CN204607901U

CN204607901U - For monitor polyamide products manufacture in the system of gel formation

Info

Publication number: CN204607901U
Application number: CN201420172793.0U
Authority: CN
Inventors: 唐纳德·J·福斯特; 查尔斯·R·克尔曼; 托马斯·A·米茨卡; 保罗·诺米科斯; 约翰·P·普安萨蒂
Original assignee: Invista Technologies SARL Switzerland
Current assignee: Invista North America LLC
Priority date: 2013-05-01
Filing date: 2014-04-10
Publication date: 2015-09-02
Anticipated expiration: 2024-04-10
Also published as: TWM493548U

Abstract

The disclosure relates to the method and system of gel formation in the manufacture for monitoring polyamide products.In one embodiment, the present embodiment provides a kind of method, and described method can comprise and the polyamide compound be partly polymerized is guided through flasher fresh feed pump, finisher pump and transmits in-line pump.The method can comprise described flasher fresh feed pump, described finisher pump and described transmission in-line pump are converted to the second operational mode from the first operational mode.The method can comprise activated gel time control unit and can activate to estimate gel time at least one in flasher, finisher and transmission pipeline.The method can comprise the reactor of described polymeric amide synthesis system is converted to described second pattern from described first operational mode.

Description

For monitor polyamide products manufacture in the system of gel formation

The cross reference of related application

This application claims the benefit of priority of the U.S. Provisional Patent Application numbers 61/818,308 submitted on May 1st, 2013, its disclosure is combined in this with its full content by reference.

Technical field

The application relates to polymeric amide synthesis technique, particularly, relates to the method and system for monitoring gel formation in polymeric amide synthesis technique.

Background technology

Polymeric amide has useful character as high weather resistance and intensity, and this makes them can use in multiple environment.Polymeric amide such as nylon, aromatic poly amide and poly-(aspartic acid) sodium are generally used for, such as, and carpet, airbag, mechanical part, dress ornament, rope and stocking.Nylon 6,6 is a kind of polymeric amide the most often used.Nylon 6, the long molecular chain of 6 and dense structure make it qualified as senior nylon fiber, and it represents high mechanical strength, rigidity and thermostability.

Polymeric amide is business synthesis in extensive producing apparatus.Polymeric amide can by by diamines and dicarboxylic acid, and sometimes with the form of the ammonium carboxylate salt of two compounds, in solvent is as water, polymerization obtains.Such as, nylon 6,6 can experience condensation reaction, to form amido linkage and to discharge water and synthesize by making hexa-methylene two ammonium adipate.In a series of assemblies comprising autoclave or reactor, flasher and finisher, heat can be applied to reaction mixture, and water little by little can be removed with driven equilibrium towards polymeric amide (such as nylon 6,6), until polymer chain reaches required molecular weight ranges.Afterwards, can extrude as pellet by the polymeric amide of melting, it can spin as fiber or the shape being processed into other.

Current experienced by some problem for the method and apparatus manufacturing polymeric amide in a continuous manner.Some parts of technique back segment may because many reasons shuts down or the free time.When parts of back segment shut down or be idle, the miscellaneous part of back segment also shuts down or idle.Shutting down or in idle process, polyamide polymer may gel in time.The gelation of polyamide polymer may hinder, and stops the flowing of polymeric amide when the device is re-booted in some cases.If polymeric amide is gel before restart facility, whole technique must be made to shut down and carry out burnouting (burnout) to remove the material of gel.Whole technique is shut down and carries out burnouting to be with heavy program and to be consuming time with high cost.Therefore, the current method and system for the manufacture of polymeric amide may require to shut down frequently and burnout.

Current method and apparatus for manufacturing polymeric amide with basis also may experience some problem.When temperature in each autoclave increases to over threshold temperature, gel may be formed.In batch processes process, the temperature in autoclave may increase to over threshold temperature every now and then.Additionally, due to about the difficult problem of autoclave or problem, temperature may increase to over threshold temperature.Gel gathering in time may cause the fault of autoclave and the deterioration of product.When autoclave fault or product are reduced to lower than quality threshold value, are shifted out by autoclave and produce and overhaul, this may be have heavy and be consuming time and expensive.Therefore, the current method and system for the manufacture of polymeric amide may experience the unexpected fault of autoclave and the product qualities of reduction.

As described herein, the theme of the present embodiment can provide the solution of these problems.

Utility model content

The disclosure can be provided for monitoring polymeric amide synthesis system, as nylon 6, and the method and system of the gel formation in the system of the manufacture of 6.The method can comprise and the polyamide compound be partly polymerized is guided through flasher fresh feed pump, finisher pump and transmits in-line pump.The method can comprise by flasher fresh feed pump, finisher pump and transmit in-line pump be converted to the second operational mode from the first operational mode.Gel time control unit can be activated to estimate gel time at least one in flasher, finisher and transmission pipeline.Gel time based at least with the temperature of the polyamide compound be partly polymerized at least one in flasher, finisher and transmission pipeline, and temperature exceedes the parameter of the time correlation of threshold temperature.The method can comprise the reactor of polymeric amide synthesis system is converted to the second reactor operational mode from the first reactor operational mode.

The disclosure provides the system of gel formation in a kind of manufacture for monitoring polyamide products.This system can comprise polymerization reactor, and described polymerization reactor is configured to one or more starting material to transform to form polymeric amide; And the back segment system in polymerization reactor downstream, this back segment system configuration is that the molecular weight of raising polymeric amide is to form polyamide products.This system can comprise gel time control unit, and described gel time control unit is operatively connected to back segment system and is configured to when back segment system is converted into the second operational mode from the first operational mode, for back segment system estimation gel time.Gel time can based at least exceeding the parameter of the time correlation of threshold temperature with the temperature of polymeric amide in back segment and temperature.

The disclosure can provide and exceed other benefits for the preparation of the method and system of polymeric amide.Such as, because multiple reason may need some parts of the back segment of traditional technology, as finisher, flasher and transmission pipeline shut down or the free time.When parts shut down or be idle, the miscellaneous part of back segment also will shut down or the free time.Shut down or the free time process in, in back segment equipment polyamide gels risk increase.As discussed in this article, after the polyamide gels in equipment, whole technique must be shut down (if not yet shutting down) and must burnout.Gel time, as the time before polyamide gels in equipment, based on the temperature variation of material in equipment.

The disclosure is provided for the real-time method of the operator determining and pass on gel time information to technique.Operator can utilize gel time to determine to make operation, and this can reduce owing to shutting down or the cost of free time and the loss of time.Such as, if needed, operator can regulate multiple parameter (such as, temperature or pressure) to increase gel time.When not knowing gel time information, if polymeric amide is at equipment inner gel, adjusting process parameter will not provide any benefit, and regulating parameter will be lost time and money.But the disclosure can to provide a process which or system, it can be determined, monitor and the gel time of communication back segment.Therefore, the whole back segment of technique of can avoiding shutting down and carry out the tediously long program that burnouts, even if when back segment shut down or idle (such as, for safeguarding) time, also allow producing apparatus to restart.

The disclosure also provides the method for gel formation in a kind of manufacture for monitoring polyamide products.The method can comprise and is fed to reactor and activated gel control unit by comprising one or more raw-material first batch.Gel control unit can be configured to generation first single batch of gel number and continuous batch of gel number.First single batch of gel number and continuous batch of gel number can at least based on the temperature of reactor higher than time of threshold temperature.The method can comprise and in the reactor one or more starting material is converted into the first polyamide products, and transmits the first polyamide products from reactor.The method can comprise and is fed to reactor and activated gel control unit by comprising one or more raw-material second batch, and described gel control unit is configured to generation second single batch of gel number and upgrades continuous batch of gel number.

The disclosure is provided for determining to accumulate the real-time method of number to the operator of technique with communication unit one batch of gel number and gel.Single batch of gel number accumulate in the process of single batch processes and introduce subsequently batch time be reset to zero.Single batch of gel number can identify operation degree of difficulty, otherwise this will cannot notice in systems in which when not having single batch of gel number.Such as, single batch of gel number can determine special batch whether have than other batch or the higher deterioration of other reactor (such as, autoclave).It is more deteriorated that single batch of gel number can also determine when that concrete autoclave continues low generation, and this can indicate concrete autoclave to have operation problem, such as, and the setting point of mistake or other defect.Therefore, method and system of the present disclosure can identify and solve the defect in concrete autoclave, otherwise when not having single batch of gel number, this can not be noted in systems in which.

Gel accumulation number continues accumulation until overhauled by autoclave, now gel is accumulated number and is reset to zero.Gel accumulation number provides the deterioration (such as, the gel formation on surface) of the accumulation of autoclave, and can provide about when autoclave will need the estimation of maintenance.Gel buildup number eliminates the indefinite property that when may need to carry out overhauling, and thus operator can be allowed to plan.Therefore, can avoid the fault that cannot expect of autoclave, this can reduce by the maintenance that cannot expect subsidiary time and cost.

Accompanying drawing explanation

Accompanying drawing is uninevitable to be drawn in proportion, and it is by the mode of example, instead of in a limiting fashion, the embodiment of example the present embodiment generally.

Fig. 1 is the block diagram of the system for the manufacture of polymeric amide according to an example.

Fig. 2 is the more detailed block diagram of a part for the system according to an example of Fig. 1.

Fig. 3 example is according to the schema of the method for the gel formation in polymeric amide synthesis system of an example.

The diagram that gel time is mapped to temperature by Fig. 4 example.

Fig. 5 is the block diagram of the system of the manufacture for polymeric amide according to an example.

Fig. 6 example is according to the schema of the method for gel formation in the monitoring polymeric amide synthesis system of an example.

Embodiment

The disclosure describes a kind of for the manufacture of polymeric amide, as nylon 6, and the method and system of 6.System and method described herein can comprise device, system and method for monitoring gel formation in polymeric amide synthesis system.

definition

With range format express value should with flexi mode explain using not only comprise as scope boundary clearly describe numerical value, and comprise all independent numerical value included within the scope of this or subrange, as stated the same by each numerical value clearly with subrange.Such as, the scope of " about 0.1% to about 5% " or " about 0.1% to 5% " should be interpreted as not only comprising about 0.1% to about 5%, and comprise independent value in pointed scope (such as, 1%, 2%, 3% and 4%) and subrange (such as, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).Unless otherwise noted, state that " about X to Y " has the implication identical with " about X to about Y ".Equally, unless otherwise noted, state that " about X, Y or about Z " has the implication identical with " about X, about Y or about Z ".

In this article, unless context is clearly pointed out in addition, use term " ", " one " or " described " to comprise one or more than one.Unless otherwise noted, term "or" is used to refer to the "or" of nonexcludability.In addition, it is to be appreciated that, adopt herein and the wording of in addition definition or term only for illustration of object and nonrestrictive.The use of any paragraph heading is intended to the understanding of help file and is not interpreted as limiting; The information relevant to paragraph heading can within special paragraph or outside occur.In addition, all publication, patent and the patent documentation quoted in this article are combined in this with its full content by reference, combine as individually through quoting.When herein usage is inconsistent between those documents be combined by reference like this, in conjunction with citing document in usage should be considered to supplementing herein; For irreconcilable contradiction, be as the criterion with usage herein.

In manufacture method described herein, multiple step can be carried out with random order and not depart from the principle of present subject matter, except when the time of explicitly pointing out or working order.In addition, concrete step can be carried out simultaneously, unless clear and definite claim language points out that they carry out dividually.Such as, the step of the X of carrying out required for protection and the step of the Y of carrying out required for protection side by side can be carried out in single operation, and the technique obtained will drop in the literal scope of technique required for protection.

As used herein term " about " can certain variable pitch in permissible value or scope, such as, in 10% of described value or the restriction of described scope, in 5%, or in 1%.

As used herein term " substantially " refers to major part, or mainly, as being at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about more than 99.999%.

As used herein, term " dicarboxylic acid " broadly refers to C ₄-C ₁₈alpha, omega-dicarboxylic acid.This term comprises C ₄-C ₁₀alpha, omega-dicarboxylic acid and C ₄-C ₈alpha, omega-dicarboxylic acid.C ₄-C ₁₈α, the example of the dicarboxylic acid that alpha, omega-dicarboxylic acid comprises comprises, but be not limited to, succsinic acid (butanedioic), pentanedioic acid (pentane diacid), hexanodioic acid (hexane diacid), pimelic acid (heptane diacid), suberic acid (octane diacid), nonane diacid (nonane diacid) and sebacic acid (decane diacid).In some instances, C ₄-C ₁₈alpha, omega-dicarboxylic acid is hexanodioic acid, pimelic acid or suberic acid.In other example again, C ₄-C ₁₈alpha, omega-dicarboxylic acid is hexanodioic acid.

As used herein, term " diamines " broadly refers to C ₄-C ₁₈α, ω-diamines.This term comprises C ₄-C ₁₀α, ω-diamines and C ₄-C ₈α, ω-diamines.By C ₄-C ₁₈the example of the diamines that α, ω-diamines comprises includes, but are not limited to, and butane-Isosorbide-5-Nitrae-diamines, pentane-1,5-diamines and hexane-1,6-diamines, also referred to as hexamethylene-diamine.In some instances, C ₄-C ₁₈α, ω-diamines is hexamethylene-diamine.

In some instances, the use that hexanodioic acid and hexamethylene-diamine combine is expected herein.

As used herein, term " polymeric amide " broadly refers to that polymeric amide is as nylon 6, nylon 7, nylon 11, nylon 12, nylon 6,6, nylon 6,9; Nylon 6,10, nylon 6,12, or their multipolymer.

As used herein, term " polymer " " can multipolymer be comprised.

As used herein, term " solvent " refers to can the liquid of dissolved solids, liquid or gas.The limiting examples of solvent is siloxanes, organic compound, water, alcohol, ionic liquid and supercutical fluid.

As used herein, term " gel time (gelation time) " or " gel time (gel time) " refer to that polymeric amide forms the time making before gel the melt viscosity of polymer samples keep under steady temperature and constant vapor pressure relative to departing from the graphic representation of heat-up time (inflection).

As used herein, term " gel " refer to be formed in product (nylon 6,6) and equipment and collect very high molecular, branching/crosslinked polymkeric substance.Gel is insoluble, such as, when when heating at 101KPa for about 280 DEG C to about 295 DEG C, insoluble in about 98% to about 100% formic acid, and usually extreme manner only can be used as slave unit removes by being burnt by gel.

As used herein, term " back segment " refers to and comprises autoclave, or the equipment of at least one in flasher and finisher.

As used herein, term " single batch of gel number " refers to the value increased continuously in the process of single batch processes, and introduce subsequently batch after be reset to zero.This value can correspond to the time value (such as, minute) of temperature higher than threshold temperature of reactor (such as, autoclave) in the process of single batch processes.

As used herein, term " gel buildup number " refers to and increases continuously until the value of overhauling autoclave.This value can correspond to the time value (such as, minute) of temperature higher than threshold temperature of reactor (such as, autoclave) in the process of the multiple single batch processes of single autoclave.

As used herein, term " burnouts " and refers to that applying heat is with the technique of the material of pyrolysis plant inner gel.

for the preparation of the system of polymeric amide

Fig. 1 is for the manufacture of polymeric amide, and especially for manufacturing the schema of instance system 10 of nylon 6,6.System 10 can comprise reservoir 12, the aqueous solution of the dicarboxylic acid of its receiving fluids or substantially liquid phase, diamines and solvent (such as, water).Dicarboxylic acid and diamines can form ammonium carboxylate salt.In an example, be configured for nylon 6 in system 10, when 6 manufacture, reservoir 12 can comprise hexa-methylene two ammonium adipate, and it can be dissolved in water in reservoir 12.Reservoir 12 can in order to mixing or the aqueous solution storing ammonium carboxylate salt.

In this example, dicarboxylic acid and diamines can be added to reservoir 12 with equimolar ratio substantially.The ammonium carboxylate salts obtained can have about 7.5, according to appointment the pH of 7.4 to about 7.6.The ammonium carboxylate salt of each molecule can comprise the diamines of a molecule and the dicarboxylic acid of a molecule.Can by the aqueous solution heating in reservoir 12, as with pre-heaters or with water vapour, the water vapour as the formation of the another part in system 10 heats.

Can will comprise the solution of dicarboxylic acid and diamines, such as, the ammonium carboxylate salt aqueous solution, is passed to vaporizer 14 from reservoir 12 via conduit 16.Vaporizer 14 can be configured to by the water of the part from the aqueous solution basically liquid phase be converted into gas phase substantially with the form of stream of water vapor 18.In instances, vaporizer 14 is by being heated to about 100 DEG C to about 230 DEG C by the aqueous solution, 100 DEG C to about 150 DEG C according to appointment, the temperature of such as about 110 DEG C, about 120 DEG C, about 130 DEG C, about 140 DEG C, about 150 DEG C, about 160 DEG C, about 170 DEG C, about 180 DEG C, about 190 DEG C, about 200 DEG C, about 210 DEG C, about 220 DEG C or about 230 DEG C forms stream of water vapor 18.Vaporizer 14 can increase the concentration of ammonium carboxylate salts.In instances, leave reservoir 12 and the concentration being fed to the ammonium carboxylate salts in vaporizer 14 is about 40 % by weight to about 80 % by weight salt in water, or about 52 % by weight to about 65 % by weight, as about 63 % by weight salt in water.Vaporizer 14 can increase the concentration of ammonium carboxylate salts, such as about 72 % by weight salt to water.

React to be formed the Polvamide prepolymer of the polymer chain that can comprise relative short dicarboxylic acid and diamines with removing dicarboxylic acid at least partially that water also can cause existing in the solution in vaporizer 14 and diamine portion via evaporation.In other words, the condensation reaction that water can start between dicarboxylic acid and diamines is removed, to form the oligopolymer of the first step that can be final polyamide chains.As noted above, vaporizer 14 can concentrated aqueous solution, such as, reduced by the water concentration of the solution by leaving vaporizer 14, as being reduced to the water concentration of water of about 5 % by weight to about 50 % by weight, the such as water of about 25 % by weight to about 35 % by weight, the according to appointment water of 25 % by weight, about 26 % by weight, about 27 % by weight, about 28 % by weight, about 29 % by weight, about 30 % by weight, about 31 % by weight, about 32 % by weight, about 33 % by weight, about 34 % by weight or about 35 % by weight.

Stream of water vapor 18 can be allowed to escape to air, or stream of water vapor 18 can condensation charging is back to reservoir 12 (not shown).Also condensed steam can be purified, as via filtering or other purification process.Also can use condensed steam as generation of can system 10 other in the water source of water vapour that uses, as discussed below.Stream of water vapor 18 self also can be used as the otherwise water vapour of system 10, as being positioned at reservoir 12 place or its downstream immediately substantially aqueous solution preheating.

Can by comprising water, the reaction mixture of unreacted dicarboxylic acid and diamines (such as, with unreacted ammonium carboxylate salt, and, if existed, the form of Polvamide prepolymer) is passed to reactor 20 from vaporizer 14 via conduit 22.In reactor 20, unreacted dicarboxylic acid and diamines can react each other, or react with Polvamide prepolymer, or both carry out simultaneously, to form the first polyamide polymer.Temperature in reactor 20 can increase to over temperature in vaporizer 14 further to remove other water.In instances, temperature in reactor can be about 150 DEG C to about 300 DEG C, 200 DEG C to about 250 DEG C according to appointment, such as about 220 DEG C to about 230 DEG C, 228 DEG C according to appointment, such as about 150 DEG C, about 160 DEG C, about 170 DEG C, about 180 DEG C, about 190 DEG C, about 200 DEG C, about 210 DEG C, about 215 DEG C, about 220 DEG C, about 225 DEG C, about 230 DEG C, about 235 DEG C, about 240 DEG C, about 245 DEG C, about 250 DEG C, about 260 DEG C, about 270 DEG C, about 280 DEG C, about 290 DEG C or about 300 DEG C.The solution of the first polyamide polymer and unreacted dicarboxylic acid and diamines that leave reactor 20 can have the water concentration of the water of the water to about 20 % by weight of about 1 % by weight, the water of the water of 5 % by weight to about 15 % by weight according to appointment, such as about 1 % by weight, about 2 % by weight, about 3 % by weight, about 4 % by weight, about 5 % by weight, about 6 % by weight, about 7 % by weight, about 8 % by weight, about 8.5 % by weight, about 9 % by weight, about 9.5 % by weight, or the water of about 10,11,12,13,14 or about 15 % by weight.

Reactor 20 can be equipped with and be communicated with reactor 20 fluid, as the rectifying tower 24 be communicated with via conduit 26 fluid.Rectifying tower 24 is passable, and then, be communicated with discharge outlet pipeline 28 fluid.

The first polyamide polymer formed in reactor 20 can be passed through to use flasher fresh feed pump 38 to be passed to flasher 30 via conduit 32 from reactor 20 together with diamines with unreacted dicarboxylic acid.In flasher 30, the temperature substance of the reaction mixture of the first polyamide polymer and unreacted dicarboxylic acid and diamines raises, as being increased to about 150 DEG C to about 400 DEG C, such as about 250 DEG C to about 350 DEG C, 260 DEG C to about 300 DEG C according to appointment, 280 DEG C according to appointment, such as about 200 DEG C, or about 210 DEG C, about 220 DEG C, about 230 DEG C, about 240 DEG C, about 250 DEG C, about 260 DEG C, about 265 DEG C, about 270 DEG C, about 275 DEG C, about 280 DEG C, about 285 DEG C, about 290 DEG C, about 295 DEG C, about 300 DEG C, about 305 DEG C, about 310 DEG C, about 320 DEG C, about 330 DEG C, the temperature of about 340 DEG C or about 350 DEG C.In the ingress of flasher 30, the pressure of reaction mixture is relatively high, according to appointment 1.9MPa to about 2.1MPa.Pressure little by little can reduce along with reaction mixture is advanced through flasher 30, and to make in the exit of flasher 30, pressure is relatively low, in some cases close to the vacuum of about 25KPa to about 50KPa.High temperature in flasher 30, the pressure reduced gradually is applied on reaction mixture by flasher 30 along with reaction mixture, and the form of the water vapour causing water to leave from reaction mixture with flash distillation removes further.Along with water vapour leaves from reaction mixture flash distillation, the first polyamide polymer can experience polymerization further to form the second polyamide polymer.At the exit end place of flasher 30, the two-phase mixture of the liquid mixture of vaporous water steam and the second polyamide polymer and unreacted dicarboxylic acid and diamines can be formed.Water vapour can be discharged from flasher 30, as passed through the discharge orifice (not shown) in flasher 30, or together with leave the product stream of flasher 30 via delivery channel 34.The solution of the second polyamide polymer and unreacted dicarboxylic acid and diamines that leave flasher 30 can have the water concentration of the water of the water to about 5 % by weight of about 0.1 % by weight, the water of the water of 0.5 % by weight to about 2 % by weight according to appointment, the water of such as about 0.1 % by weight, about 0.2 % by weight, about 0.4 % by weight, about 0.5 % by weight, about 0.6 % by weight, about 0.8 % by weight, about 0.9 % by weight, about 1 % by weight, about 1.1 % by weight, about 1.2 % by weight, about 1.4 % by weight, about 1.5 % by weight, about 1.6 % by weight, about 1.8 % by weight or about 2 % by weight.Flasher 30 can comprise at least one pipe relatively grown, and it is wound around by flasher 30, also referred to as the coil pipe of flasher 30.The entrance of reaction mixture from flasher 30 can deliver to outlet by this pipe.This pipe can be initial with little sectional area such as minor diameter in ingress, and can along the length expansion of pipe, until it has relatively larger sectional area in exit, such as, and relatively large diameter.Sectional area can provide the reduction on pressure from the entrance of flasher 30 to outlet from entrance to the increase of outlet, as mentioned above.

Catalyzer can be added to reaction mixture to help lend some impetus to the condensation reaction of formation polymeric amide described herein.In instances, can by catalyzer at vaporizer 14 place (such as, to in the entrance of vaporizer 14), at reactor 20 place (such as, to in the entrance of reactor 20) or be added to reaction mixture flasher 30 place (such as, in the entrance of flasher 30).Although can catalyzer be added, polymerizing polyamide whether must be made to react and to occur.In an example, catalyzer can comprise at least one in sodium hypophosphite, manganous hypophosphite and phenyl phosphinic acid.

Second polyamide polymer that can be formed in flasher 30, and unreacted dicarboxylic acid and diamines are passed to finisher 36 via conduit 34 from flasher 30 by using finisher pump 44.

Finisher 36 can provide water remove further make the second polyamide polymer experience further polymerization to form the final polyamide polymer with final molecular weight or molecular weight ranges.Selected final molecular weight or molecular weight ranges can depend on the final required character of polyamide products.In finisher 36, remove water to be obtained by reaction mixture vacuum pressure is applied in finisher 36.By controlling the vacuum pressure being applied to finisher 36, and the residence time of reaction mixture in finisher 36, the final scope of the molecular weight of final polyamide polymer can be controlled.Temperature in finisher 36 can be about 150 DEG C to about 400 DEG C, 250 DEG C to about 350 DEG C according to appointment, such as about 260 DEG C to about 300 DEG C, 284 DEG C or about 285 DEG C according to appointment, such as about 210 DEG C, about 220 DEG C, about 230 DEG C, about 240 DEG C, about 250 DEG C, about 260 DEG C, about 265 DEG C, about 270 DEG C, about 275 DEG C, about 280 DEG C, about 285 DEG C, about 290 DEG C, about 295 DEG C, about 300 DEG C, about 305 DEG C, about 310 DEG C, about 320 DEG C, about 330 DEG C, about 340 DEG C or about 350 DEG C.The final polyamide polymer leaving finisher can have the water concentration of the water of about 0.0001 % by weight to about 2 % by weight, the such as water of about 0.001 % by weight to about 1 % by weight, the water of 0.01 % by weight to about 1 % by weight according to appointment, such as about 0.0001 % by weight, about 0.001 % by weight, about 0.01 % by weight, about 0.05 % by weight, about 0.1 % by weight, about 0.2 % by weight, about 0.3 % by weight, about 0.4 % by weight, about 0.5 % by weight, about 0.6 % by weight, about 0.7 % by weight, about 0.8 % by weight, about 0.9 % by weight, about 1 % by weight, about 1.2 % by weight, about 1.4 % by weight, about 1.5 % by weight, about 1.6 % by weight, the water of about 1.8 % by weight or about 2 % by weight.

Final polyamide polymer can leave finisher 36 by transmitting pipeline 40.Transmitting pipeline 40 can be fed in final treatment system 42 via transfer line pump 46, and wherein final polyamide polymer can through further mechanical treatment, as one or more in what spin, extrude with in granulation.Such as, final polyamide polymer can be extruded by the die head with multiple little kapillary, to prepare multiple polyamide thread material continuously.Line material can be cut into polymeric amide pellet in tablets press.

Additive can be added to polyamide polymer to provide or to improve multiple features of obtained polyamide products.Such as, pigment can be added to control the color of polyamide products, as titanium dioxide (TiO ₂) can white pigment be used as.By end-capping reagent, the end of technique can be added to stop polymerization as acetic acid.End-capping reagent can also be added to the salt in reservoir 12.If use catalyzer, can, by inactivating agent, as sodium bicarbonate, add to make catalyst deactivation at the end of technique.

Fig. 2 comprises the view of the block diagram of a part 50 for the system of the Fig. 1 according to an example.Except content in FIG, the part 50 of system 10 comprises sensor 52A-C (being referred to as herein " sensor 52 "), and gel time control unit 54A-C (being referred to as herein " gel time control unit 54 ").Additionally, the part 50 of system 10 comprises the outlet valve 66 of reactor 20, and conduit 22 comprises the water inlet valve 70 being connected to water source 68 via conduit 72.

Outlet valve 66 can also for when back segment (such as, comprise flasher 30, finisher 36 and transmit pipeline 40) is shut down or idle time off-response device 20 outlet.In another example, when outlet valve 66 can be worked as the back segment free time or shut down, by the Output transfer from reactor 20 to reservoir (not shown).Additionally, conduit 22 is connected to water inlet valve 70, and it can control the flowing (as given Fig. 1) from vaporizer 14 and allow water to flow to reactor 20 from water source 68, with the content of diluting reactor 20.As discussed in this article, when back segment is idle, outlet valve 66 can stop from the flowing of reactor 20 or the flowing from reactor 20 be shifted, and water inlet valve 70 can cut out from the flowing of vaporizer 14 or water is introduced into reactor 20 to reduce gel formation.

When back segment is converted to the second operational mode from the first operational mode, gel time control unit 54 can for back segment system estimation gel time.Gel time can based at least exceeding the parameter of the time correlation of threshold temperature with the temperature of polymeric amide in back segment and temperature.The part 50 of system 10 can comprise sensor 52A-C (being referred to as " sensor 52 ").As shown in FIG. 2 in the example, sensor 52A is relative, and flasher 30 is positioned at upstream, and sensor 52B is relative, and finisher 36 is positioned at upstream, and sensor 52C transmits in-line pump 46 is relatively positioned at upstream.The number of sensor 52 and position can change between the systems.In an example, the part 50 of system 10 comprises and is less than three sensor 52A-C.In another example, the part 50 of system 10 comprises more than three sensor 52A-C.

Sensor 52 can comprise temperature sensor, flow-sensint unit or be configured to provide gel time control unit 54 to determine other parts of the parameter of gel time based on it.In an example, sensor 52A can comprise flasher temperature sensor, and sensor 52B can comprise finisher temperature sensor, and sensor 52C can comprise transmission line temperature sensor.Sensor 52 can pass through passage 64A-C (being referred to as " passage 64 ") and be connected to gel time control unit 54.Passage 64 can comprise wired or cableless communication connection.

In the example provided in fig. 2, gel time control unit 54A-C comprises treater 56A-C (being referred to as " treater 56 "), storer 58A-C (being referred to as " storer 58 "), interface 60A-C (being referred to as at " interface 60 "), and warning horn 62A-C (being referred to as " warning horn 62 ").In an example, each in gel time control unit 54 can be independent gel control unit separately.In another example, gel time control unit 54 can be the single gel control unit with the communication of each sensor 52.

Gel time control unit 54 and sensor 52 can form one or more computer or its part.As shown in example, each gel time control unit 54 comprises treater 56, storer 58 and interface 60.Optionally, gel time control unit 54 can comprise warning horn 62.Storer 58, interface 60, sensor 52 are communicated with treater 56 with warning horn 62.Treater 56 is configured to perform instruction to perform the algorithm for estimating gel time.This algorithm can comprise at least one the generation gel time in flasher 30, finisher 36 and transmission pipeline 40.As discussed in this article, gel time can based on following parameter, described parameter at least with at least based on coming the flasher 30 of signal of sensor 52, finisher 36 and transmitting the time correlation that the temperature of the polyamide compound be partly polymerized at least one in pipeline 40 and temperature exceed threshold temperature.

In instances, gel time started at 19 hours and reciprocal with the hours of equal value at 285 DEG C.Such as, nylon 6,6 will at 285 DEG C of gels after 19 hours.Such as, when material does not move, when moving with the flow velocity being less than per minute 1 liter, gel time control unit 54 can be activated.When the flow velocity of material is less than per minute 1 liter, gel time control unit 54 can activate manually or automatically.Time equivalent when algorithm can determine that the material in equipment is 285 DEG C.

At least one gel time value (gel time such as, in flasher gel time, finisher gel time and transmission pipeline gel time) can compare with threshold value by gel time control unit 54.Gel time control unit 54 can produce alarm when such as at least one gel time value is less than threshold value.Such as, threshold value can be material gel in back segment before in hour time (such as, four hours).If gel time value is less than four hours, gel time control unit 54 can produce the alarm that instruction was less than four hours before back segment gel.

Storer 58 provides storage for the instruction and data relevant to gel time.Interface 60 can comprise keyboard, touch pad, screen, printer, socket, or be configured to allow user to observe and monitoring countdown gel time (such as, 19:00:00,18:59:59,18:59:58 etc.) or control the heat transmission medium at flasher 30 place, the heat transmission medium at finisher 36 place or transmit the miscellaneous part of temperature of heat transmission medium at pipeline 40 place.

Fig. 3 example is according to the method 100 of the gel formation in the monitoring polymeric amide synthesis system of an example.In step 102 place, method 100 comprises and the polyamide compound be partly polymerized is guided through flasher fresh feed pump, finisher pump and transmits in-line pump.In step 104 place, method 100 comprise by flasher fresh feed pump, finisher pump and transmit in-line pump be converted to the second operational mode from the first operational mode.At 106 places, method 100 comprises activated gel time control unit, and described gel time control unit is configured to estimate gel time at least one in flasher, finisher and transmission pipeline.At 108 places, method 100 comprises the reactor of polymeric amide synthesis system is converted to the second pattern from the first operational mode.

At 102 places, the polyamide compound be partly polymerized can be guided through flasher fresh feed pump 38, finisher pump 44 and transmit in-line pump 46, as discussed with reference to figure 1 herein.At 104 places, flasher fresh feed pump 38, finisher pump 44 and transmission in-line pump 46 are converted to the second operational mode from the first operational mode.In an example, the first operational mode is enable mode, and the second operational mode is idle pulley.Enable mode can comprise and system 10 being run under for the manufacture of the usual operational conditions of polymeric amide.Idle pulley can comprise the polyamide compound be partly polymerized by flasher fresh feed pump 38, finisher pump 44 with transmit the flow velocity of in-line pump 46 and be reduced by least in per minute 1 liter.In an example, idle pulley can comprise the polyamide compound be partly polymerized by flasher fresh feed pump 38, finisher pump 44 with transmit the flow velocity of in-line pump 46 and be reduced to per minute zero liter.In another example, the first operational mode can be enable mode and the second operational mode can be running stop mode, and wherein flasher fresh feed pump 38, finisher pump 44 and transmission in-line pump 46 are idle separately or shut down completely.

In instances, method 100 can be included in flasher fresh feed pump 38, transmit detection event before in-line pump 46 and finisher pump 44 are converted to the second operational mode from the first operational mode.In instances, this event can comprise detection flasher fresh feed pump fault, finisher failure of pump, transmit pipeline failure of pump, power-off (power outage), and at least one in their combination.

At 106 places, method 100 comprises activated gel time control unit, and described gel time control unit is configured to estimate gel time for flasher 30, finisher 36 and at least one transmission in pipeline 40.Activated gel time control unit 54 manually completes when can work as the back segment free time or shut down, or automatically completes when being less than threshold value by flasher 30, finisher 36 and the flowing of at least one of transmitting in pipeline 40.In some instances, threshold value is per minute 1 liter.

Gel time control unit 54 is configured to estimate gel time for flasher 30, finisher 36 and at least one transmission in pipeline 40.As discussed in this article, gel time can based at least exceeding the parameter of the time correlation of threshold temperature with flasher 30, finisher 36 and the temperature of polyamide compound transmitting in pipeline 40 to be partly polymerized at least one and temperature.

The diagram that gel time is mapped to temperature by Fig. 4 example.Such as, at 285 DEG C, material (such as, polymeric amide) will at 19 hours gels.Can be calculated by formula I at the gel time (in hour) of specified temp:

(formula I)

Wherein T is the temperature (DEG C) of the material measured by sensor 52A-C.In another example, T is the temperature calculated by heat transmission medium pressure and temperature.Such as, in an example, the T in formula I can be calculated by formula II:

(formula II)

T = \frac{43651.11}{(12.4469 - Log P) - 188.46}

Wherein T be heat transmission medium with the measuring tempeature of degree Celsius, and P be heat transmission medium with the measuring stress of pound/square inch absolute manometer, wherein 1psia equals about 6,895Pa.

In the process of the second pattern, the temperature of material can change.The algorithm used in gel time control unit 54 can be determined at the time equivalent of 285 DEG C to provide real-time gel time.Such as, after the time equivalent 19 hours of 285 DEG C, the material in equipment is by gel.The time equivalent of 285 DEG C can be determined by formula III:

(formula III)

Wherein the time of current temperature be material current temperature in hour time, the gel time of current temperature be use formula I based on current temperature in hour gel time, and be 19 hours at the gel time of 285 DEG C.

When activated gel time control unit 54, algorithm determination gel time.In an example, gel time is determined by count-down device, and it started with 19 hours and with the hours countdown of equal value of 285 DEG C.In an example, gel time adds up from initial value.Along with in equipment in the second mode process, gel time upgrades by the temperature variation of material continuously.

In an example, gel time is determined by formula (IV):

(formula IV)

Wherein the time of material in current temperature in the time of current temperature, the gel time of current temperature be use formula I based on current temperature in hour gel time, and 19 is gel times at 285 DEG C.

Method 100 can comprise, and at gel time control unit 54 place, flasher 30, finisher 36 and at least one transmission in pipeline 40 is received at least one parameter of heat transmission medium.Method 100 can also comprise: respond at least one parameter received, and upgrades at least one in flasher gel time, finisher gel time and transmission pipeline gel time.In an example, flasher gel time, finisher gel time and each transmission in pipeline gel time can be substantially the same.In another example, flasher gel time, finisher gel time and at least two of transmitting in pipeline gel time are different.

Method 100 can comprise and at least one gel time value being compared with threshold value.Such as, flasher gel time, finisher gel time and transmission pipeline gel time can be compared with threshold value.In an example, when any one in flasher gel time, finisher gel time and transmission pipeline gel time is lower than threshold value, alarm can be produced as alarm 62.Method 100 can comprise and show gel time via interface 60 for flasher gel time, finisher gel time and at least one transmission in pipeline gel time.

At 108 places, method 100 comprises the reactor 20 of polymeric amide synthesis system is converted to the second pattern from the first operational mode.Such as, the reactor 20 of polymeric amide synthesis system is converted to from the first operational mode the outlet valve 66 that the second pattern can comprise off-response device 20.Additionally, the reactor 20 of polymeric amide synthesis system is converted to the second pattern from the first operational mode can comprise the guide of flow of the polyamide compound be partly polymerized to the reservoir being different from flasher 30.Be in the example of baffle plate reactor at reactor 20, the reactor 20 of polymeric amide synthesis system be converted to the second pattern from the first operational mode and comprise the concentration reducing the mixture be partly polymerized in reactor 20.This concentration can by fetching boiling water inlet valve 70 and water is introduced into reactor 20 from water source 68 reduces.

As discussed in this article, gel time be to material in a device gel time countdown.When exceeding gel time, equipment can not be converted to the first operational mode when not carrying out burnouting to remove gel from the second operational mode.Method 100 can comprise, and before gel time passage, flasher fresh feed pump 38, transmission in-line pump 46 and finisher pump 44 is converted to the first operational mode from the second operational mode.In this case, method 100 can comprise gel time control unit 54 is failed.When exceeding gel time, method 100 can comprise, and such as, when the second pattern is idle pulley, whole technique is shut down, and the whole back segment that burnouts, such as, comprise flasher 30, finisher 36 and transmit pipeline 40.

Fig. 5 is for the manufacture of polymeric amide, and especially for manufacturing the schema of instance system 200 of nylon 6,6.System 200 can comprise reservoir 202.Reservoir 202 can the aqueous solution containing liquid or the dicarboxylic acid of liquid phase, diamines and solvent (such as, water) substantially.Dicarboxylic acid and diamines can form ammonium carboxylate salt.In an example, be configured for nylon 6 in system 200, when 6 manufacture, reservoir 202 can comprise hexa-methylene two ammonium adipic acid ester salt, and it can be dissolved in water in reservoir 202.Reservoir 202 may be used for the aqueous solution mixing or store ammonium carboxylate salt.

In an example, dicarboxylic acid and diamines can be added to reservoir 202 with equimolar ratio substantially.The ammonium carboxylate salts obtained can have about 7.5, according to appointment the pH of 7.4 to about 7.6.Each molecule of ammonium carboxylate salt can comprise the diamines of a part and the dicarboxylic acid of a part.The aqueous solution in reservoir 202 can be heated, as with pre-heaters or with water vapour, as the water vapour heating formed at another part of system 200.

Can will comprise the solution of dicarboxylic acid and diamines, such as, the ammonium carboxylate salt aqueous solution, is passed to vaporizer 208 from reservoir 202 via conduit 204.Vaporizer 208 can be configured to by the water of the part from the aqueous solution basically liquid phase be converted into gas phase substantially with the form of stream of water vapor 206.In an example, vaporizer 208 is by being heated to about 100 DEG C to about 230 DEG C by the aqueous solution, 100 DEG C to about 150 DEG C according to appointment, the temperature of such as about 110 DEG C, about 120 DEG C, about 130 DEG C, about 140 DEG C, about 150 DEG C, about 160 DEG C, about 170 DEG C, about 180 DEG C, about 190 DEG C, about 200 DEG C, about 210 DEG C, about 220 DEG C or about 230 DEG C forms stream of water vapor 206.Vaporizer 208 can increase the concentration of ammonium carboxylate salts.In an example, the concentration leaving reservoir 202 and the ammonium carboxylate salts that is fed to vaporizer 208 is about 40 % by weight to about 80 % by weight salt in water, or in water about 52 % by weight to about 65 % by weight, 63 % by weight salt according to appointment.Vaporizer 208 by the concentration of ammonium carboxylate salts, such as, can be increased to about 72 % by weight salt in water.

React to be formed the Polvamide prepolymer that can comprise dicarboxylic acid and the relative short polymer chain of diamines with removing dicarboxylic acid at least partially that water can also cause existing in the solution in vaporizer 208 and diamine portion via evaporation.In other words, removing water can make the condensation reaction between dicarboxylic acid and diamines start to be formed the oligopolymer of the first stage that can be final polyamide chains.Vaporizer 208 can concentrated aqueous solution, such as, by the water concentration from vaporizer 208 solution is out reduced, as to about 5 % by weight to about 50 % by weight the water concentration of water, the such as water of about 25 % by weight to about 35 % by weight, the according to appointment water of 25 % by weight, about 26 % by weight, about 27 % by weight, about 28 % by weight, about 29 % by weight, about 30 % by weight, about 31 % by weight, about 32 % by weight, about 33 % by weight, about 34 % by weight or about 35 % by weight.

Aqueous mixture, it comprises water, unreacted dicarboxylic acid and diamines, and such as, with the form of unreacted ammonium carboxylate salt, and if present, Polvamide prepolymer, can be passed to reactor 212 from vaporizer 208 via conduit 210.In the example of example in Figure 5, reactor 212 is autoclaves.In reactor 212, unreacted dicarboxylic acid and diamines can react each other, or react with Polvamide prepolymer, or both carry out simultaneously, to form polyamide products.Reactor 212 can provide water remove further make Polvamide prepolymer experience further polymerization to form the final polyamide polymer with final molecular weight or molecular weight ranges.Water can leave reactor via conduit 214, and it optionally can be connected to rectifying tower by fluid.Selected final molecular weight or molecular weight ranges can depend on the final required character of polyamide products.

The water concentration of the water of about 0.0001 % by weight to about 20 % by weight can be had from reactor 212 final polyamide polymer out, the such as water of about 0.001 % by weight to about 15 % by weight, the water of 0.01 % by weight to about 15 % by weight according to appointment, such as about 0.0001 % by weight, about 0.001 % by weight, about 0.01 % by weight, about 0.05 % by weight, about 0.1 % by weight, about 0.2 % by weight, about 0.3 % by weight, about 0.4 % by weight, about 0.5 % by weight, about 0.6 % by weight, about 0.7 % by weight, about 0.8 % by weight, about 0.9 % by weight, about 1 % by weight, about 1.2 % by weight, about 1.4 % by weight, about 1.5 % by weight, about 1.6 % by weight, about 1.8, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, the water of 19 % by weight or about 20 % by weight.

Final polyamide polymer can leave reactor 212 by transmitting pipeline 216.Transmit pipeline 216 can be fed in final treatment system 228, wherein final polyamide polymer can experience further mechanical treatment, as one or more in what rotate, extrude with in granulation.

System 200 can also comprise the sensor 230 being connected to gel time control unit 218.Gel time control unit 218 can determine single batch of gel number and continuous batch of gel number.Single batch of gel number and continuous batch of gel number both can at least based on the temperature of reactor 212 higher than time of threshold temperature.In instances, sensor 230 can comprise temperature sensor or be configured to provide other parts of parameter (determining single batch of gel number and continuous gel number based on its gel time control unit 218).

In the example provided in fig. 2, gel time control unit 218 comprises treater 220, storer 222, interface 224 and notifies 226.Gel time control unit 218 and sensor 230 can form one or more computer or its part.As shown in this example, storer 222, interface 224, sensor 230 and notify that 226 are communicated with treater 220.Treater 220 can be configured to perform instruction to perform the algorithm for estimate sheet one batch of gel number and continuous gel number.

Be correlated with for each batch in single batch of gel number and reactor 212 (such as, autoclave).In an example, in each batch process, when the temperature in reactor 212 is greater than 265 DEG C, single batch of gel number keeps increasing.In an example, the number of minutes of equal value when single batch of gel number originates in zero and be greater than threshold temperature (such as, 265 DEG C) with the temperature of reactor 212 adds up.When by batch to introduce from vaporizer 208 subsequently, single batch of gel number is reset to zero.Single batch of gel number of each batch of the manufacture of polyamide products can be stored in storer 222 and to draw via interface 224.When in reactor 212 special batch have than other batch higher deteriorated time, can identification form one batch of gel number.Identify that when special batch has higher deterioration (such as, single batch of gel number is higher, and deterioration is higher), can identify can at reactor 212 fault or the operation problem be found before manufacturing low-quality product.Such as, special reactor 212 may have the problem (such as, misspecification point) causing high deterioration.

Continuous gel number is relevant to reactor 212 and accumulate until overhaul reactor 212 continuously.In an example, the number of minutes of equal value when continuous gel number originates in zero and is greater than threshold temperature (such as, 265 DEG C) with the temperature of reactor adds up.In the process of multiple batches, continuous gel number continues to increase along with the temperature of reactor 212 is greater than 265 DEG C.In other words, continuous gel number continues to increase until to be taken out and clean to remove gel formation from production by reactor 212 along with each batch.Continuous gel number can provide special reactor (such as, reactor 212) how close to the information of overhauling.In an example, when continuous gel number reaches continuous gel number maximum value or exceedes threshold value, needs overhaul by reactor 212.Continuous gel number can compare with continuous gel number maximum value by gel time control unit 218.When continuous gel number is higher than continuous gel number threshold value, gel time control unit 218 can notify 226 via interface 224 display.Notify that 226 can provide warning condition signal or provide notice or the concrete condition detected.

Storer 222 provides storage for the instruction and data relevant to gel time.Interface 224 can comprise keyboard, touch pad, screen, printer, socket, or be configured to allow user to observe and monitoring countdown gel time (such as, 19:00:00,18:59:59,18:59:58 etc.) or control the heat transmission medium at flasher 30 place, the heat transmission medium at finisher 36 place or transmit the miscellaneous part of temperature of heat transmission medium at pipeline 40 place.

Fig. 6 example is according to the method 300 of the gel formation in the monitoring polymeric amide synthesis system of an example.In step 302 place, method 300 comprises and is fed to reactor by comprising one or more raw-material first batch.At 304 places, method 300 comprises activated gel control unit, and described gel control unit is configured to generation first single batch of gel number and continuous batch of gel number.As discussed in this article, first single batch of gel number and continuous batch of gel number are at least based on the time of temperature of reactor higher than threshold temperature.At 306 places, method 300 comprises and in the reactor one or more starting material is converted into the first polyamide products.At 308 places, method 300 comprises transmits the first polyamide products from reactor.At 310 places, method 300 comprises and is fed to reactor by comprising one or more raw-material second batch.At 312 places, the method can comprise activated gel control unit, and described gel control unit is configured to generation second single batch of gel number and upgrades continuous batch of gel number.

Embodiment

the general-purpose system of embodiment 1 to embodiment 2

In continuous nylon 6,6 manufacturing process, hexanodioic acid and hexamethylene-diamine are blended in water with roughly equimolar ratio, to be formed containing nylon 6,6 salt and there is the aqueous mixture of about 50 % by weight water.Salt brine solution is delivered to vaporizer with about 90L/ minute.Salt brine solution is heated to about 125-135 DEG C (130 DEG C) and is removed by the salt brine solution of water from heating by vaporizer, makes water concentration be about 30 % by weight.The salt mixture of evaporation is delivered to tubular reactor with about 75L/ minute.The temperature of the salt mixture of evaporation is increased to about 218-250 DEG C (235 DEG C) by reactor, thus allow reactor to be removed further by the salt mixture of water from the evaporation of heating, make water concentration reach about 10 % by weight, and salt is polymerized further.The mixture of reaction is delivered to flasher with about 60L/ minute.The mixture of reaction is heated to about 270-290 DEG C (280 DEG C) to remove water further from the mixture of reaction by flasher, makes water concentration reach about 0.5 % by weight, and the mixture reacted is polymerized further.Flasher comprises the pipe of the vicissitudinous sectional area of tool, and it starts with the pressure of less area and about 2MPa in the front end of pipe, and the pressure of the larger sectional area be little by little expanded in rear end and about 34KPa.The mixture of flash distillation of the relative viscosity with about 13 is delivered to finisher with about 54L/ minute; polyblend is made to stand vacuum to remove water further; water concentration is made to reach about 0.1 % by weight and relative viscosity reaches about 60; thus making polymeric amide obtain suitable final polymerization degree scope, the polyblend crossed by aftercondensated is afterwards delivered to forcing machine and tablets press with about 54L/ minute.

embodiment 1, comparative example, the fault of flasher pump, does not comprise gel time control unit.

Flasher fresh feed pump fault.Responsively, flasher fresh feed pump, finisher pump and transmission in-line pump are converted to idle pulley from enable mode.Flasher, finisher and transmission line temperature are remained on 285 DEG C, flasher is maintained at about 138KPa, repair is carried out 33 hours to flasher fresh feed pump simultaneously.After the reparation of finisher pump completes, increase flasher, transmit the temperature and pressure of pipeline and finisher for flasher fresh feed pump, finisher pump and transmission in-line pump to be converted to the preparation of enable mode from idle pulley.But after flasher fresh feed pump, finisher pump and transmission in-line pump are converted to activation running status, material can not be pumped across flasher by flasher pump.

At idle mode in wireless, flasher experiences 33 hours at 285 DEG C and 138KPa, and the complete gel of flasher.Make system enter idle pulley, flasher pump and flasher are taken off off-line, and burnout to remove gel to flasher.After burnouting, flasher pump and flasher to be restarted and material can be pumped across flasher by flasher fresh feed pump.Flasher and be connected equipment are taken off off-line to carry out burnouting be costliness and increase manufacturing cost.

the fault of embodiment 2, flasher pump, adopts gel time control unit in the system adopting baffle plate reactor.

Flasher fresh feed pump fault.Responsively, flasher fresh feed pump, finisher pump and transmission in-line pump are converted to idle pulley from enable mode, temperature are remained on 285 DEG C and the pressure of flasher is remained on 138KPa.Respond and flasher fresh feed pump, finisher pump and transmission in-line pump are converted to idle pulley, gel time control unit is activated.Response activated gel time control unit, produces gel time.Gel time is shown as 6 hours.Baffle plate reactor is converted into idle pulley, wherein reactor is introduced in baffle plate reactor to reduce the concentration of polymeric amide to the port closing of flasher and by the water of about 500L.By the temperature communication (transmission) of material in flasher, finisher and transmission pipeline to gel time control unit, and upgrade gel time continuously based on current temperature 285 DEG C.Estimate the work that 30-35 hour will be needed to the repair of flasher fresh feed pump.The estimation gel time of the 6h indicated by gel time control unit to operator provide must change free time-condition of pattern, to prevent gel event consuming time and expensive in other parts of flasher and system.The temperature of flasher, finisher and transmission pipeline is regulated down to 240 DEG C (by regulating heat transmission medium temperature and pressure).Gel time control unit indicates the gel time of 40 hours.33 hours are carried out to the repair of flasher fresh feed pump.

The reparation of flasher fresh feed pump was completed before gel counter expires.Regulate flasher, transmit the temperature (by heat transmission medium temperature and pressure) of material in pipeline and finisher to normal running (operation) conditions to prepare flasher fresh feed pump, finisher pump and transmission in-line pump to be converted to enable mode from idle pulley.Open the outlet of reactor.After flasher fresh feed pump, finisher pump and transmission in-line pump are converted to enable mode, material is pumped across system.

Compared with embodiment 1, there is not gel event.Gel time control unit provides warning to indicate for there is gel in process the repair time estimated by flasher pump, makes it possible to the idle condition in regulation system.

the general-purpose system of embodiment 3 and embodiment 4

In nylon 6,6 manufacturing process in batches, hexanodioic acid and hexamethylene-diamine are blended in water with roughly equimolar ratio, to be formed containing nylon 6,6 salt and there is the aqueous mixture of about 50 % by weight water.Salt brine solution is delivered to vaporizer with about 90L/ minute.Salt brine solution is heated to about 125-135 DEG C (130 DEG C) and is removed by the salt brine solution of water from heating by vaporizer, makes water concentration be about 30 % by weight.The salt mixture of evaporation is delivered to autoclave with about 75L/ minute, makes the salt mixture of the evaporation of about 10,000L fill autoclave.Autoclave by this heating materials to 270-290 DEG C (280 DEG C); water concentration is made to reach about 0.1 % by weight and relative viscosity reaches about 60; to make polymeric amide obtain suitable final polymerization degree scope, the polyblend crossed by aftercondensated is afterwards delivered to forcing machine and tablets press with about 60L/ minute.By polyamide products from after autoclave is extruded, the temperature in autoclave can be reduced to 160 DEG C.The salts solution another batch being carried out the evaporation of flash-pot is delivered to autoclave, and autoclave cycle starts again.

embodiment 3, comparative example, the fault of autoclave, does not comprise gel time control unit.

After multiple batches, autoclave is owing to the unexpected earth fault of the gel gathered wherein.Response autoclave fault, removes autoclave from production and overhauls, wherein cleaned by all surface and remove gel formation.

the fault of embodiment 4, autoclave, comprises gel time control unit.

After multiple batches, the setting point of single batch of gel number instruction autoclave is 285 DEG C, in other words, and too high 5 DEG C of the performance based on the past.Setting point is readjusted to 280 DEG C and single batch of gel number is monitored for autoclave.After multiple batches, the continuous gel number receiving autoclave increases above the notice of continuous gel number threshold value (running more than 10,000h more than 260 DEG C), indicates autoclave possible breakdown and in lower 50 batches, needs maintenance.Plan is predetermined shuts down to make the time, the loss of money and product can minimize.After the maintenance of autoclave, continuous gel number is reset to zero.

Described herein and example that is claimed invention theme is not limited by specific examples disclosed herein, because these examples are intended to the example of several aspects of present disclosure in scope.Any equivalent example is intended in the scope of present disclosure.In fact, state bright in the past, except provide herein and describe those except the multiple amendment of example will be obvious for those skilled in the art.This amendment is also intended to fall in the scope of claims.

The all publications mentioned in this manual, comprise non-patent literature (such as, scientific journal article), patent application is open, and patent combines by reference, just as by each particularly and pointing out individually to combine by reference.

statement in addition.

Theme of the present invention provides following statement, and its sequence number is not interpreted as providing significance level:

Embodiment 1 can comprise theme (as device, device, method or one or more means of carrying out action), as comprised the method for gel formation in monitoring polymeric amide synthesis system.Described method can comprise the polyamide compound be partly polymerized is guided through flasher fresh feed pump, finisher pump and transmission in-line pump, by described flasher fresh feed pump, described finisher pump and described transmission in-line pump are converted to the second operational mode from the first operational mode, activated gel time control unit, described gel time control unit is configured to for flasher, finisher and at least one transmission in pipeline estimate gel time, wherein said gel time based at least with described flasher, the temperature of the polyamide compound be partly polymerized at least one in described finisher and described transmission pipeline, and temperature exceedes the parameter of the time correlation of threshold temperature, and the reactor of described polymeric amide synthesis system is converted to the second reactor operational mode from the first reactor operational mode.

Embodiment 2 can comprise, or can optionally with the subject combination of embodiment 1, optionally to comprise, wherein said gel time control unit comprises graphical interfaces, and described method also comprises and shows described gel time via described graphical interfaces.

Embodiment 3 can comprise, or can optionally with the subject combination of in embodiment 1 and 2 or arbitrary combination, optionally to comprise, at least one gel time value is compared with threshold value.

Embodiment 4 can comprise, or can optionally with the subject combination of in embodiment 1-3 or arbitrary combination, optionally to comprise, compare generation alarm based on described.

Embodiment 5 can comprise, or can optionally with the subject combination of in embodiment 1-3 or arbitrary combination, optionally to comprise, wherein said gel time control unit determination flasher gel time, finisher gel time and transmission pipeline gel time.

Embodiment 6 can comprise, or can optionally with the subject combination of in embodiment 1-5 or arbitrary combination, optionally to comprise, wherein said flasher gel time is at least determined based on the temperature at described flasher place heat transmission medium.

Embodiment 7 can comprise, or can optionally with the subject combination of in embodiment 1-6 or arbitrary combination, optionally to comprise, wherein said transmission pipeline gel time is at least determined based on the temperature of described transmission pipeline place heat transmission medium.

Embodiment 8 can comprise, or can optionally with the subject combination of in embodiment 1-7 or arbitrary combination, optionally to comprise, wherein said finisher gel time is at least based on the temperature of condensation kettle place heat transmission medium in the rear.

Embodiment 9 can comprise, or can optionally with the subject combination of in embodiment 1-8 or arbitrary combination, optionally to comprise, at least one parameter of the heat transmission medium of at least one in described flasher, described finisher and described transmission pipeline is received at described gel time control unit place, and respond at least one parameter described of receiving, to upgrade in described flasher gel time, described finisher gel time and described transmission pipeline gel time corresponding one.

Embodiment 10 can comprise, or can optionally with the subject combination of in embodiment 1-9 or arbitrary combination, optionally to comprise, wherein said first operational mode and described first reactor operational mode are enable modes, and described second operational mode and described second reactor operational mode are idle pulleys.

Embodiment 11 can comprise, or can optionally with the subject combination of in embodiment 1-10 or arbitrary combination, optionally to comprise, wherein described flasher fresh feed pump, described finisher pump and described transmission in-line pump are converted to described second operational mode from described first operational mode and comprise the described polyamide compound be partly polymerized to be decreased to by the flow velocity of described flasher fresh feed pump, described finisher pump and described transmission in-line pump and be less than per minute 1 liter.

Embodiment 12 can comprise, or can optionally with the subject combination of in embodiment 1-11 or arbitrary combination, optionally to comprise, wherein described flasher fresh feed pump, described finisher pump and described transmission in-line pump are converted to described second operational mode from described first operational mode and comprise the described polyamide compound be partly polymerized is decreased to per minute zero liter by the flow velocity of described flasher fresh feed pump, described finisher pump and described transmission in-line pump.

Embodiment 13 can comprise, or can optionally with the subject combination of in embodiment 1-12 or arbitrary combination, optionally to comprise, wherein described reactor is converted to described second reactor operational mode from described first reactor operational mode and comprises the outlet valve of closing described reactor.

Embodiment 14 can comprise, or can optionally with the subject combination of in embodiment 1-13 or arbitrary combination, optionally to comprise, wherein described reactor is converted to described second reactor operational mode from described first reactor operational mode and comprises the output stream of the described polyamide compound be partly polymerized from described reactor-lead to reservoir.

Embodiment 15 can comprise, or can optionally with the subject combination of in embodiment 1-14 or arbitrary combination, optionally to comprise, wherein said reactor is baffle plate reactor, and by described reactor from described first reactor operational mode be converted to described second reactor operational mode comprise reduce in described reactor described in the concentration of polyamide compound of being partly polymerized.

Embodiment 16 can comprise, or can optionally with the subject combination of in embodiment 1-15 or arbitrary combination, optionally to comprise, the concentration of polyamide compound of being partly polymerized described in wherein reducing comprises and demineralized water being introduced in described reactor.

Embodiment 17 can comprise, or can optionally with the subject combination of in embodiment 1-16 or arbitrary combination, optionally to comprise, before described flasher fresh feed pump, described transmission in-line pump and described finisher pump are converted to described second operational mode from described first operational mode, detect event.

Embodiment 18 can comprise, or can optionally with the subject combination of in embodiment 1-17 or arbitrary combination, optionally to comprise, wherein said detection event comprises at least one in detection the following: flasher fresh feed pump fault, finisher failure of pump, transmission pipeline failure of pump, power-off, and their combination.

Embodiment 19 can comprise, or can optionally with the subject combination of in embodiment 1-18 or arbitrary combination, optionally to comprise, before described gel time expires, described flasher fresh feed pump, described transmission in-line pump and described finisher pump are converted to described first operational mode from described second operational mode.

Embodiment 20 can comprise, or can optionally with the subject combination of in embodiment 1-19 or arbitrary combination, optionally to comprise, when described flasher fresh feed pump, described transmission in-line pump and described finisher pump are converted into described first operational mode from described second operational mode, make described gel time control unit outage.

Embodiment 21 can comprise, or can optionally with the subject combination of in embodiment 1-19 or arbitrary combination, optionally to comprise, when described gel time passage, described flasher, described finisher and described transmission pipeline are burnouted.

Embodiment 22 can comprise, or can optionally with the subject combination of in embodiment 1-21 or arbitrary combination, optionally to comprise, wherein said gel time be in described polymeric amide synthesis system, form gel before time.

Embodiment 23 can comprise, or can optionally with the subject combination of in embodiment 1-22 or arbitrary combination, optionally to comprise, wherein said polymeric amide synthesis system is by the dicarboxylic acid of straight chain and the diamines of straight chain or by the oligopolymer synthesizing polyamides from the dicarboxylic acid of straight chain and the diamines of straight chain.

Embodiment 24 can comprise, or can optionally with the subject combination of in embodiment 1-35 or arbitrary combination, to comprise theme (as device, device, method, or carry out one or more means of action), as the system of gel formation in the manufacture for monitoring polyamide products can be comprised.Described system can comprise polymerization reactor, described polymerization reactor is configured to one or more starting material are reacted to form polymeric amide, the back segment system in described polymerization reactor downstream, described back segment system configuration be increase described polymeric amide molecular weight to form described polyamide products, and gel time control unit, described gel time control unit is operatively connected to described back segment system, and be configured to when described back segment system is converted into the second operational mode from the first operational mode, for described back segment system estimation gel time, wherein gel time based at least with the temperature of the described polymeric amide in described back segment, and described temperature exceedes the parameter of the time correlation of threshold temperature.

Embodiment 25 can comprise, or can optionally with the subject combination of in embodiment 1-24 or arbitrary combination, optionally to comprise, wherein said gel time control unit comprises the treater being connected to storer, and wherein said treater is configured to perform the instruction stored in which memory.

Embodiment 26 can comprise, or can optionally with the subject combination of in embodiment 1-25 or arbitrary combination, optionally to comprise, wherein said gel time control unit comprises graphical interfaces, and described graphical interfaces is configured to show described gel time.

Embodiment 27 can comprise, or can optionally with the subject combination of in embodiment 1-26 or arbitrary combination, optionally to comprise, wherein said gel time control unit comprises warning horn, and described warning horn is configured to when described gel time value activates lower than during threshold value.

Embodiment 28 can comprise, or can optionally with the subject combination of in embodiment 1-27 or arbitrary combination, optionally to comprise, at pre-heaters and the vaporizer of described polymerization reactor located upstream.

Embodiment 29 can comprise, or can optionally with the subject combination of in embodiment 1-28 or arbitrary combination, optionally to comprise, wherein said polymerization reactor comprises outlet valve, described outlet valve be configured to when described back segment system in the second mode of operation time close.

Embodiment 30 can comprise, or can optionally with the subject combination of in embodiment 1-29 or arbitrary combination, optionally to comprise, wherein said polymerization reactor comprises baffle plate reactor.

Embodiment 31 can comprise, or can optionally with the subject combination of in embodiment 1-30 or arbitrary combination, optionally to comprise, wherein said polymerization reactor is connected to source line, described source line is connected to the vaporizer in described polymerization reactor located upstream, and wherein said source line comprises water-in.

Embodiment 32 can comprise, or can optionally with the subject combination of in embodiment 1-31 or arbitrary combination, optionally to comprise, wherein said first operational mode is enable mode, and described second operational mode is idle pulley.

Embodiment 33 can comprise, or can optionally with the subject combination of in embodiment 1-32 or arbitrary combination, optionally to comprise, wherein when described back segment system in the second mode of operation time, described polymeric amide has the flow velocity being less than 1 liter per second.

Embodiment 34 can comprise, or can optionally with the subject combination of in embodiment 1-33 or arbitrary combination, optionally to comprise, wherein said back segment system comprises: flasher, described flasher is positioned at described polymerization reactor downstream, and the described polymeric amide wherein leaving described flasher has the water percentage ratio of about 1 % by weight; Finisher, described finisher is positioned at the downstream of described flasher, and the described polymeric amide wherein leaving described finisher has the water percentage ratio of about 0.1 % by weight; And transmission pipeline, described transmission pipeline is positioned at the downstream of described finisher, and so that described polyamide products is passed to forcing machine from described finisher, described forcing machine is configured to extrude described polyamide products to form one or more polyamide thread material.

Embodiment 35 can comprise, or can optionally with the subject combination of in embodiment 1-34 or arbitrary combination, optionally to comprise, wherein said back segment system comprises: flasher fresh feed pump, and described flasher fresh feed pump is connected to described flasher; Finisher pump, described finisher pump is connected to described finisher; And transmission in-line pump, described transmission in-line pump is connected to described transmission pipeline.

Embodiment 36 can comprise, or can optionally with the subject combination of in embodiment 1-35 or arbitrary combination, optionally to comprise, wherein said flasher comprises flasher temperature sensor, and shown flasher temperature sensor being operable is connected to described gel time control unit.

Embodiment 37 can comprise, or can optionally with the subject combination of in embodiment 1-36 or arbitrary combination, optionally to comprise, wherein said finisher comprises finisher temperature sensor, and shown finisher temperature sensor is operatively connected to described gel time control unit.

Embodiment 38 can comprise, or can optionally with the subject combination of in embodiment 1-37 or arbitrary combination, optionally to comprise, wherein said transmission pipeline comprises transmission line temperature sensor, and shown transmission line temperature sensor is operatively connected to described gel time control unit.

Embodiment 39 can comprise, or can optionally with the subject combination of in embodiment 1-38 or arbitrary combination, optionally to comprise, wherein said polymerization reactor is configured to receive one or more starting material described, the oligopolymer that one or more starting material described comprise unbranched dicarboxylic acid and straight diamine or formed by unbranched dicarboxylic acid and straight diamine.

Embodiment 40 can comprise, or can optionally with the subject combination of in embodiment 1-39 or arbitrary combination, optionally to comprise, wherein said polymerization reactor is configured to receive one or more starting material described, the mixture that one or more starting material described comprise hexanodioic acid and hexamethylene-diamine or the oligopolymer formed by the mixture of hexanodioic acid and hexamethylene-diamine.

Embodiment 41 can comprise, or can optionally with the subject combination of in embodiment 1-40 or arbitrary combination, optionally to comprise, being polymerized that one or more monomers comprise one or more conversion of monomers is the first polymeric amide.

Embodiment 42 can comprise, or can optionally with the subject combination of in embodiment 1-35 or arbitrary combination, to comprise theme (as device, device, method, or carry out one or more means of action), as the method for gel formation in monitoring polymeric amide synthesis system.Described method comprises and is fed to reactor by comprising one or more raw-material first batch, activated gel control unit, described gel control unit is configured to generation first single batch of gel number and continuous batch of gel number, wherein said first single batch of gel number and described continuous batch of gel number at least based on the temperature of described reactor higher than time of threshold temperature, in described reactor, one or more starting material described are converted into the first polyamide products, described first polyamide products is transmitted from described reactor, described one or more raw-material second batch will be comprised and be fed to described reactor, and activate described gel control unit, described gel control unit is configured to generation second single batch of gel number and upgrades described continuous batch of gel number.

Claims

1. for monitor polyamide products manufacture in the system of gel formation, described system comprises:

Polymerization reactor, described polymerization reactor is configured to one or more starting material are reacted to form polymeric amide;

The back segment system in described polymerization reactor downstream, described back segment system configuration be increase described polymeric amide molecular weight to form described polyamide products; With

Gel time control unit, described gel time control unit is operatively connected to described back segment system, and wherein said gel time control unit comprises graphical interfaces, and described graphical interfaces is configured to show described gel time.

2. according tosystem according to claim 1, wherein said gel time control unit comprises warning horn, and described warning horn is configured to when described gel time value activates lower than during threshold value.

3. according tosystem according to claim 1, described system also comprises the pre-heaters and vaporizer that are positioned at described polymerization reactor upstream.

4. according tosystem according to claim 1, wherein said polymerization reactor comprises baffle plate reactor.

5. according tosystem according to claim 1, wherein said polymerization reactor is connected to source line, and described source line is connected to the vaporizer being positioned at described polymerization reactor upstream, and wherein said source line comprises water-in.

6. according tosystem according to claim 1, wherein said back segment system comprises:

Flasher, described flasher is positioned at described polymerization reactor downstream, and the described polymeric amide wherein leaving described flasher has the water percentage ratio of 1 % by weight;

Finisher, described finisher is positioned at described flasher downstream, and the described polymeric amide wherein leaving described finisher has the water percentage ratio of 0.1 % by weight; With

Transmit pipeline, described transmission pipeline is positioned at described finisher downstream, and so that described polyamide products is passed to forcing machine from described finisher, described forcing machine is configured to extrude described polyamide products to form one or more polyamide thread material.

7. according tosystem according to claim 6, wherein said back segment system comprises:

Flasher fresh feed pump, described flasher fresh feed pump is connected to described flasher;

Finisher pump, described finisher pump is connected to described finisher; With

Transmit in-line pump, described transmission in-line pump is connected to described transmission pipeline.

8. according tosystem according to claim 7, wherein said flasher comprises flasher temperature sensor, and described flasher temperature sensor being operable is connected to described gel time control unit.

9. according tosystem according to claim 7, wherein said finisher comprises finisher temperature sensor, and described finisher temperature sensor is operatively connected to described gel time control unit.

10. according tosystem according to claim 7, wherein said transmission pipeline comprises transmission line temperature sensor, and described transmission line temperature sensor is operatively connected to described gel time control unit.

11. according tosystem according to claim 1, wherein said polymerization reactor is configured to receive one or more starting material described, the oligopolymer that one or more starting material described comprise unbranched dicarboxylic acid and straight diamine or formed by unbranched dicarboxylic acid and straight diamine.

12. according tosystem according to claim 1, wherein said polymerization reactor is configured to receive one or more starting material described, the mixture that one or more starting material described comprise hexanodioic acid and hexamethylene-diamine or the oligopolymer formed by the mixture of hexanodioic acid and hexamethylene-diamine.