaterer, unqualified slice point is fallen through sieve after slice dehydration, then slices synthesis method to drying
Tower.
6）Extraction
Extraction workshop section mainly PA6 be sliced in monomer and oligomer the hot water counter-current extraction in extraction tower walk.
Slice is transported to the knockout drum at the top of extraction tower by mashing pump, then enters at the top of extraction tower from tank and move from top to down
The dynamic conveying water by upstream water hot extraction, come out from knockout drum is pumped back after filtering continues cycling through use.
There are twice circulation waterway and twice water charging system in extraction tower, it is upstream when top slice starts extraction
Extraction water section leaves extraction tower from top and enters recovery system and uses as slices synthesis method water, weighs after another part is heated
Newly enter extraction tower to be recycled.
Extraction tower bottom have twice water charging system, be together by process requirement amount after the concentration of recycling condensed water,
Another road is the return water being sliced after conveying extraction by extraction tower liquid automatic control rate of water make-up.
Further, there are also a circulations in extraction water inlet top, extraction tower to guarantee the solubility gradient in tower
With the stabilization of temperature gradient.
Slice extracted is transported to centrifuge separation sieve through mashing pump by tower bottom and enters subsequent drying process, and conveying water is then
Returned recycling.
Further, to improve extraction efficiency, extraction Deethanizer design also devises (nitrogen) extraction with pressure.
7）It is dry
Drying system runs under micro-positive pressure, and drying tower is by about 110% designing surely.
Slice, which enters, is sent to drying tower, slowly moves down from tower top and is dried by upstream flow of warm nitrogen gas.
Slice after drying is sent to by rotary valve by delivery system after recirculated cooling water is cooling in the cooler under tower bottom
System is sent to feed bin.
Further, in drying tower, drying nitrogen outlet used is connected with cyclone dust collector,.
The present invention has the beneficial effect that：1）It is simple process, safe and reliable using conventional equipment and conventional chemical process；2）
Product elongation at break obtained, bending strength, notch impact strength etc. all increase, and properties of product are excellent；3）It prepared
Water resource realization in journey recycles, non-wastewater discharge, energy-saving and emission-reduction；4）In the caprolactam and entrance melting tank of fusing
Solid caprolactam, which is mixed together, can accelerate it in the melting of tank, and melting efficiency is high；5）In 66 salt and entrance dissolving tank dissolved
66 salt of solid be mixed together and can accelerate its dissolving in tank, dissolve high-efficient.
Specific embodiment
The embodiment of the present invention is described below in detail.
Embodiment 1：
The present invention provides a kind of preparation method of copolymer nylon, includes the following steps：
1）Caprolactam melt and storage
Solid caprolactam in packaging bag is transported in pulverizer, and pulverizer will squeeze broken under filtering ventilation protection
Caprolactam is through screw rod transmission into the melting tank with nitrogen protection, and the caprolactam of melting tank fusing is after filtering by pumping section
Divide and deliver into storage tank and then be subsequent technique use, another part example in mass ratio is adjusted, and is entered after heated with just crushing
Solid caprolactam in melting tank is mixed together to accelerate it in the melting of tank.（The caprolactam of fusing：Solid caprolactam
=1：2）
The caprolactam of fusing is first sent by tank car to independent pans, conveys storage tank again after sampling is qualified.
The caprolactam reserves of each line in tank field are designed as 96 hours continuously with required consumption when the operating of 110% specified production capacity,
Meanwhile it being based on separately running between each line tank field in design principle, but each line storage tank when necessary can motor-driven connection use feed.
The pipelines of all melting zones melts and holding vessel uses hot water heating, the caprolactam in storage tank after filtration by
Pump is conveyed toward subsequent process island.
2）Dissolution, storage, the concentration of salt
Synthesize 66 salt techniques：It is mixed using 20% methanol solution of adipic acid and 50% methanol solution of hexamethylene diamine, reaction temperature 60
DEG C, pH control is 6.7, and methanol eddy product separates through crystallisation by cooling, cleaning, dry 66 salt.
66 salt of solid is transported in pulverizer, and it is defeated by screw rod that pulverizer will squeeze 66 broken salt under filtering ventilation protection
It is sent in the dissolving tank with nitrogen protection, storage tank is delivered by pump portion after filtering in 66 saline solutions that dissolving tank dissolves
And then used for subsequent concentration technique, another part example in mass ratio, which is adjusted after heat exchanger heats and just crushed, enters dissolving tank
In 66 salt of solid be mixed together to accelerate it in the dissolution of tank.（66 saline solutions dissolved：66 salt=1 of solid：3）
The solution reserves of 66 salt 60% of tank field are designed as 48 hours continuously with required consumption when the operating of 110% specified production capacity.
The pipeline and holding vessel of all dissolution zones use 90 degree or more hot water heatings, according to setting yield needs, in storage tank
66 salt concentration tank is transported to by pump after filtration.
As energy conservation measure, the water of concentration and evaporation and fresh water mixing circulation are used as dissolution water.
3）Auxiliary agent is prepared
The configuration of 3.1 auxiliary agent A D21
AD21 is automatically controlled by the pressure of the second polymer reactor, its liquid with other auxiliary agents and from tank area is fresh in oneself
Amide is continuously introduced into the mixing channel before the second polymerizer by process requirement flow and enters back into reactor after mixing.
3.2 auxiliary agent A D26 is configured
Stabilizer AD26 and desalted water are agitated uniformly mixed by the volume ratio of setting.It is filtered after sampling confirmation, is continuously introduced into the
Mixing channel before dimerization clutch.
The configuration of 3.3 high effective and modified doses 28 (HPA28)
The aqueous solution that a certain amount of liquid CPL is made into 70% is transported to preparing tank, given HPA28 amount is added under stiring, simultaneously
It heats up by given time and dissolves by heating high effective and modified dose 28 (HPA28), be pressed into storage tank, HPA28 solution with nitrogen after sampling is qualified
Mixing channel before being continuously introduced into the second polymer reactor in storage tank through filtering.
4）Three-step approach continuous polymerization
4.1 first step high pressure prepolymerizations
Caprolactam in storage tank and 66 salting liquids from concentration tank convey through pump and add via high temperature heating agent such as biphenyl
The pipeline and special heater of heat are transported in mixer and enter back into the first polymer reactor, 66 salting liquids being concentrated herein and
Caprolactam in storage tank after forcing turbulent condition to be sufficiently mixed by pump by being conveyed into high pressure pre-polymerizer, by the stop of setting
After time aggregation reaction, discharge vapor is purified from overhead reflux, reaction pre-polymer melt delivers into second step polymerization together
Pressure can when the mixing such as reactor and fresh caprolactam, auxiliary agent A D26, HPA28 continuation polymerization reaction first step high pressure polymerisation
Reach 36 Bar.
Be in pre-polymerization reactor technological design reactor with pressure and design yield 70-110% range stable operation,
Residence time ensure that sudden reaction and subsequent polycondensation reach balance under corresponding process conditions enough.
The polymerization of 4.2 second steps
It is compared with the high pressure of the first polymer reactor and overhead reflux draining, the second polymer reactor is closed and pressure does not surpass
Cross 8 bar, the dynamic mixing channel mixing of fresh caprolactam and auxiliary agent before the reactor inlet, subsequently into the second polymerization reaction
Special Mixed device in device and the mixing of the prepolymer from the first polymer reactor continue polymerization reaction, are entering the
Most water are detached from by the fractionating column at the top of the first polymer reactor before dimerization reactor, thus guarantee polymerization reaction after
The continuous pressure for quickly pushing ahead the second polymer reactor is 6 bar.
Pressure difference between two reactors, does not have delivery pump between first reactor and second reactor.
In second polymer reactor technological design it is reactor with pressure and stablizes fortune in the range of design yield 70-110%
Row, residence time guarantee that poly- reaction reaches balance under corresponding process conditions enough.
The polymerization of 4.3 third steps
The prepolymer come out from the second polymer reactor is conveyed through melt drier by gear pump into post-polymerization device, molten
In gas dryer, because the excessive water of pressure change in prepolymer melt from separating and by the bubble-cap at the top of post polymerizer
It mixes, cool down with protection nitrogen in tower, then feed liquor sealing groove condenses together.The low molecule raw material of moisture entrainment is cold in bubble column
Coalescence passes back into post polymerizer.
Post-polymerization device works under normal pressure and with nitrogen protection, which can be divided into for four stages, and each stage has
Its corresponding special setting is to guarantee that polymer melt is completely maintained in technologic stable homogeneous distribution.In the technique of residence time
It ensure that corresponding addition polymerization and polycondensation reaction reach balance enough in different output range (70-110%) in design.
Three-step approach continuous polymerization technique section is all heated or cooled by liquid biphenyl or biphenyl steam jacket.
5）Cast Strip pelletizing
Production line pelletizing uses a set of USG pelletizing system, and melt is cooled down again after pattern hole extrusion through pump conveying, is then delivered to
Cutter pelletizing, transport platform have water circulation system cooling, and slice is delivered directly to dewaterer, is sliced after dehydration through sieve unqualified
Slice point falls, then slices synthesis method to drying tower.
6）Extraction
Monomer and oligomer the hot water counter-current extraction in extraction tower in PA6 slice is walked.
Slice is transported to the knockout drum at the top of extraction tower by mashing pump, then enters at the top of extraction tower from tank and move from top to down
The dynamic conveying water by upstream water hot extraction, come out from knockout drum is pumped back after filtering continues cycling through use.
There are twice circulation waterway and twice water charging system in extraction tower, it is upstream when top slice starts extraction
Extraction water section leaves extraction tower from top and enters recovery system and uses as slices synthesis method water, weighs after another part is heated
Newly enter extraction tower to be recycled.
Extraction tower bottom have twice water charging system, be together by process requirement amount after the concentration of recycling condensed water,
Another road is the return water being sliced after conveying extraction by extraction tower liquid automatic control rate of water make-up.
On extraction water inlet top, there are also a circulations in extraction tower to guarantee solubility gradient and the temperature gradient in tower
Stabilization.
Slice extracted is transported to centrifuge separation sieve through mashing pump by tower bottom and enters subsequent drying process, and conveying water is then
Returned recycling.
To improve extraction efficiency, extraction Deethanizer design also devises (nitrogen) extraction with pressure.
7）It is dry
Drying system runs under micro-positive pressure, and drying tower is by about 110% designing surely.
Slice, which enters, is sent to drying tower, slowly moves down from tower top and is dried by upstream flow of warm nitrogen gas.
Slice after drying is sent to by rotary valve by delivery system after recirculated cooling water is cooling in the cooler under tower bottom
System is sent to feed bin.
In drying tower, drying nitrogen outlet used is connected with cyclone dust collector,.
1. the present embodiment nylon monomer of table and copolymer nylon performance comparison
Embodiment 2：
The present invention provides a kind of preparation method of copolymer nylon, includes the following steps：
1）Caprolactam melt and storage
Solid caprolactam in packaging bag is transported in pulverizer, and pulverizer will squeeze broken under filtering ventilation protection
Caprolactam is through screw rod transmission into the melting tank with nitrogen protection, and the caprolactam of melting tank fusing is after filtering by pumping section
Divide and deliver into storage tank and then be subsequent technique use, another part example in mass ratio is adjusted, and is entered after heated with just crushing
Solid caprolactam in melting tank is mixed together to accelerate it in the melting of tank.（The caprolactam of fusing：Solid caprolactam
=4：1）
The caprolactam of fusing is first sent by tank car to independent pans, conveys storage tank again after sampling is qualified.
The caprolactam reserves of each line in tank field are designed as 96 hours continuously with required consumption when the operating of 110% specified production capacity,
Meanwhile it being based on separately running between each line tank field in design principle, but each line storage tank when necessary can motor-driven connection use feed.
The pipelines of all melting zones melts and holding vessel uses hot water heating, the caprolactam in storage tank after filtration by
Pump is conveyed toward subsequent process island.
2）Dissolution, storage, the concentration of salt
Synthesize 66 salt techniques：It is mixed using 20% methanol solution of adipic acid and 50% methanol solution of hexamethylene diamine, reaction temperature 70
DEG C, pH control is 7.0, and methanol eddy product separates through crystallisation by cooling, cleaning, dry 66 salt.
66 salt of solid is transported in pulverizer, and it is defeated by screw rod that pulverizer will squeeze 66 broken salt under filtering ventilation protection
It is sent in the dissolving tank with nitrogen protection, storage tank is delivered by pump portion after filtering in 66 saline solutions that dissolving tank dissolves
And then used for subsequent concentration technique, another part example in mass ratio, which is adjusted after heat exchanger heats and just crushed, enters dissolving tank
In 66 salt of solid be mixed together to accelerate it in the dissolution of tank.（66 saline solutions dissolved：66 salt=4 of solid：1）
The solution reserves of 66 salt 60% of tank field are designed as 48 hours continuously with required consumption when the operating of 110% specified production capacity.
The pipeline and holding vessel of all dissolution zones use 90 degree or more hot water heatings, according to setting yield needs, in storage tank
66 salt concentration tank is transported to by pump after filtration.
As energy conservation measure, the water of concentration and evaporation and fresh water mixing circulation are used as dissolution water.
3）Auxiliary agent is prepared
The configuration of 3.1 auxiliary agent A D21
AD21 is automatically controlled by the pressure of the second polymer reactor, its liquid with other auxiliary agents and from tank area is fresh in oneself
Amide is continuously introduced into the mixing channel before the second polymerizer by process requirement flow and enters back into reactor after mixing.
3.2 auxiliary agent A D26 configuration
Stabilizer AD26 and desalted water are agitated uniformly mixed by the volume ratio of setting.It is filtered after sampling confirmation, is continuously introduced into the
Mixing channel before dimerization clutch.
The configuration of 3.3 high effective and modified doses 28 (HPA28)
The aqueous solution that a certain amount of liquid CPL is made into 70% is transported to preparing tank, given HPA28 amount is added under stiring, simultaneously
It heats up by given time and dissolves by heating high effective and modified dose 28 (HPA28), be pressed into storage tank, HPA28 solution with nitrogen after sampling is qualified
Mixing channel before being continuously introduced into the second polymer reactor in storage tank through filtering.
4）Three-step approach continuous polymerization
4.1 first step high pressure prepolymerizations
Caprolactam in storage tank and 66 salting liquids from concentration tank convey through pump and add via high temperature heating agent such as biphenyl
The pipeline and special heater of heat are transported in mixer and enter back into the first polymer reactor, 66 salting liquids being concentrated herein and
Caprolactam in storage tank after forcing turbulent condition to be sufficiently mixed by pump by being conveyed into high pressure pre-polymerizer, by the stop of setting
After time aggregation reaction, discharge vapor is purified from overhead reflux, reaction pre-polymer melt delivers into second step polymerization together
Pressure can when the mixing such as reactor and fresh caprolactam, auxiliary agent A D26, HPA28 continuation polymerization reaction first step high pressure polymerisation
Reach 40 Bar.
Be in pre-polymerization reactor technological design reactor with pressure and design yield 70-110% range stable operation,
Residence time ensure that sudden reaction and subsequent polycondensation reach balance under corresponding process conditions enough.
The polymerization of 4.2 second steps
It is compared with the high pressure of the first polymer reactor and overhead reflux draining, the second polymer reactor is closed and pressure does not surpass
Cross 8 bar, the dynamic mixing channel mixing of fresh caprolactam and auxiliary agent before the reactor inlet, subsequently into the second polymerization reaction
Special Mixed device in device and the mixing of the prepolymer from the first polymer reactor continue polymerization reaction, are entering the
Most water are detached from by the fractionating column at the top of the first polymer reactor before dimerization reactor, thus guarantee polymerization reaction after
The continuous pressure for quickly pushing ahead the second polymer reactor is 8 bar.
Pressure difference between two reactors, does not have delivery pump between first reactor and second reactor.
In second polymer reactor technological design it is reactor with pressure and stablizes fortune in the range of design yield 70-110%
Row, residence time guarantee that poly- reaction reaches balance under corresponding process conditions enough.
The polymerization of 4.3 third steps
The prepolymer come out from the second polymer reactor is conveyed through melt drier by gear pump into post-polymerization device, molten
In gas dryer, because the excessive water of pressure change in prepolymer melt from separating and by the bubble-cap at the top of post polymerizer
It mixes, cool down with protection nitrogen in tower, then feed liquor sealing groove condenses together.The low molecule raw material of moisture entrainment is cold in bubble column
Coalescence passes back into post polymerizer.
Post-polymerization device works under normal pressure and with nitrogen protection, which can be divided into for four stages, and each stage has
Its corresponding special setting is to guarantee that polymer melt is completely maintained in technologic stable homogeneous distribution.In the technique of residence time
It ensure that corresponding addition polymerization and polycondensation reaction reach balance enough in different output range (70-110%) in design.
Three-step approach continuous polymerization technique section is all heated or cooled by liquid biphenyl or biphenyl steam jacket.
5）Cast Strip pelletizing
Production line pelletizing uses a set of USG pelletizing system, and melt is cooled down again after pattern hole extrusion through pump conveying, is then delivered to
Cutter pelletizing, transport platform have water circulation system cooling, and slice is delivered directly to dewaterer, is sliced after dehydration through sieve unqualified
Slice point falls, then slices synthesis method to drying tower.
6）Extraction
Monomer and oligomer the hot water counter-current extraction in extraction tower in PA6 slice is walked.
Slice is transported to the knockout drum at the top of extraction tower by mashing pump, then enters at the top of extraction tower from tank and move from top to down
The dynamic conveying water by upstream water hot extraction, come out from knockout drum is pumped back after filtering continues cycling through use.
There are twice circulation waterway and twice water charging system in extraction tower, it is upstream when top slice starts extraction
Extraction water section leaves extraction tower from top and enters recovery system and uses as slices synthesis method water, weighs after another part is heated
Newly enter extraction tower to be recycled.
Extraction tower bottom have twice water charging system, be together by process requirement amount after the concentration of recycling condensed water,
Another road is the return water being sliced after conveying extraction by extraction tower liquid automatic control rate of water make-up.
On extraction water inlet top, there are also a circulations in extraction tower to guarantee solubility gradient and the temperature gradient in tower
Stabilization.
Slice extracted is transported to centrifuge separation sieve through mashing pump by tower bottom and enters subsequent drying process, and conveying water is then
Returned recycling.
To improve extraction efficiency, extraction Deethanizer design also devises (nitrogen) extraction with pressure.
7）It is dry
Drying system runs under micro-positive pressure, and drying tower is by about 110% designing surely.
Slice, which enters, is sent to drying tower, slowly moves down from tower top and is dried by upstream flow of warm nitrogen gas.
Slice after drying is sent to by rotary valve by delivery system after recirculated cooling water is cooling in the cooler under tower bottom
System is sent to feed bin.
In drying tower, drying nitrogen outlet used is connected with cyclone dust collector,.
2. the present embodiment nylon monomer of table and copolymer nylon performance comparison
The present invention has the beneficial effect that：1）It is simple process, safe and reliable using conventional equipment and conventional chemical process；2）It is made
Product elongation at break, bending strength, notch impact strength etc. all increase, properties of product are excellent；3）In preparation process
Water resource realization recycle, non-wastewater discharge, energy-saving and emission-reduction；4）Solid in the caprolactam and entrance melting tank of fusing
Caprolactam, which is mixed together, can accelerate it in the melting of tank, and melting efficiency is high；5）Consolidating in 66 salt and entrance dissolving tank dissolved
66 salt of body, which is mixed together, can accelerate its dissolving in tank, dissolve high-efficient.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of copolymer nylon, which is characterized in that include the following steps：
1）Caprolactam melt and storage
Solid caprolactam in packaging bag is transported in pulverizer, and pulverizer will squeeze broken under filtering ventilation protection
Caprolactam is through screw rod transmission into the melting tank with nitrogen protection, and the caprolactam of melting tank fusing is after filtering by pumping section
Divide and deliver into storage tank and then be subsequent technique use, another part example in mass ratio is adjusted, and is entered after heated with just crushing
Solid caprolactam in melting tank is mixed together；（The caprolactam of fusing：Solid caprolactam=1：4-4：1）
2）Dissolution, storage, the concentration of salt
66 salt of solid is transported in pulverizer, and pulverizer will squeeze 66 broken salt under filtering ventilation protection and be arrived by screw rod transmission
In dissolving tank with nitrogen protection, storage tank is delivered into turn by pump portion after filtering in 66 saline solutions that dissolving tank dissolves
For the use of subsequent concentration technique, another part example in mass ratio, which is adjusted after heat exchanger heats and just crushed, to be entered in dissolving tank
66 salt of solid is mixed together；（66 saline solutions dissolved：66 salt=1 of solid：2-6：1）
3）Auxiliary agent is prepared；
4）Three-step approach continuous polymerization
4.1 first step high pressure prepolymerizations
Caprolactam in storage tank and 66 salting liquids from concentration tank are through pump conveying and defeated via the pipeline of biphenyl heating
It is sent in mixer and enters back into the first polymer reactor, the caprolactam in 66 salting liquids and storage tank is by forcing turbulent condition to be filled
It is conveyed by pump into high pressure pre-polymerizer after dividing mixing, after the residence time polymerization reaction of setting, purifies and be discharged from overhead reflux
Vapor, reaction pre-polymer melt deliver into together second step polymer reactor and fresh caprolactam, auxiliary agent A D26,
The mixing such as HPA28 continue polymerization reaction, and pressure can reach 36-40 Bar when first step high pressure polymerisation；
The polymerization of 4.2 second steps
It is compared with the high pressure of the first polymer reactor and overhead reflux draining, the second polymer reactor is closed and pressure does not surpass
6-8 bar is crossed, the dynamic mixing channel mixing of fresh caprolactam and auxiliary agent before the reactor inlet is anti-subsequently into the second polymerization
It answers the Special Mixed device in device and the prepolymer from the first polymer reactor to mix and continues polymerization reaction, entering
Most water are detached from by the fractionating column at the top of the first polymer reactor before second polymer reactor；
The polymerization of 4.3 third steps
The prepolymer come out from the second polymer reactor is conveyed by gear pump, through melt drier into post-polymerization device,
In melt drier, because the excessive water of pressure change in prepolymer melt from separating and by the bubble at the top of post polymerizer
It mixes, cool down with protection nitrogen in cover tower, then feed liquor sealing groove condenses together, and the low molecule raw material of moisture entrainment is in bubble column
It condenses and passes back into post polymerizer；
5）Cast Strip pelletizing
Melt cools down after pattern hole extrusion again through pump conveying, is then delivered to cutter pelletizing, transport platform has water circulation system cold
But, slice is delivered directly to dewaterer, unqualified slice point is fallen through sieve after slice dehydration, then slices synthesis method to drying
Tower；
6）Extraction
Slice is transported to the knockout drum at the top of extraction tower by mashing pump, then enters from tank and move quilt from top to down at the top of extraction tower
Upstream water hot extraction, the conveying water come out from knockout drum is pumped back after filtering continues cycling through use；
Slice extracted is transported to centrifuge separation sieve through mashing pump by tower bottom and enters subsequent drying process, and conveying water is then sent
Also it is recycled；
7）It is dry
Slice, which enters, is sent to drying tower, slowly moves down from tower top and is dried by upstream flow of warm nitrogen gas, cutting after drying
Piece is sent to by rotary valve after recirculated cooling water is cooling in the cooler under tower bottom and is sent to feed bin by transportation system.
2. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 1）The fusing oneself in
Amide is first sent by tank car to independent pans, conveys storage tank again after sampling is qualified.
3. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 2）The concentration tank concentration
The water of evaporation and fresh water mixing circulation are used as dissolution water.
4. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 3）The auxiliary agent configuration packet
It includes：
The configuration of auxiliary agent A D21
AD21 is automatically controlled by the pressure of the second polymer reactor, its liquid with other auxiliary agents and from tank area is fresh in oneself
Amide is continuously introduced into the mixing channel before the second polymerizer by process requirement flow and enters back into reactor after mixing；
Auxiliary agent A D26 configuration
Stabilizer AD26 and desalted water by setting volume ratio it is agitated be uniformly mixed, filtered after sampling confirmation, be continuously introduced into the
Mixing channel before dimerization clutch；
The configuration of high effective and modified dose 28 (HPA28)
A certain amount of liquid CPL is made into aqueous solution and is transported to preparing tank, is added given HPA28 amount under stiring, while by giving
Heating of fixing time dissolves by heating high effective and modified dose 28 (HPA28), is pressed into storage tank with nitrogen after sampling is qualified, and HPA28 solution is from storage
Through filtering the mixing channel before being continuously introduced into the second polymer reactor in tank.
5. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 4）The three-step approach is continuous
Polymerization technique section is all heated or cooled by liquid biphenyl or biphenyl steam jacket.
6. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 6）Have in the extraction tower
Twice circulation waterway and twice water charging system, extraction tower bottom have twice water charging system；There are also a recirculated waters in the extraction tower
System.
7. a kind of preparation method of copolymer nylon according to claim, which is characterized in that step 7）In the drying tower, institute
Cyclone dust collector is connected with drying nitrogen outlet.
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| CN201810599410.0A CN108929436A (en) | 2018-06-12 | 2018-06-12 | A kind of preparation method of copolymer nylon |
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| CN201810599410.0A CN108929436A (en) | 2018-06-12 | 2018-06-12 | A kind of preparation method of copolymer nylon |
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| CN110408020A (en) * | 2019-08-30 | 2019-11-05 | 温州邦鹿化工有限公司 | A kind of 165 tonnes of nylon-6 paradigmatic systems of production single line and polymerization technique |
| CN111763314A (en) * | 2020-08-17 | 2020-10-13 | 温州邦鹿化工有限公司 | High-viscosity high-strength nylon-666 copolymerization polymerization continuous polymerization device |
| CN111925519A (en) * | 2020-08-17 | 2020-11-13 | 温州邦鹿化工有限公司 | Continuous production device for multi-component copolymerized nylon |
| CN113461935A (en) * | 2021-07-02 | 2021-10-01 | 中国纺织科学研究院有限公司 | Preparation method of copolyamide and copolyamide |
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