CN1310736A - Control system for continuous polyamidation process - Google Patents
Control system for continuous polyamidation process Download PDFInfo
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- CN1310736A CN1310736A CN99809020A CN99809020A CN1310736A CN 1310736 A CN1310736 A CN 1310736A CN 99809020 A CN99809020 A CN 99809020A CN 99809020 A CN99809020 A CN 99809020A CN 1310736 A CN1310736 A CN 1310736A
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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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
-
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/48—Polymers modified by chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
Abstract
An improved polyamidation system and control system for producing a polyamide from molten dicarboxylic acid monomer and molten diamine monomer. The polyamidation control system measures the molar ratio of the molten dicarboxylic acid monomer and molten diamine monomer with a partially polymerized mixture. A feed forward control algorithm is employed within the control system to determine the extent to which the ratio of the initial reactants must be altered prior to mixing in order to produce the resulting polyamide having stoichiometrically balanced molar ratio.
Description
Background of invention
I. invention field
The present invention relates generally to process by dicarboxylic acid monomer and diamine monomer production polymeric amide.More specifically, the polymerization system and the Controlling System that the present invention relates to improve, therefore, this system is by measuring the mol ratio of initiated polymerization afterreaction thing, and the flow rate of regulating the frit reaction raw material, can keep the mass flow rate of required frit reaction thing.
II. the discussion of prior art
Subject matter in the polymeric amide production is that the chemical combination that guarantees reactant is enough to make carboxyl end group and/or amine-terminated number balance in the gained polymeric amide.If reactant chemical combination causes carboxyl end group and/or amine-terminated number inconsistent, will produce adverse influence to some characteristic of gained polymeric amide.For example, when by hexanodioic acid and 1,6-hexanediamine (HMD) was produced nylon at 6,6 o'clock, found that the inconsistent end group of quantity has adverse influence to the dyeability of nylon, and can reduce the ability of producing high molecular weight nylon 6,6.Therefore, in order to make the best in qualityization of polymeric amide, producer has laid stress on the mol ratio of reactant in the equilibrium polymerization process.
A kind of prior art of producing polymeric amide comprises two-step approach, and dicarboxylic acid and diamines react in water and form a kind of salt in the method, then this salt are heated with initiated polymerization.Yet this two-stage polymerization method is imperfect, because it need add water, and the water that adds will use evaporator room to form salt to remove the time.Because evaporator room is very unpredictable and be difficult to by the model manufacturing, thereby will control this process to guarantee that mol balance suitable in the final polymkeric substance also is difficult.
In above-mentioned two-stage polymerization method, adopted various control mechanism.A kind of known controlling mechanism comprises taking a sample from reaction mass with physical method and is used for end group analysis.Yet this method is imperfect, because not only during operational cost and because institute's sample thief may not reflect the characteristic of reaction mass rightly, thereby tends to cause error.
Other known controlling mechanism comprises the on-line analysis of carrying out end group, does one's utmost to make in the polymeric amide of gained to keep suitable mol balance.Above-mentioned on-line Control mechanism helps avoid the needs to the sampling of reaction mass physics.A kind of technology comprises that the salifiable pH of shape of institute evaluates mol balance indirectly in the two-stage polymerization process by measuring.Yet this pH determination techniques is restricted, because pH is not the accurate especially index of end group equilibrated in the gained polymeric amide.
Another kind of online end group analysis technology comprises the end group ratio of measuring frit reaction thing in the polymerization process, and according to this mensuration, an amount of reactant is injected the melt polymerization mixture, so that the mol balance in the gained polymeric amide meets the requirements.This system is imperfect, because it need increase expensive measuring apparatus and circuit could inject the melt polymerization mixture with the reactant that appends.This system also is limited, makes reactant and the melt polymerization mixture chemical combination that adds subsequently because it need be taken time in addition.
Attempted under the situation that does not add water, directly to produce polymeric amide from monomer.Yet it is quite difficult having confirmed to control reactant bonded degree, because one or another kind of reactant is excessive, and all can be to the molecular weight of product and thus to its physicals generation adverse influence.The other problem of this class direct polymerization method also comprises because (1) is long-time (for example, several hours) keep at high temperature, (2) molten monomer contacts with oxygen, and (3) are subjected to the influence of trace metal impurity in the material of manufacturing process equipment and the monomer that produces and/or the degraded of polymeric articles.
This system just needs a kind of polymerization system and Controlling System of having improved for a long time, because can overcome above-mentioned shortcoming of the prior art.
Summary of the invention
One aspect of the present invention be a kind of be used for from dicarboxylic acid monomer and diamine monomer produce polymeric amide improvement polymerization system.First measuring apparatus that is used to measure fusion dicarboxylic acid monomer charging is provided.Second measuring apparatus that is used to measure the charging of fusion diamine monomer is provided.First and second measuring apparatus are combined, like this, fusion dicarboxylic acid monomer charging and fusion diamine monomer charging chemical combination and form the fused polymerization reaction mixture.Providing at least a is used to make the polymerization reaction mixture polymeric not have the reactor of venting port.Provide some to be used for detecting the device of polymerization reaction mixture fusion dicarboxylic acid monomer and fusion diamine monomer mol ratio.Control device is connected with the proofing unit and first and second measuring apparatus in the mode of communication.Control device is optionally regulated the mass flow rate of at least a fusion dicarboxylic acid monomer and the charging of fusion diamine monomer, with the mol ratio of fusion dicarboxylic acid monomer in the equilibrium polymerization reaction mixture and fusion diamine monomer.
Another aspect of the present invention is the polymerization Control System that is used for from dicarboxylic acid monomer and diamine monomer production polymeric amide.First device that is used to measure fusion dicarboxylic acid monomer charging is provided.Provide and be used for the fusion dicarboxylic acid monomer charging that infeeds second device with the fusion diamine monomer charging metering that forms the melt polymerization mixture.Some devices that are used for detecting polymerization reaction mixture fusion dicarboxylic acid monomer and fusion diamine monomer mol ratio are provided.A kind of controller that is connected with proofing unit and at least one first and second measuring apparatus in the mode of communication is provided.This controller is according to coming the mol ratio input signal of self-test device to control at least one first measuring apparatus and second measuring apparatus, regulating the mass flow rate of at least a fusion dicarboxylic acid monomer and fusion diamine monomer, so that the mol ratio of fusion dicarboxylic acid monomer and fusion diamine monomer in the equilibrium polymerization reaction mixture.
But above-mentioned Controlling System operate continuously can have in the gained polymeric amide under the carboxyl end group of equal number and the amine-terminated equilibrium condition with the polymerization of guaranteeing reactant and to carry out.Before forming the melt polymerization mixture, the flow rate of all reactants is adjusted.That is, regulate first and second measuring apparatus to change the mass flow rate of at least a fusion carboxylic acid monomer and fusion diamine monomer.After the mixing, append dicarboxylic acid monomer or diamine monomer again without any necessity.
Controlling System of the present invention is particularly suitable for using the polymerization system of directly producing polymeric amide from monomer.Like this, just water is added in dicarboxylic acid, diamines or the melt polymerization mixture without any necessity.
In at least a reactor that does not have a venting port, the temperature of this polymerization reaction mixture is about 220 ℃ to about 300 ℃.In at least a reactor that does not have a venting port, preferred pressure is about 0-500 pound/square inch (gauge pressure), is more preferably 50-250 pound/square inch (gauge pressure), is most preferably the 120-180 pound/square inch (gauge pressure).In at least a reactor that does not have a venting port, the residence time of this polymerization reaction mixture preferably is about 0.01 minute to about 30 minutes, is more preferably 0.5-30 minute, is most preferably 1-5 minute.At least aly do not have a polymerization reaction mixture of discharging the reactor of venting port from this, contain usually and be lower than 40% (weight) unconverted monomer, preferably be lower than 10% (weight) unconverted monomer.
In certain embodiments, can use at least a reactor that venting port is arranged in that at least a reactor downstream that does not have a venting port is optional, in order to remove in the polymerization process formed water and/or as the further usefulness of polymerization.When used as such, the residence time of polymerization reaction mixture at least a reactor that venting port arranged is preferably about 1 minute to about 60 minutes.
Also can use gas recovery system, in order to reclaim the diamine monomer and/or the dicarboxylic acid monomer of having gasified in the waste gas that produces by at least a reactor that venting port arranged.The diamine monomer that this exhaust flow generally includes water vapor and gasified.Waste gas contacts with the fusion dicarboxylic acid monomer in recovery tower, and whereby, the diamine monomer that at least a portion has gasified can react the formation polymeric amide with the dicarboxylic acid monomer.This is enough to form the efflux flow that comprises polymeric amide and unreacted fusion dicarboxylic acid monomer in this recovery tower.This efflux flow can mix with the fusion diamine monomer subsequently.
In one embodiment, the nylon 6 in the reactor of the venting port polymerization reaction mixture of discharging never, 6 relative viscosity (RV) is about 0 to about 3, and the relative viscosity of the nylon 6,6 from the polymerization reaction mixture that the reactor that venting port is arranged is discharged is about 3 to about 15.Relative viscosity used herein is the viscosity (representing with centipoise) and 25 ℃ of ratios that descend the viscosity (representing with centipoise) of 90% independent formic acid of 25 ℃ of following 8.4% (weight) polymeric amide solution in 90% formic acid (90% weight formic acid and 10% weight water).
Polyamidation process of the present invention can be produced its finished product and will do not added in the reactant by water, and does not have the salifiable intermediate steps of shape.In addition, process of the present invention can operate continuously, and in the high temperature section of this process the residence time of frit reaction thing and molten polymer very short.This reduces water loss, waste water quantum of output and the energy expenditure of this process significantly.This also can save some processing unit in the prior art process or reduce its desired size, for example is used for removing the vaporizer of the process water of interpolation.In addition, also can avoid making reactant and product be subjected to the over-drastic thermal exposure.
Relate to the continuous fusion dicarboxylic acid, for example hexanodioic acid of the present invention this on the one hand, the practicality and the economic method of the fusion dicarboxylic acid that continuous supply is used for polyamidation process or other purposes is provided.It is high-quality colour-fast or do not have the fusion acid of other thermal destruction that this method can provide.Purified fusion acid product helps to produce high-quality polymeric amide.
The accompanying drawing summary
Fig. 1 is the feel flow draw of block of the polyamidation system improved of explanation the present invention;
Fig. 2 is the feel flow draw of block of explanation polymerization Control System of the present invention;
Fig. 3 is second feel flow draw of block that polymerization Control System of the present invention as shown in Figure 2 is described; With
Fig. 4 is the feel flow draw of block of another alternative polymerization Control System of explanation the present invention.
The narration of illustrative embodiment
Polymerization system of the present invention and polymerization Control System can be used for producing various polymeric amide from diacid and diamine monomer.These systems are specially adapted to from hexanodioic acid and 1, and the 6-hexanediamine is produced nylon 6,6.
Fig. 1 demonstrates the process flow sheet of an embodiment of this method.Supply with fused 1,6-hexanediamine (HMD) from the storage tank 20 of fusion HMD.The method that some suitable supply fusion HMD are arranged.A kind of is the workshop that the processing unit of polyamidation is arranged on the close HMD of production, so that can directly with pipeline fusion HMD stream be transported to groove 20.Other method provides the HMD aqueous solution, with water evaporation and make the HMD fusion.
The method that for example can choose wantonly by the heat-transferring jacket around the groove 20 heats groove 20.Temperature in this groove preferably is about 70 ℃.With the metering system 22 of fusion HMD pumping by HMD, this system can accurately control the HMD amount that flows to downstream unit then.
Hexanodioic acid is dried crystalline form usually, supplies with from hexanodioic acid storage bin 24.Hexanodioic acid from the feed bin slippage to batch deoxygenation groove 26.In groove 26, remove air.Preferably with nitrogen in batches the metathetical mode change by periodic vacuum and reach the purpose that the air in the groove 26 is removed.Can form vacuum by vacuum pump 28.Can regulate between vacuum and the nitrogen pressure periodically variable frequency to reach required deoxygenation degree.
Preferred deoxygenation groove 26 in batches comprises a pressurized vessel, and this container has and is shaped to towards its end the funnel-shaped bottom portion of diameter reduction gradually.Each limit of this batch deoxygenation groove funnel part is preferably formed and becomes at least 70 ° angle with horizontal plane, so that logistics is easy to the bottom of spout.
Adipic acid crystals is substantially free of molecular oxygen, the molten-bath 30 from batch deoxygenation groove 26 slippages (preferably by gravity, simultaneously by nitrogen gas pressure in this batch deoxygenation groove) to hexanodioic acid.Preferred molten still 30 is chuck stills of continuously stirring, and this chuck still is operated under the temperature (promptly being higher than 153 ℃) of a little higher than hexanodioic acid fusing point, condition with the little pressurization of nitrogen.Enter fusion on the surface of the very fast fusion hexanodioic acid therein of adipic acid crystals in the still by the still top.Therefore, but this process continuous fusion hexanodioic acid.Preferred molten still 30 has the inlet nozzle of back taper to reduce resistance to flow.Also preferred this molten-bath 30 has the metal alloy of dysgenic impurity to make by seldom containing or not containing to molten monomer.Hastolloy C and 316 stainless steels are the materials that suit.
For the possibility that makes thermal destruction reduces to minimum, can be from this molten-bath the additional unit of further deoxygenation to be included may be useful.A kind of method that realizes this purpose is that the fusion hexanodioic acid in molten-bath 30 is supplied with vibrational energy, for example passes through ultrasonic unit.Vibrational energy can impel the air of carrying secretly to overflow from fusion acid, causes bubble to rise on the surface of this fusion acid.
Preferably the residence time of fusion hexanodioic acid in molten-bath 30 is reduced to the shortest, to reduce thermal exposure to this reactant.Preferred its residence time less than 3 hours, be more preferably 1-2 hour.Discharge the fusion hexanodioic acid from molten-bath 30 bottoms and it is pumped into the metering system 32 of fusion hexanodioic acid, this system can accurately control the hexanodioic acid amount that flows to downstream unit.
In batches the combination of deoxygenation groove 26 and hexanodioic acid molten-bath 30 can the continuous fusion adipic acid crystals, and can thermal destruction or fade.
In a preferred embodiment, fusion hexanodioic acid stream 36 is under about 170 ℃ temperature, and fusion HMD stream 34 is in about 70 ℃, and the pressure at Y-node 38 places is about 150 pounds/square inch (gauge pressures).Preferred this online static mixer is the Kenics static mixer with 24 unit (element).
The wall of Y-node and on-line mixing device 42 all is preferably maintained in the range of from about 268 ℃.The residence time of monomer in mixing tank 42 is preferably about 1-30 second, more preferably about 3 seconds.The polymerization reaction mixture that leaves mixing tank 42 enters the pipeline that does not have venting port, can make it for example under 260 ℃ and 150 pounds/square inch (gauge pressure) be arranged the 10-60 reaction times of second again.
Though process of the present invention can not wrapped under the aqueous situation in reactant and operated, yet, and do not require that this reactant is anhydrous fully.For example, the HMD incoming flow can contain up to about the water of 5% (weight), and hexanodioic acid stream can contain up to about the water of 2% (weight), and this process still can normally be moved.Reactant flow with such low levels water is referred to herein as " exsiccant basically ".
Some reactions of HMD and hexanodioic acid begin to enter to them generation constantly in time of heat exchanger 44 in the time that Y-node 38 contact each other from them.Can be selected the temperature and the residence time that this process was adopted in this stage, cause to stop when complete polymerization taking place when reaching this set-point or reaching at set complete polymerization takes place.Under latter event, the product that partial reaction takes place by monomeric contact is referred to as " prepolymer " in this article.Prepolymer in the pipe downstream of mixing tank 42 has 60-90% to change nylon 6,6 into usually.Can not stop up, because the condition that is adopted can prevent the half-finished crystallization of low melting point.Importantly make the optimized operation of process, promptly pipeline 40 and mixing tank 42 do not have venting port, and pressure wherein is lower, for example are about 0-500 pound/square inch (gauge pressure), are most preferably 150 pounds/square inch (gauge pressures).
In the embodiment depicted in fig. 1, this prepolymer is then by heat exchanger 44 and enter the prepolymer reactor 46 of venting port.It is not crucial using heat exchanger herein.Any required heating all can replace providing by the inside heating coil in the reactor 46 or around the chuck of this reactor.The prepolymer that leaves heat exchanger 44 after the heating preferably in being lower than reactor 46 position on liquid material surface enter.Further polymerization reaction take place in the reactor 46, preferably this reactor is a continuously stirred tank reactor (CSTR).Can choose wantonly reactor underflow 48 is divided into recirculation flow 50 and second shunting 52 of sending to further processing.If employing recirculation, then the flow rate of preferred recirculation flow 50 is bigger 15 times than the flow rate of the fresh prepolymer that infeeds reactor 46 at least.Preferred reactor 46 is filling under about 50% the liquid material operation so that provide big vapor/liquid to divide phase surface.
The generation at the high surface area interface that in this process, be starved of backmixing that polymer terminal group is provided, can promote the molten materials devolatilization, and the high heat transfer rate that can improve melting material temperature rapidly.These advantages can for example adopt continuously stirred tank reactor (CSTR) or adopt the plug flow reactor and make product stream recirculation and obtain.
The overhead stream 54 that leaves reactor 46 is to comprise the water vapor moisture of the vaporization that is produced by polycondensation (that is) and the steam of some HMD normally.Overhead stream 54 enters HMD recovery tower 56, also water 58 is infeeded this tower simultaneously.The condensation logistics 60 that contains some HMD and water is recycled to reactor 46, and remaining steam is cooled off by heat exchanger 62, discharges as a part of exhaust flow 64 then.
In one embodiment, prepolymer is heated to about 260 ℃ in heat exchanger 44, so reactor 46 is just in about 260 ℃ and 150 pounds/square inch (gauge pressure) operation down.As the example of a suitable relative flow rate, if per hour under 100 pounds the speed fresh prepolymer is being infeeded reactor 46, then the underflow recirculation flowrate of preferred this reactor is about per hour 2,000 pounds.Cao Zuo reactor 46 under these conditions, after reactant stayed in wherein 20 minutes, the conversion of monomer that can obtain more than 95% was the nylon 6,6 of 3% (weight) water-content.
According to the present invention, a kind of be used to the regulate feeding rate of at least a fusion dicarboxylic acid monomer and fusion diamine monomer or the Controlling System of mass flow rate are provided, to guarantee suitable mol ratio.In a preferred embodiment, according to the mass flow rate of the carboxyl end group and at least a reactant of amine-terminated balance adjustment of reactant in the polymerization reaction mixture.The on-line determination of this end group can carry out at arbitrary place in Y-node 38 downstreams.Show that in this embodiment the end group equilibrated is determined in the logistics 52 of leaving reactor 46 and carries out.Spectrography is carboxyl end group and an amine end groups equilibrated preferred method of measuring molten monomer in the polymerization reaction mixture.In this embodiment preferred, near infrared (NIR) analyser 66 is tested and appraised monomeric spectral luminosity value in the polymerization reaction mixture, detects carboxyl end group and amine end groups number in this mixture.
In one embodiment, Controlling System of the present invention comprises near infrared (NIR) instrument 66, receives controller 67, HMD metering system 22 and fusion hexanodioic acid metering system 32 from the input signal of NIR analyser 66.
The NIR analyser 66 that provides as an example is not limited to the device of measuring fusion dicarboxylic acid monomer and fusion diamine monomer mol ratio in the polymerization reaction mixture when acting on.Carboxyl end group and amine end groups number that NIR analyser 66 leaves by continuous detecting in the partially polymerized material of reactor 46 are realized said determination.Though it is preferred adopting NIR analyser 66, yet can expect, Controlling System of the present invention can be used for measuring the mol ratio of polymerization process fusion dicarboxylic acid and fusion diamines or the device of mol balance uses with many.
The carboxyl end group and the amine end groups equilibrated input signal of fusion dicarboxylic acid monomer and fusion diamine monomer are given controller 67 in an indication of the NIR analyser 66 generations polymerization reaction mixture.Controller 67 utilizes this input signal can regulate the mass flow rate of fusion diamine monomer and/or fusion diamine monomer, like this, will have required mol ratio by the polymeric amide that the polymerization reaction mixture polymerization is formed.In a preferred embodiment, controller 67 utilizes the feed forward control algorithm to change the feeding rate of fusion diamine monomer according to the input signal from NIR analyser 66.Adopt this feed forward control algorithm, can when signal is imported, control the ratio of fusion dicarboxylic acid monomer and fusion diamine monomer, with produce polymerization with predetermined molar ratio the finished product.In a preferred embodiment, this can realize by the feeding rate by means of HMD metering system 22 fine setting fusion diamine monomers.Discuss in more detail with reference to the control and the operation of Fig. 2-4 pair of HMD metering system 22 and fusion hexanodioic acid metering system 32 below.
It should be noted,, yet can expect that NIR analyser 66 can be placed on arbitrary position in Y-node 38 downstreams though the analyser of NIR shown in the figure is the direction configuration along logistics 52.For example, NIR analyser 66 can be placed in the reactor 46 between position, static mixer 42 and the reactor 46 below the liquid levels, in the static mixer 42 or between static mixer 42 and the Y-node 38.
Though the polymerization during the course of the material at this position,, polymeric degree in some embodiment of this process, and the polymericular weight that therefore obtains and relative viscosity (RV) will can be high to the required degree of the finished product.Therefore, can be with this partially polymerized material by flasher 68 to supply with additional heat, enter second reactor 70 then.Thereby the purposes of second reactor 70 is molecular weight and the RV that make this product of material further polymerization the raising.Should have the required molecular weight of the finished product from the polymerisate in the underflow 72 of second reactor.Temperature in preferred second reactor 70 is about 260 ℃ to about 280 ℃, and pressure is normal atmosphere.
Remove in the overhead stream 74 that HMD steam that produces in second reactor 70 and water vapor are entering scrubber 76.Also current 78 are infeeded this scrubber, like this, just make this vapor condensation, can be used as effluent stream 80 and discharge.All the other steams leave scrubber 76 with top stream 82, and become the part of exhaust flow 64.
Polymeric articles can be transported to tablets press 84 or deliver to by-pass line 86.If handle by this tablets press, again this polymer beads sent into moisture eliminator 88 thereafter.Adopting nitrogen feed 90, nitrogen gas blower 92 and nitrogen heater 94 that nitrogen is infeeded can be with polymer beads exsiccant container 88.The bottom of dried particle from moisture eliminator 88 emitted, and deliver to water spray cooler 96, sifter 98, by gas blower 100 it is transplanted on product storage area 102 then.
Now, consult Fig. 2, demonstrate the feel flow draw of block (summarize with 120 expression) of the Controlling System of the preferred embodiment of the invention among the figure, this Controlling System be used for improvement shown in Figure 1 polymerization system.Controlling System 120 comprises fusion diamines (HMD) metering system 22, fusion hexanodioic acid metering system 32, controller 67 and NIR analyser 66.Controlling System 120 is used for controlling the amount of fusion hexanodioic acid, and forming polymerization reaction mixture, and this polymerization reaction mixture is gone into static mixing tank 42 in that the route that leads to prepolymer reactor 46 is enterprising to this hexanodioic acid at Y-node 38 places and fusion two amine compounds.
The metering system 22 of fusion diamines comprises the combination 126 of diamines volume pump 124 and diamines under meter.In a preferred embodiment, diamines volume pump 124 is positive-displacement pumps, and it comprises the positive-displacement pump of driving motor 128, a plurality of main lifting pump (main pumping head) 130-134 and a fine setting lifting pump (trim head) 136.Driving motor 128 comprises the transmission shaft 138 that extends in each main lifting pump 130-134 and the fine setting lifting pump 136.Some special piston (not shown) are configured in main lifting pump 130-134 and the fine setting lifting pump 136.These piston (not shown) are connected on the transmission shaft 138 so that the fusion diamine monomer from fusion diamines groove 20 positive displacements process flow meter 126, is delivered to Y-node 38 forward then so that enter static mixer 42.
Main lifting pump 130-134 all has been equipped with servosystem 144-148, stroke position encoder 152-156 and stroke position controller 160-164.The servosystem 144-148 piston (in figure do not demonstrate) interior with being configured in corresponding main lifting pump 130-134 is connected.Stroke position encoder 152-156 monitors the shaft position of each servosystem 144-148, and will indicate the signal of stroke volume (0-100%) to send controller 67 to.Stroke position controller 160-164 receives the input signal of self-controller 67, and the shaft position of control servosystem 144-148 is so that produce predetermined stroke volume (0-100%) in main lifting pump 130-134.Preferred main lifting pump 130-134 can provide suitable flow rate, so that according to the scale of operation the fusion diamines of q.s is supplied with this system.
Fine setting lifting pump 136 has been equipped with servosystem 150, stroke position encoder 158 and stroke position controller 166 similarly.Servosystem 150, stroke position encoder 158 and stroke position controller 166 are operated synergistically according to the identical pattern of main lifting pump 130-134.Main difference is to finely tune lifting pump 136 accessible flow rates little than main lifting pump 130-134 basically.This is because fine setting lifting pump 136 is used for the fusion diamines than low discharge is transported to the big flow of next autonomous lifting pump 130-134, so that fine setting is transported to the aggregate supply of the fusion diamines of static mixer 42.As following detailed description, the meaning of these characteristics is that it can make Controlling System 120 of the present invention change the ratio of initial reactant (fusion hexanodioic acid and fusion diamines) before mixing, like this, has stoichiometrical balance mol ratio with regard to the polymeric amide that makes gained.
The flow meter 126 of fusion diamines metering system 22 comprises under meter 168 and flow transmitter 170.Configuration flow transmitter 170 is the flow rates that are used for monitoring the fusion diamine monomer that is detected by under meter 168, send out simultaneously a representative enter static mixer 42 the diamines flow rate output signal to controller 67.Under meter 168 and flow transmitter 170 can comprise any commercially available under meter and flow transmitter.Flow meter 126 and two amine pumps 124 cooperate the configuration of formation closed loop feedback jointly with controller 67, are made for the flow rate of optionally regulating the fusion diamines that enters static mixer 42.
The metering system 32 of fusion hexanodioic acid comprises hexanodioic acid volume pump 172 and flow meter 174.In a preferred embodiment, hexanodioic acid volume pump 172 is the positive-displacement pumps with driving motor 176 and a plurality of lifting pump 178-182.Driving motor 176 has the patrilineal line of descent with only one son in each generation moving axis 184 that extends among each lifting pump 178-182.Some special pistons (not demonstrating among the figure) are configured in the lifting pump 178-182, and be connected on the transmission shaft 184 so that the fusion hexanodioic acid from hexanodioic acid molten-bath 30 positive displacements process flow meter 174, is delivered to Y-node 38 forward then so that enter static mixer 42.
The flow meter 174 of fusion hexanodioic acid metering system 32 comprises under meter 196 and flow transmitter 198.Configuration flow transmitter 198 is to be used for monitoring the monomeric flow rate of fusion hexanodioic acid that is detected by under meter 196, send out simultaneously a representative enter static mixer 42 the hexanodioic acid flow rate output signal to controller 67.Under meter 196 and flow transmitter 198 can comprise any commercially available under meter and flow transmitter.
In one embodiment, this can realize by the feeding rate of diamines metering system 22 by fine setting fusion diamine monomer.The control of diamines metering system 22 and fusion hexanodioic acid metering system 32 and operation will be described in a more detailed discussion with reference to Fig. 2-4 below.
Consult Fig. 3, controller 67 can comprise the programmable logic controller that can buy on any market, and they include but not limited to dcs (DCS), programmable arithmetic facility or based on the Personal Computer of microprocessor.It is possible adopting the feed forward control configuration in controller 67 because the improvement shown in Fig. 1 the each several part of polyamidation system with regard to its feature with regard to the influence of polyamidation process, be predictable.That is, owing to cancelled by adding the salifiable step of water shape, the present invention need not use vaporizer in the polyamidation process.Vaporizer with regard to it to being unpredictable with regard to the influence of polyamidation and may demonstrating many variations during the course.
Now, will be in conjunction with the operation of reference Fig. 2 and 3 narration Controlling System 120.At first referring to Fig. 3, the initial step in the Controlling System 120 includes a bit manipulation person set(ting)value (capacity SP) is input in the controller 67.For simplicity, controller 67 is presented at Fig. 3 with the state that comprises terminal 67a that imports set(ting)value and the forward direction analog controller 67b that is used for management system 120 operations.After the user imported required set(ting)value (capacity SP), the terminal 67a of this computer was sent to forward direction analog controller 67b with this information.
So forward direction analog controller 67b is provided with motor speed control to the rotational speed governor 188 of the driving motor 176 that is used for hexanodioic acid volume pump 172.In a preferred embodiment, the flow rate of hexanodioic acid metering system 32 is further controlled by manual regulation Fill argon clamping fixture 190-194, like this, make the fusion hexanodioic acid move forward into static mixer 42 according to the predetermined flow rate that conforms to the selected set(ting)value of operator.In case set, the flow rate of this fusion hexanodioic acid should preferably no longer change according to the control signal of coming self-controller 67 or not change with regulating manual Fill argon clamping fixture 190-194.
Forward direction analog controller 67b also can be provided with motor speed control to the rotational speed governor 142 relevant with the driving motor 128 of diamines volume pump 124.Forward direction analog controller 67b monitors the output signal from NIR analyser 66 continuously, to obtain the evaluation to the mol ratio of fusion dicarboxylic acid monomer in the polymerization reaction mixture and fusion diamine monomer.In an importance, forward direction analog controller 67b utilizes the output signal of this NIR to produce and transmits the fine setting duty setting signal and give the stroke position controller 166 of the servosystem 150 relevant with fine setting lifting pump 136.The fine setting duty setting signal that sends stroke position controller 166 to is to produce according to the feed forward control algorithm that draws among the controller 67b.This feed forward control algorithm can be taked the form of internal memory look-up table, this look-up table comprises the data that expression must change to the ratio of reactant (fusion hexanodioic acid and fusion diamines) a certain degree, to obtain the desired volume set(ting)value that the operator selects according to the input of NIR analyser 66.
In this embodiment preferred, before the mixing, the flow rate of diamines metering system 22 is regulated continuously to reach suitable reactant (fusion hexanodioic acid and fusion diamines) ratio, like this, make the polymeric amide of gained have stoichiometric balance mol ratio.
Consult Fig. 2, controller 67 is realized above-mentioned requirements by at least one of at first controlling among driving motor 128 and the servosystem 144-148, like this, makes the fusion diamines be transferred to static mixer 42 from main lifting pump 130-134.Then, controller 67 is regulated fine setting lifting pump 136, thereby transfers the ratio of the reactant that carefully is transported to static mixer 42.Fine setting is carried out according to following several respects: the flow rate of fusion hexanodioic acid (being measured by flow meter 174), the flow rate of fusion diamines (measuring) by flow meter 126, stroke volume in measuring result of each reactant weight percentage within reactor 46 or in the partially polymerized mixture afterwards (being measured by NIR analyser 66) and the diamines volume pump 124 and motor speed information are (by position coder 152-158, positioner 160-166, rotating speed coder 140 and rotational speed governor 142 are measured).
Measure according to the end group equilibrated, the mass flow rate of using the feed forward control algorithm to regulate the fusion dicarboxylic acid belongs to scope of the present invention.Consult Fig. 4, the flow rate of fusion diamine monomer is remained under the constant flow rate, the dicarboxylic acid monomer is finely tuned make the ratio of reactant suitable simultaneously, thereby can draw required volume settings value.Can recognize that the control loop that is shown in Fig. 4 is to come from the loop conversion that is shown in Fig. 2, like this, with regard to the unnecessary operation that goes through embodiment among Fig. 4.
More than to the narration of specific embodiments of the present invention and do not mean that it is whole explanations of every kind of possible embodiment of the present invention.It will be understood by those skilled in the art that specific embodiments as herein described may be modified, yet all such modifications all should belong to scope of the present invention.For example, though narrated some detailed embodiment herein, i.e. hexanodioic acid and 1, nylon 6,6 is produced in the reaction of 6-hexanediamine, and other monomer that those skilled in the art may adopt them to know is produced other polymeric amide.
Claims (6)
1. one kind is used for from the Controlling System of dicarboxylic acid monomer and diamine monomer production polymeric amide, and this Controlling System comprises:
(a) being used to measure first of fusion dicarboxylic acid monomer charging installs;
(b) be used for infeeding second device that described fusion dicarboxylic acid monomer charging is measured with the fusion diamine monomer charging that forms the melt polymerization mixture;
(c) be used for detecting the device of polymerization reaction mixture fusion dicarboxylic acid monomer and fusion diamine monomer mol ratio; With
(d) a kind of controller that is connected with proofing unit and at least one first and second measuring apparatus in the mode of communication, this controller is according to coming the mol ratio input signal of self-test device to control at least one first measuring apparatus and second measuring apparatus, regulating the mass flow rate of at least a fusion dicarboxylic acid monomer and fusion diamine monomer, so that the mol ratio of fusion dicarboxylic acid monomer and fusion diamine monomer in the equilibrium polymerization reaction mixture.
2. the Controlling System of claim 1, wherein said proofing unit are to be used for measuring the carboxylic monomer end group in the polymerization process melt polymerization mixture and the near-infrared analyzer of diamine monomer terminal number.
3. the Controlling System of claim 1, in addition, described first device that is used to measure comprises first pump that links to each other with described fusion dicarboxylic acid monomer charging, and described second device that is used to measure comprises second pump that links to each other with the charging of described fusion diamine monomer.
4. the Controlling System of claim 1, wherein said dicarboxylic acid monomer is a hexanodioic acid, described diamine monomer is 1, the 6-hexanediamine, and described polymeric amide is a nylon 6,6.
5. one kind is used for from the system of dicarboxylic acid monomer and diamine monomer production polymeric amide, and this system comprises:
(a) provide first measuring apparatus that is used to measure fusion dicarboxylic acid monomer charging;
(b) provide second measuring apparatus that is used to measure the charging of fusion diamine monomer, first and second measuring apparatus have been combined, made fusion dicarboxylic acid monomer charging and fusion diamine monomer charging chemical combination to form the fused polymerization reaction mixture;
(c) at least aly be used to make the polymerization reaction mixture polymeric not have the reactor of venting port;
(d) be used for detecting the device of polymerization reaction mixture fusion dicarboxylic acid monomer and fusion diamine monomer mol ratio; With
(e) a kind of control device that is connected with the proofing unit and first and second measuring apparatus in the mode of communication, this control device is adjustable to less the mass flow rate of a kind of fusion dicarboxylic acid monomer and the charging of fusion diamine monomer, with the mol ratio of fusion dicarboxylic acid monomer in the equilibrium polymerization reaction mixture and fusion diamine monomer.
6. the system of claim 5, wherein this dicarboxylic acid monomer is a hexanodioic acid, this diamine monomer is 1, the 6-hexanediamine, and this polymeric amide is a nylon 6,6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8729298P | 1998-05-29 | 1998-05-29 | |
| US60/087,292 | 1998-05-29 |
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| CN1310736A true CN1310736A (en) | 2001-08-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99809020A Pending CN1310736A (en) | 1998-05-29 | 1999-05-26 | Control system for continuous polyamidation process |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP1080129A1 (en) |
| JP (1) | JP2002516365A (en) |
| KR (1) | KR20010070956A (en) |
| CN (1) | CN1310736A (en) |
| AU (1) | AU748194B2 (en) |
| BR (1) | BR9910791A (en) |
| CA (1) | CA2332937A1 (en) |
| EE (1) | EE200000695A (en) |
| HU (1) | HUP0101992A3 (en) |
| IL (1) | IL139815A0 (en) |
| MX (1) | MXPA00011755A (en) |
| NO (1) | NO20006013L (en) |
| PL (1) | PL344401A1 (en) |
| RU (1) | RU2000133318A (en) |
| SK (1) | SK17622000A3 (en) |
| TR (1) | TR200003533T2 (en) |
| TW (1) | TW442517B (en) |
| WO (1) | WO1999061510A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308374C (en) * | 2002-08-30 | 2007-04-04 | 东洋纺织株式会社 | Method for continuous production of polyamide |
| CN100494246C (en) * | 2004-02-04 | 2009-06-03 | 株式会社日立制作所 | Polymer synthesizing device |
| CN110684192A (en) * | 2019-11-07 | 2020-01-14 | 蓝星（成都）新材料有限公司 | P-phenylenediamine dissolving system and method for continuous polymerization of aramid fibers 1414 |
| CN112390945A (en) * | 2020-03-28 | 2021-02-23 | 成都肆零壹科技有限公司 | Continuous nylon polymerization method |
| CN114196009A (en) * | 2020-08-31 | 2022-03-18 | 中国石油化工股份有限公司 | Method for continuously preparing poly (m-xylylene adipamide) |
| CN114471426A (en) * | 2022-01-20 | 2022-05-13 | 济宁正东化工有限公司 | Fine sulfanilamide integrated preparation system |
| CN114746477A (en) * | 2019-12-19 | 2022-07-12 | 帝斯曼知识产权资产管理有限公司 | Continuous solid state polymerization process and reactor column for use therein |
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| EP1172353A1 (en) * | 2000-07-10 | 2002-01-16 | The Procter & Gamble Company | Retardation of discolouration of dicarboxylic acids |
| JP2002194079A (en) * | 2000-12-22 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | Production method for polyamide |
| US8420772B2 (en) * | 2008-07-11 | 2013-04-16 | Kingfa Science & Technology Co., Ltd | Semi-aromatic polyamide and a method for preparation with low wastewater discharge |
| JP5487782B2 (en) * | 2008-07-31 | 2014-05-07 | 東レ株式会社 | Polyamide prepolymer and continuous production method of polyamide |
| TW201446836A (en) | 2013-05-01 | 2014-12-16 | Invista Tech Sarl | Process for producing a partially balanced acid solution |
| TW201443103A (en) | 2013-05-01 | 2014-11-16 | Invista Tech Sarl | Nylon salt solution production from a partially balanced acid solution |
| CN104710317B (en) | 2013-12-17 | 2019-01-25 | 英威达纺织（英国）有限公司 | With the nylon salt solution production method for the container production PBA solution for having dispersing head |
| CN108929436A (en) * | 2018-06-12 | 2018-12-04 | 江苏海阳锦纶新材料有限公司 | A kind of preparation method of copolymer nylon |
| RU2761414C1 (en) * | 2020-09-14 | 2021-12-08 | Общество с ограниченной ответственностью "Спецлак" (ООО "Спецлак") | Method for control by high-frequency titration of the polycondensation stage in the production of alkyd lacquers |
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| BE756454A (en) * | 1969-09-23 | 1971-03-22 | Fiber Industries Inc | METHOD AND APPARATUS FOR PRODUCTION OF POLYAMIDES BY CONTINUOUS POLYMERIZATION |
| JPS5211354B2 (en) * | 1972-05-18 | 1977-03-30 | ||
| US4582520A (en) * | 1982-09-30 | 1986-04-15 | Owens-Corning Fiberglas Corporation | Methods and apparatus for measuring and controlling curing of polymeric materials |
| CH685003A5 (en) * | 1992-08-11 | 1995-02-28 | Buehler Ag | A method of continuously crystallizing and polymerizing plastic material, and apparatus therefor. |
| US5674974A (en) * | 1994-11-23 | 1997-10-07 | E. I. Du Pont De Nemours And Company | Continuous polymerization process for polyamides |
| US5532487A (en) * | 1994-11-23 | 1996-07-02 | E. I. Du Pont De Nemours And Company | Near-infrared measurement and control of polyamide processes |
| US5674972A (en) * | 1995-07-27 | 1997-10-07 | Albemarle Corporation | Polyamide-based formulations |
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1999
- 1999-05-26 IL IL13981599A patent/IL139815A0/en unknown
- 1999-05-26 JP JP2000550907A patent/JP2002516365A/en not_active Withdrawn
- 1999-05-26 HU HU0101992A patent/HUP0101992A3/en unknown
- 1999-05-26 KR KR1020007013251A patent/KR20010070956A/en not_active Application Discontinuation
- 1999-05-26 BR BR9910791-0A patent/BR9910791A/en not_active Application Discontinuation
- 1999-05-26 WO PCT/US1999/011577 patent/WO1999061510A1/en not_active Application Discontinuation
- 1999-05-26 SK SK1762-2000A patent/SK17622000A3/en unknown
- 1999-05-26 CA CA002332937A patent/CA2332937A1/en not_active Abandoned
- 1999-05-26 EE EEP200000695A patent/EE200000695A/en unknown
- 1999-05-26 RU RU2000133318/09A patent/RU2000133318A/en not_active Application Discontinuation
- 1999-05-26 EP EP99924508A patent/EP1080129A1/en not_active Withdrawn
- 1999-05-26 CN CN99809020A patent/CN1310736A/en active Pending
- 1999-05-26 PL PL99344401A patent/PL344401A1/en not_active Application Discontinuation
- 1999-05-26 TR TR2000/03533T patent/TR200003533T2/en unknown
- 1999-05-26 AU AU40990/99A patent/AU748194B2/en not_active Ceased
- 1999-07-29 TW TW088108917A patent/TW442517B/en not_active IP Right Cessation
-
2000
- 2000-11-28 MX MXPA00011755 patent/MXPA00011755A/en unknown
- 2000-11-28 NO NO20006013A patent/NO20006013L/en not_active Application Discontinuation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308374C (en) * | 2002-08-30 | 2007-04-04 | 东洋纺织株式会社 | Method for continuous production of polyamide |
| CN100494246C (en) * | 2004-02-04 | 2009-06-03 | 株式会社日立制作所 | Polymer synthesizing device |
| CN101108894B (en) * | 2004-02-04 | 2011-09-28 | 株式会社日立工业设备技术 | Polymerization processor |
| CN110684192A (en) * | 2019-11-07 | 2020-01-14 | 蓝星（成都）新材料有限公司 | P-phenylenediamine dissolving system and method for continuous polymerization of aramid fibers 1414 |
| CN114746477A (en) * | 2019-12-19 | 2022-07-12 | 帝斯曼知识产权资产管理有限公司 | Continuous solid state polymerization process and reactor column for use therein |
| CN112390945A (en) * | 2020-03-28 | 2021-02-23 | 成都肆零壹科技有限公司 | Continuous nylon polymerization method |
| CN112390945B (en) * | 2020-03-28 | 2022-10-28 | 成都肆零壹科技有限公司 | Continuous nylon polymerization method |
| CN114196009A (en) * | 2020-08-31 | 2022-03-18 | 中国石油化工股份有限公司 | Method for continuously preparing poly (m-xylylene adipamide) |
| CN114471426A (en) * | 2022-01-20 | 2022-05-13 | 济宁正东化工有限公司 | Fine sulfanilamide integrated preparation system |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2000133318A (en) | 2002-11-27 |
| EE200000695A (en) | 2002-04-15 |
| IL139815A0 (en) | 2002-02-10 |
| MXPA00011755A (en) | 2002-04-01 |
| BR9910791A (en) | 2001-02-13 |
| TW442517B (en) | 2001-06-23 |
| PL344401A1 (en) | 2001-11-05 |
| SK17622000A3 (en) | 2001-05-10 |
| AU748194B2 (en) | 2002-05-30 |
| CA2332937A1 (en) | 1999-12-02 |
| EP1080129A1 (en) | 2001-03-07 |
| KR20010070956A (en) | 2001-07-28 |
| NO20006013L (en) | 2001-01-25 |
| NO20006013D0 (en) | 2000-11-28 |
| WO1999061510A1 (en) | 1999-12-02 |
| HUP0101992A3 (en) | 2003-01-28 |
| AU4099099A (en) | 1999-12-13 |
| TR200003533T2 (en) | 2001-04-20 |
| JP2002516365A (en) | 2002-06-04 |
| HUP0101992A2 (en) | 2001-09-28 |
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