TWM493548U - Systems for monitoring for gel formation in a polyamide synthesis process - Google Patents

Abstract

The present disclosure relates to methods and systems for monitoring for gel formation in the production of a polyamide product. In one embodiment, the present invention provides a method that can include directing a partially polymerized polyamide mixture through a flasher feed pump, a finisher pump, and a transfer line pump. The method can include switching the flasher feed pump, the finisher pump, and the transfer line pump from a first operating mode to a second operating mode. The method can include activating a gel time control unit and can be activated to estimate a gelation time for at least one of a flasher, a finisher, and a transfer line. The method can include switching a reactor of the polyamide synthesis system from the first operating mode to the second mode.

Description

System for monitoring gel formation in polyamine synthesis methods Cross-reference to related applications

The present application claims priority to U.S. Provisional Patent Application Serial No. 61/818, 308, filed on Jan. 1, 2013, the disclosure of which is hereby incorporated by reference.

Polyamides have suitable properties such as extreme durability and strength that make them suitable for a variety of settings. Polyamines such as nylon, aromatic polyamines and poly(aspartic acid) sodium are commonly used in, for example, carpets, airbags, machine parts, garments, ropes and hoses. Nylon 6,6 is one of the most commonly used polyamines. The long molecular chain and dense structure of nylon 6,6 make it qualified for high-grade nylon fibers, which exhibit polymer strength, rigidity and thermal stability.

Polyamide is commercially synthesized in large-scale production facilities. Polyamine can be obtained by polymerizing a diamine with a dicarboxylic acid (sometimes in the form of a two-component ammonium carboxylate salt in a solvent such as water). For example, nylon 6,6 can be synthesized by subjecting a hexamethylene diammonium adipate salt to a condensation reaction to form a guanamine bond and releasing water. In a series of assemblies including autoclaves or reactors, flashers, and finishing machines, heat can be applied to the reaction mixture and water can be gradually removed to drive the equilibrium toward the polyamine (eg, nylon 6,6) until polymerization The chain reaches the desired molecular weight range. The molten polyamine can then be extruded into agglomerated particles which can be spun into fibers or processed into other shapes.

Current methods and apparatus for producing polyamines in a continuous manner experience certain problems. Certain components of the process after the process can be turned off or left idle for a variety of reasons. When one of the latter stages of the process When components are closed or idle, other components of the back-end process are also turned off or idle. The polyamine polymer can gel over time during shutdown or idle periods. Gelation of the polyamine polymer can hinder and, in some cases, prevent the flow of polyamine when the device is restarted. If the polyamine is gelled before the device is restarted, it will be necessary to shut down the entire process and perform a burnout to remove the cementitious material. Closing the entire process and performing burnout can be a difficult and cumbersome procedure and time consuming and expensive. Therefore, current reactions and systems used to make polyamines may require frequent shutdowns and burnouts.

Current methods and apparatus for producing polyamines in a batch manner can also experience certain problems. A gel is formed each time the temperature of the autoclave rises above the threshold temperature. During the batch process, the temperature in the autoclave sometimes rises above the threshold temperature. In addition, because of the issues and problems associated with autoclaves, the temperature can rise above the threshold temperature. Accumulation of the gel over time can lead to autoclave failure and product degradation. When the autoclave length or product has fallen below the quality threshold, the autoclave is removed from manufacturing and serviced, which can be cumbersome and time consuming. Thus, current methods and systems for making polyamines can experience unexpected autoclave failures and reduced product quality.

As explained herein, this creation provides a solution to these problems.

The present work can provide methods and systems for monitoring gel formation in a polyamide synthesis system, such as systems for making nylon 6,6. The method can include directing a partially polymerized polyamine mixture through a flasher feed pump, a finishing machine pump, and a transfer line pump. The method can include switching a flasher feed pump, a finisher pump, and a transfer line pump from a first mode of operation to a second mode of operation. The gel time control unit can be activated to estimate the gel time of at least one of the flasher, the finisher, and the transfer line. The gel time is based on at least one temperature of the partially polymerized polyamine mixture in at least one of the flasher, the finishing machine, and the transfer line, and a parameter related to the time at which the temperature is greater than the threshold temperature. The method can include switching the reactor of the polyamine synthesis system from a first reactor mode of operation to a second reactor mode of operation.

This creation provides a system for monitoring gel formation in the manufacture of polyamide products. The system can include a polymerization reactor configured to convert one or more starting materials to form a polyamine, and a downstream processing system downstream of the polymerization reactor, the post-stage processing system configured to enhance polyamine The molecular weight forms a polyamine product. The system can include a gel time control unit operatively coupled to the back end process system and configured to estimate a gel time of the back end process system, at which time the back end process system switches from the first mode of operation to the second mode of operation. The gel time can be based on parameters relating to at least one temperature of the polyamine in the back-end process and a time when the temperature is greater than the threshold temperature.

This creation provides advantages over other methods and systems for preparing polyamines. For example, certain components of the post-process process, such as finishers, flashers, and transfer lines, may need to be turned off or left idle for a variety of reasons. When a component is closed or idle, other components of the back-end process are also turned off or idle. During shutdown or idle periods, the risk of gelation of polyamido in the back-end process equipment increases. As described herein, after the polyamide has gelled in the device, it must be turned off (if not turned off) and burned out of the process. The gel time is the time before the polyamide condenses in the device, which is based on the temperature of the material within the device.

This creation provides an instant method for determining and communicating gel time information to process operators. The operator can use the gel time to make operational decisions that reduce the cost and time lost due to shutdown or idle. For example, an operator can adjust multiple parameters (such as temperature or pressure) to increase gel time if necessary. If the polyamine is gelled in the device, it is not known that adjusting the process parameters will not provide any benefit, and adjusting the parameters will waste time and money. However, this creation provides a method or system for determining, monitoring, and delivering the gel time of the back end process. As a result, the entire back-end process of the process can be avoided and the lengthy burn-out process can be performed, even if the manufacturing process is restarted when the back-end process is closed or idle (eg, maintenance).

This work also provides a method for monitoring gel formation in the manufacture of polyamide products. The method can include feeding a first batch comprising one or more starting materials to the reactor and starting Gel control unit. The gelation control unit can be configured to produce a first single batch gel number and a continuous batch gel number. The first individual batch gel number and the continuous batch gel number may be based on at least one of the reactor temperature being above the threshold temperature. The method can include converting one or more starting materials to a first polyamine product in a reactor and transferring the first polyamine product from the reactor. The method can include feeding a second batch comprising one or more starting materials to the reactor and initiating a gelation control unit configured to generate a second individual batch gel number and update the continuous batch gel number .

This creation provides an instant method for determining and communicating to a process operator a single batch of gel number and a cumulative number of gels. The individual batch gel counts accumulate during a single batch process and are reset to zero when a subsequent batch is introduced. The number of gels per batch can identify operational difficulties that are not noticeable in systems that do not have a single batch of gel count. For example, a single batch gel number can determine whether a particular batch has a higher degradation than other batches or other reactors (eg, autoclaves). The number of gels in a single batch can also determine when a particular autoclave consistently forms more degradation, which may indicate that a particular autoclave has operational problems, such as erroneous set points or other deficiencies. Thus, the present authoring method and system can identify and address deficiencies in a particular autoclave that is not noticeable in systems that do not have a single batch of gel number.

The cumulative number of gelation continues to accumulate until the autoclave is overhauled, at which point the cumulative number of gels is reset to zero. The cumulative number of gels provides a cumulative degradation of the autoclave (e.g., gel formation on the surface) and provides an estimate of when the autoclave needs to be serviced. The cumulative number of gels eliminates the ambiguity when it may be necessary to perform an overhaul and allows the operator to plan accordingly. Therefore, unexpected failure of the autoclave can be avoided, which can reduce the time and cost associated with accidental overhaul.

10‧‧‧System

12‧‧‧Reservoir

14‧‧‧Evaporator

16‧‧‧ Pipes

18‧‧‧Water Vapor Logistics

20‧‧‧Reactor

22‧‧‧ Pipes

24‧‧‧Rectifier

26‧‧‧ Pipes

28‧‧‧Exhaust line

30‧‧‧Flasher

32‧‧‧ Pipes

34‧‧‧Export pipeline

36‧‧‧ Finishing machine

38‧‧‧Flasher feed pump

40‧‧‧Transfer pipeline

42‧‧‧Final processing system

44‧‧‧ Finishing machine pump

46‧‧‧Transfer line pump

50‧‧‧ part of the system

52A‧‧‧ sensor

52B‧‧‧ sensor

52C‧‧‧ sensor

54A‧‧‧gel time control unit

54B‧‧‧gel time control unit

54C‧‧‧gel time control unit

56A‧‧‧ processor

56B‧‧‧ processor

56C‧‧‧ processor

58A‧‧‧ memory

58B‧‧‧ memory

58C‧‧‧ memory

60A‧‧ interface

60B‧‧ interface

60C‧‧ interface

62A‧‧‧Announcer

62B‧‧‧Announcer

62C‧‧‧Announcer

64A‧‧‧ channel

64B‧‧‧ channel

64C‧‧‧ channel

66‧‧‧Export valve

68‧‧‧Water source

70‧‧‧Water inlet valve

72‧‧‧ Pipes

100‧‧‧ method

102‧‧‧Steps

104‧‧‧Steps

106‧‧‧Steps

108‧‧‧Steps

200‧‧‧ system

202‧‧‧Reservoir

204‧‧‧ Pipes

206‧‧‧Water Vapor Logistics

208‧‧‧Evaporator

210‧‧‧ Pipes

212‧‧‧Reactor

214‧‧‧ Pipes

216‧‧‧Transfer line

218‧‧‧gel time control unit

220‧‧‧ processor

222‧‧‧ memory

224‧‧" interface

226‧‧ Notice

228‧‧‧Final Processing System

230‧‧‧ sensor

300‧‧‧ method

302‧‧‧Steps

304‧‧‧Steps

306‧‧‧Steps

308‧‧‧Steps

310‧‧‧Steps

312‧‧ steps

The drawings are not necessarily to scale unless the

Figure 1 is a schematic flow diagram of a system for making polyamines according to one example.

2 is a more detailed schematic flow diagram of a portion of the system of FIG. 1 in accordance with an example.

Figure 3 illustrates a flow diagram of a method of gel formation in a polyamine synthesis system, according to one example.

Figure 4 illustrates a graphical representation of the gel time versus temperature.

Figure 5 is a schematic flow diagram of a system for making polyamines, according to one example.

Figure 6 illustrates a flow diagram of a method of monitoring gel formation in a polyamine synthesis system, according to one example.

This work describes a method and system for making polyamines such as nylon 6,6. The systems and methods described herein can include devices, systems, and methods for monitoring gel formation in a polyamine synthesis system.

definition

Values expressed in a range format are to be interpreted in a flexible manner to include not only the numerical values that are explicitly stated as the limits of the scope, but also all individual values or sub-ranges that are encompassed by the scope of the invention, as the various values and sub-ranges are clearly stated. For example, the range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values within the specified range (for example, 1%). , 2%, 3%, and 4%) and sub-ranges (eg, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). Unless otherwise stated, the statement "about X to Y" has the same meaning as "about X to about Y". Also, unless otherwise stated, the statement "about X, Y or about Z" has the same meaning as "about X, about Y or about Z".

In this document, the terms "a" or "an" are used to include one or more unless the context clearly indicates otherwise. Unless otherwise stated, the term "or" is used to mean a non-exclusive "or". In addition, it is to be understood that the terms and terms are not intended to be Any use of paragraph headings is intended to help The literature is read and not interpreted as a limitation; information relating to the title of a paragraph may appear within or outside a particular paragraph. In addition, all publications, patents, and patent documents mentioned in this specification are hereby incorporated by reference in their entirety in their entirety in their entirety herein In the case of contradictions between the use of this document and the documents incorporated by reference, the use incorporation in the reference should be considered as a supplement to this document; for uncoordinated contradictions, the use in this document is quasi.

In the manufacturing methods described herein, the steps may be performed in any order without departing from the principles of the present invention, unless a temporary or operational order is explicitly stated. In addition, the prescribed steps can be performed at the same time unless there is a clear claim that the language statement is carried out separately. For example, the proposition step of performing X and the proclaiming step of performing Y may be performed simultaneously in a single operation, and the resulting process will be within the literal scope of the claimed process.

The term "about" as used herein may allow a degree of variation within a value or range, such as within 10%, within 5%, or within 1% of the stated value or the stated range.

As used herein, the term "substantially" means most or most, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99% or at least about 99.999% or 99.999% or more.

As used herein, the term "dicarboxylic acid" generally refers to a C ₄ -C ₁₈ α, ω- dicarboxylic acid. This term encompasses C ₄ -C ₁₀ α,ω-dicarboxylic acids and C ₄ -C ₈ α,ω-dicarboxylic acids. Examples of dicarboxylic acids encompassed by C ₄ -C ₁₈ α,ω-dicarboxylic acids include, but are not limited to, succinic acid, butanedioic acid, glutaric acid, pentanedioic acid, adipic acid ( Adipic acid, hexanedioic acid), pimelic acid, heptanedioic acid, suberic acid, octanedioic acid, azelic acid, nonanedioic acid, and sebacic acid, decanedioic acid . In some examples, the C ₄ -C ₁₈ α,ω-dicarboxylic acid is adipic acid, pimelic acid or suberic acid. In other examples, the C ₄ -C ₁₈ α,ω-dicarboxylic acid is adipic acid.

As used herein, the term "diamine" refers to a generally C ₄ -C ₁₈ α, ω- diamine. This term encompasses C ₄ -C ₁₀ α,ω-diamine and C ₄ -C ₈ α,ω-diamine. Examples of diamines encompassed by C ₄ -C ₁₈ α,ω-diamine include, but are not limited to, butane-1,4-diamine, pentane-1,5-diamine, and hex-1,6-diamine, It is called hexamethylenediamine. In some examples, the C ₄ -C ₁₈ α,ω-diamine is hexamethylenediamine.

In some examples, the use of a combination of adipic acid and hexamethylenediamine is contemplated herein.

As used herein, the term "polyamine" refers broadly to polyamines such as nylon 6, nylon 7, nylon 11, nylon 12, nylon 6,6, nylon 6,9, nylon 6,10, nylon 6,12 or Its copolymer.

As used herein, the term "polymer" can include a copolymer.

As used herein, the term "solvent" refers to a liquid that dissolves a solid, liquid or gas. Non-limiting examples of solvents are polyoxo, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

As used herein, the term "gel time" or "gel time" refers to the formation of a gel of polyamine to maintain the melt viscosity of the polymer sample at a constant temperature and constant vapor pressure before the inflection point of the heating time curve. time.

As used herein, the term "gel" refers to the product (nylon 6,6) and the very high molecular weight branched/crosslinked polymer formed and collected in the apparatus. The gel is insoluble, for example, insoluble in from about 98% to about 100% formic acid when heated to about 280 ° C to about 295 ° C at 101 KPa, and typically can only be removed from the device using extreme measures (such as by burning off the gel) ).

As used herein, the term "rear process" means a device comprising at least one of an autoclave or a flasher and a finishing machine.

As used herein, the term "single batch gel number" refers to a value that is continuously increased during a single batch process and reset to zero after the introduction of a subsequent batch. This value may correspond to a time value (eg, minutes) at which the reactor (eg, autoclave) temperature is above the threshold temperature during a single batch process.

As used herein, the term "cumulative cumulative number of times" means continuous increase until high pressure The value of the kettle for maintenance. This value may correspond to a time value (e.g., minutes) at which the temperature of the reactor (e.g., autoclave) is above the threshold temperature during a plurality of individual batch processes of a single autoclave.

As used herein, the term "burnout" refers to the process of applying heat to thermally decompose a cementitious material within a device.

System for preparing polyamine

1 is a flow diagram of an example system 10 for making polyamines, and in particular for making nylon 6,6. System 10 can include a reservoir 12 containing an aqueous solution of a dicarboxylic acid, a diamine, and a solvent (e.g., water) in a liquid or substantially liquid phase. The dicarboxylic acid and the diamine can form an ammonium carboxylate salt. In one example, if system 10 is configured for nylon 6,6, then reservoir 12 can include a hexamethylene diammonium adipate salt that is soluble in the water in reservoir 12. The reservoir 12 can be used to mix or store an aqueous solution of an ammonium carboxylate salt.

In one example, the dicarboxylic acid and the diamine can be added to the reservoir 12 at substantially equal molar ratios. The resulting ammonium carboxylate salt solution may have a pH of about 7.5, such as from about 7.4 to about 7.6. Each molecule of the ammonium carboxylate salt may include a diamine molecule and a dicarboxylic acid molecule. The aqueous solution in the reservoir 12 can be heated, such as with a preheater or steam, such as a vapor formed in another portion of the system 10.

A solution comprising a dicarboxylic acid and a diamine (e.g., an aqueous solution of an ammonium carboxylate salt) can be transferred from the reservoir 12 to the evaporator 14 via line 16. The evaporator 14 can be configured to convert a portion of the water in the aqueous solution from a substantially liquid phase to a substantially gaseous phase in the form of a water vapor stream 18. In one example, the evaporator 14 is heated by heating the aqueous solution to a temperature of from about 100 ° C to about 230 ° C, such as from about 100 ° C to about 150 ° C, such as about 110 ° C, about 120 ° C, about 130 ° C, about 140 ° C, about 150. The water vapor stream 18 is formed at a temperature of °C, about 160 °C, about 170 °C, about 180 °C, about 190 °C, about 200 °C, about 210 °C, about 220 °C, or about 230 °C. The evaporator 14 can increase the concentration of the ammonium carboxylate solution. In one example, the concentration of the ammonium carboxylate solution leaving the reservoir 12 and fed to the evaporator 14 is from about 40% to about 80% by weight salt in water or from about 52% to about 65% by weight in water. , such as about 63% by weight of salt. The evaporator 14 can make the concentration of the ammonium carboxylate solution Increase to, for example, about 72% by weight salt in water.

Removal of water by evaporation may also partially react at least a portion of the dicarboxylic acid and diamine present in the solution in the evaporator 14 to form a polyamido prepolymer which may comprise a relatively short polymer chain of dicarboxylic acid and amine. In other words, removal of water can initiate a condensation reaction between the dicarboxylic acid and the diamine to form an oligomer, which can be the first stage of the final polyamine chain. As described above, the evaporator 14 can be reduced, for example, by reducing the water concentration of the solution produced by the evaporator 14 to, for example, from about 5% by weight to about 50% by weight water, such as from about 25% by weight to about 35% by weight water, such as about 25 wt%, about 26 wt%, about 27 wt%, about 28 wt%, about 29 wt%, about 30 wt%, about 31 wt%, about 32 wt%, about 33 wt%, about 34 wt% or about The aqueous solution was concentrated by a water concentration of 35 wt% water.

The water vapor stream 18 may be allowed to escape to the atmosphere, or the water vapor stream 18 may condense and feed back to the reservoir 12 (not shown). The condensed water vapor can also be purified, such as by filtration or other purification methods. The condensed water vapor can also be used as a source of steam to generate steam, which can be used in other aspects of the system 10 as described below. The water vapor stream 18 itself may also be used as a vapor for other aspects of the system 10, such as preheating the aqueous solution at or substantially downstream of the reservoir.

A reaction mixture comprising water, unreacted dicarboxylic acid, and a diamine (e.g., in the form of an unreacted ammonium carboxylate salt and, if present, a polyamidamine prepolymer) can be transferred from evaporator 14 to reactor 20 via line 22. In reactor 20, the unreacted dicarboxylic acid and diamine may be reacted with each other, or with a polyamido prepolymer, or both to form a first polyamidole polymer. The temperature in reactor 20 can be further increased to exceed the temperature of evaporator 14, removing additional water. In one example, the temperature in the reactor can range from about 150 °C to about 300 °C, such as from about 200 °C to about 250 °C, such as from about 220 °C to about 230 °C, such as about 228 °C, such as about 150 °C, about 160. °C, about 170 ° C, about 180 ° C, about 190 ° C, about 200 ° C, about 210 ° C, about 215 ° C, about 220 ° C, about 225 ° C, about 230 ° C, about 235 ° C, about 240 ° C, about 245 ° C, About 250 ° C, about 260 ° C, about 270 ° C, about 280 ° C, about 290 ° C or about 300 ° C. First polyamine condensation produced by reactor 20 The water concentration of the solution of the compound and the unreacted dicarboxylic acid and diamine may range from about 1% by weight water to about 20% by weight water, such as from about 5% by weight water to about 15% by weight water, for example 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 about 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight or about 15% by weight of water.

Reactor 20 may be equipped with a rectification column 24 that is in fluid communication with reactor 20, such as via conduit 26. Rectification column 24, in turn, can be in fluid communication with exhaust line 28.

The first polyamine polymer formed in reactor 20, along with unreacted dicarboxylic acid and diamine, can be transferred from reactor 20 to flasher 30 via line 32 using a flasher feed pump 38. Within the flasher 30, the temperature of the reaction mixture of the first polyamine polymer with the unreacted dicarboxylic acid and diamine is substantially increased, such as from about 150 ° C to about 400 ° C, such as from about 250 ° C to about 350 ° C. , such as from about 260 ° C to about 300 ° C, such as about 280 ° C, such as about 200 ° C, or about 210 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, about 265 ° C, about 270 ° C, about 275 ° C, about 280 ° C, about 285 ° C, about 290 ° C, about 295 ° C, about 300 ° C, about 305 ° C, about 310 ° C, about 320 ° C, about 330 ° C, about 340 ° C or about 350 ° C temperature. At the inlet of flasher 30, the pressure of the reaction mixture is relatively high, such as from about 1.9 MPa to about 2.1 MPa. The pressure may gradually decrease as the reaction mixture travels through the flasher 30 such that at the exit of the flasher 30, the pressure is relatively low, in some cases almost vacuum (about 25 KPa to about 50 KPa). At the elevated temperature within the flasher 30, as the reaction mixture passes through the flasher 30, the gradual reduced pressure applied to the reaction mixture results in further removal of water from the reaction mixture as a flash distillation vapor. As the vapor is rapidly distilled from the reaction mixture, the first polyamide polymer can undergo further polymerization to form a second polyamide polymer. At the exit end of flasher 30, a two phase mixture of gaseous vapor with a second polyamidole polymer and a liquid mixture of unreacted dicarboxylic acid and diamine can be formed. The vapor may be released from the flasher 30, such as through a vent (not shown) in the flasher 30, or from the flasher 30 along with the product stream exiting the flasher 30 via the outlet conduit 34. Second polyamine polymerization produced by flasher 30 The water concentration of the solution of the compound and the unreacted dicarboxylic acid and diamine may be from about 0.1% by weight water to about 5% by weight water, such as from about 0.5% by weight water to about 2% by weight water, for example 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 water. The flasher 30 can include at least one relatively long conduit that wraps around the flasher 30, also known as a serpentine tube of the flasher 30. The line can carry the reaction mixture from the inlet of the flasher 30 to the outlet. The tubing may begin at the inlet with a small cross-sectional area (eg, a small diameter) and may extend along the length of the tubing until there is a relatively large cross-sectional area (eg, a relatively large diameter) at the outlet. As described above, the increase in cross-sectional area from the inlet to the outlet causes pressure to decrease from the inlet to the outlet of the flasher 30.

A catalyst can be added to the reaction mixture to help promote the condensation reaction of the polyamine described herein. In one example, the catalyst can be added to the reaction at evaporator 14 (e.g., into the inlet of evaporator 14), reactor 20 (e.g., into the inlet of reactor 20), or flasher 30 (e.g., into the inlet of flasher 30). In the mixture. Although a catalyst can be added, it is not necessary to polymerize polyamine. In one example, the catalyst can comprise at least one of sodium hypophosphite, manganese hypophosphite, and phenylphosphinic acid.

The second polyamine polymer and the unreacted dicarboxylic acid and diamine formed in the flasher 30 can be transferred from the flasher 30 to the finisher 36 via the conduit 34 using the finisher pump 44.

Finisher 36 may provide for further removal of water such that the second polyamide polymer undergoes further polymerization to form a final polyamine polymer having a final desired molecular weight or molecular weight range. The final desired molecular weight or molecular weight range selected may depend on the final desired properties of the polyamine product. Water removal in the finisher 36 can be accomplished by applying vacuum pressure to the reaction mixture within the finisher 36. The final molecular weight range of the final polyamine polymer can be controlled by controlling the vacuum pressure applied to the finisher 36 and the residence time of the reaction mixture within the finisher 36. The temperature in the finisher 36 can range from about 150 ° C to about 400 ° C, such as from about 250 ° C to about 350 ° C, such as from about 260 ° C to about 300 ° C, such as about 284 ° C or about 285 ° C, such as about 210 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, about 265 ° C, about 270 ° C, about 275 ° C, about 280 ° C, about 285 ° C, about 290 ° C, about 295 ° C About 300 ° C, about 305 ° C, about 310 ° C, about 320 ° C, about 330 ° C, about 340 ° C or about 350 ° C. The final polyamine polymer produced by the finishing machine may have a water concentration of from about 0.0001% by weight to about 2% by weight water, such as from about 0.001% by weight to about 1% by weight water, such as from about 0.01% by weight to about 1% by weight water. , for example, 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% by weight or about 2% by weight %water.

The final polyamine polymer can exit the finisher 36 via transfer line 40. Transfer line 40 can be fed to final processing system 42 via transfer line pump 46, where the final polyamine polymer can be further machined, such as one or more of spinning, extrusion, and granulation. For example, the final polyamine polymer can be pressed through a mold having a plurality of small capillaries to continuously produce a plurality of polyamidamine strands. The strands can be cut into polyamine pellets in a granulator.

Additives may be added to the polyamine polymer to provide or enhance various characteristics of the resulting polyamine product. For example, pigments may be added to control the color of the product polyamide, such may be used as a white pigment of titanium dioxide (TiO _2). A capping agent such as acetic acid can be added at the end of the process to terminate the polymerization. A capping agent can also be added to the salt in the reservoir 12. If a catalyst is used, a deactivating agent such as sodium bicarbonate can be added at the end of the process to deactivate the catalyst.

2 includes a diagram of a schematic flow diagram of a portion 50 of the system of FIG. 1 in accordance with an example. In addition to that illustrated in Figure 1, portion 50 of system 10 includes inductors 52A-C (collectively referred to herein as "sensors 52") and gel time control units 54A-C (collectively referred to herein as "gel time control units" 54"). In addition, portion 50 of system 10 includes an outlet valve 66 of reactor 20 and conduit 22 includes a water inlet valve 70 that is connected to water source 68 via conduit 72.

The outlet valve 66 can be used to close the outlet of the reactor 20 when the after-stage process (e.g., including the flasher 30, the finisher 36, and the transfer line 40) is closed or idle. In another example, the outlet valve 66 can separate the output of the reactor 20 to a reservoir (not shown) when the after-stage process is idle or closed. In addition, the conduit 22 is coupled to a water inlet valve 70 that controls the flow of the evaporator 14 (as shown in FIG. 1) and allows water from the water source 68 to flow into the reactor 20, diluting the contents of the reactor 20. As described herein, the outlet valve 66 can shut off the flow of the reactor 20 or separate the flow from the reactor 20 when the back-end process is idle, and the water inlet valve 70 can shut off the flow of the evaporator 14 or introduce water into the reactor 20. To reduce gel formation.

When the back-end process is switched from the first mode of operation to the second mode of operation, the gel time control unit 54 can estimate the gel time of the back-end process system. The gel time can be based on parameters relating to at least one temperature of the polyamine in the back-end process and a time when the temperature is greater than the threshold temperature. Portion 50 of system 10 can include sensors 52A-C (collectively referred to as "sensors 52"). As illustrated in the example of FIG. 2, inductor 52A is positioned upstream relative to flasher 30, inductor 52B is positioned upstream relative to finisher 36, and inductor 52C is positioned upstream relative to transfer line pump 46. The number and location of sensors 52 can vary from system to system. In one example, portion 50 of system 10 includes three or fewer inductors 52A-C. In another example, portion 50 of system 10 includes more than three inductors 52A-C.

The sensor 52 can include a temperature sensor, a flow sensor, or other component configured to provide a parameter by which the gel time control unit 54 determines the gel time. In one example, inductor 52A can include a flasher temperature sensor, inductor 52B can include a finisher temperature sensor, and inductor 52C can include a transfer line temperature sensor. The sensor 52 can be coupled to the gel time control unit 54 via channels 64A-C (collectively referred to as "channels 64"). Channel 64 can include a wired or wireless communication link.

In the example shown in FIG. 2, gel time control units 54A-C include processors 56A-C (collectively referred to as "processor 56"), memory 58A-C (collectively referred to as "memory 58"), interface 60A-C (collectively referred to as "Interface 60") and alarm 62A-C (collectively referred to as "Report Police 62"). In one example, each of the gel time control units 54 can each be an individual gelation control unit. In another example, the gel time control unit 54 can be a single gelation control unit that communicates with each of the sensors 52.

Gel time control unit 54 and sensor 52 may form or may be part of one or more computers. As illustrated in the examples, each gel time control unit 54 includes a processor 56, a memory 58 and an interface 60. The gel time control unit 54 may include an alarm 62 as appropriate. Memory 58, interface 60, sensor 52, and alarm 62 are in communication with processor 56. Processor 56 is configured to execute instructions for an algorithm that estimates gel time. The algorithm can include generating a gel time for at least one of the flasher 30, the finisher 36, and the transfer line 40. As described herein, the gel time can be based on at least one signal from the inductor 52 based on at least one of the temperature of the partially polymerized polyamine mixture in at least one of the flasher 30, the finisher 36, and the transfer line 40 and A parameter related to the time when the temperature is greater than the threshold temperature.

In one example, the gel time begins at 19 hours and counts down at 285 ° C in equivalent hours. For example, nylon 6,6 will gel after 19 hours at 285 °C. The gel time control unit 54 is activated when the material does not move, such as when moving at a flow rate of less than 1 L/min. When the material flow rate is less than 1 L/min, the gel time control unit 54 can be manually activated or automatically activated. The algorithm measures the equivalent time of the material in a device at 285 °C.

The gel time control unit 54 can compare at least one gel time value (eg, one of the flasher gel time, the finisher gel time, and the transfer line gel time) to a threshold value. The gel time control unit 54 may generate an alarm when, for example, at least one gel time value is less than a threshold. For example, the threshold may be the time in hours (eg, 4 hours) before the material in the back-end process is gelled. If the gel time value is less than 4 hours, the gel time control unit 54 can generate an alarm indicating less than 4 hours prior to gelation of the back end process.

Memory 58 provides instructions relating to gel time and storage of data. Interface 60 can This includes the keyboard, trackpad, screen, printer, network interface, or gel time configured to allow the user to observe and monitor the countdown (eg 19:00:00, 18:59:59, 18: 59:58, etc.) or other components of the heat transfer medium at flasher 30, the heat transfer medium at finisher 36, or the temperature of the heat transfer medium at transfer line 40.

Figure 3 illustrates a method 100 of monitoring gel formation in a polyamine synthesis system, according to one example. At step 102, method 100 includes directing a partially polymerized polyamine mixture through a flasher feed pump, a finishing machine pump, and a transfer line pump. At step 104, method 100 includes switching a flasher feed pump, a finisher pump, and a transfer line pump from a first mode of operation to a second mode of operation. At 106, method 100 includes activating a gel time control unit configured to estimate a gel time of at least one of a flasher, a finisher, and a transfer line. At 108, method 100 includes switching a reactor of a polyamine synthesis system from a first mode of operation to a second mode.

At 102, a partially polymerized polyamine mixture can be directed through a flasher feed pump 38, finisher pump 44, and transfer line pump 46 as described herein with respect to FIG. At 104, the flasher feed pump 38, the finisher pump 44, and the transfer line pump 46 are switched from the first mode of operation to the second mode of operation. In one example, the first mode of operation is an active mode and the second mode of operation is an idle mode. The activity mode can include the operating system 10 under standard operating conditions for the manufacture of polyamine. The idle mode may include reducing the flow rate of the partially polymerized polyamine mixture fed through the flasher feed pump 38, the finisher pump 44, and the transfer line pump 46 to less than 1 L/min. In one example, the idle mode can include reducing the flow rate of the partially polymerized polyamine mixture fed through the flasher feed pump 38, the finisher pump 44, and the transfer line pump 46 to 0 L/min. In another example, the first mode of operation can be the active mode and the second mode of operation can be the off mode, wherein the flasher feed pump 38, the finisher pump 44, and the transfer line pump 46 are each idle or fully closed.

In an example, the method 100 can include detecting the flasher feed pump 38, the transfer line pump 46, and the finishing machine pump 44 before switching from the first mode of operation to the second mode of operation. Pieces. In an example, the event can include detecting at least one of a flasher feed pump fault, a finisher pump fault, a transfer line pump fault, a power interruption, and combinations thereof.

At 106, method 100 includes activating a gel time control unit configured to estimate a gel time of at least one of flasher 30, finisher 36, and transfer line 40. The start gel time control unit 54 can be manually performed when the rear stage process is idle or closed, and can be automatically performed when the flow rate through at least one of the flasher 30, the finisher 36, and the transfer line 40 is less than the threshold. In some instances, the threshold is 1 L/min.

The gel time control unit 54 is configured to estimate the gel time of at least one of the flasher 30, the finisher 36, and the transfer line 40. As described herein, the gel time can be based on at least one temperature of the partially polymerized polyamine mixture in at least one of flasher 30, finishing machine 36, and transfer line 40, and the temperature is greater than the temperature of the threshold temperature. parameter.

Figure 4 illustrates a graphical representation of the gel time versus temperature. For example, at 285 ° C, the material (eg, polyamine) will gel within 19 hours. The gel time (in hours) at a particular temperature can be calculated by Equation I:

Where T is the temperature (°C) of the material measured by the sensors 52A-C. In another example, T is the temperature calculated from the heat transfer medium pressure and temperature. For example, in one example, T in Equation I can be calculated by Equation II:

Wherein T is the measured temperature in degrees Celsius of the heat transfer medium and P is the measured pressure in pounds per square inch absolute pressure of the heat transfer medium, wherein 1 psia is equal to about 6,895 Pa.

During the second mode, the material temperature can vary. The algorithm used in gel time control unit 54 measures the equivalent time at 285 ° C to provide instant gel time. For example, at 19 hours after the equivalent time at 285 ° C, the material in the device will gel. The equivalent time at 285 ° C can be determined by Equation III:

The time at the current temperature is the time in hours of the material at the current temperature, and the gel time at the current temperature is the gel time in hours based on the current temperature using Equation I, and at 285 ° C. The gel time was 19 hours.

When the gel time control unit 54 is activated, the algorithm determines the gel time. In one example, the gel time is determined by a countdown timer that starts at 19 hours and counts down at an equivalent hour at 285 °C. In one example, the gel time is counted from the initial value. The gel time is continuously updated as the material temperature in the device changes during the second mode.

In one example, the gel time is determined by equation (IV):

The time at the current temperature is the time of the material at the current temperature, and the gel time at the current temperature is the gel time in hours based on the current temperature using Equation I, and 19 is the gel at 285 ° C. time.

The method 100 can include receiving at least one parameter of a thermal transfer medium of at least one of the flasher 30, the finisher 36, and the transfer line 40 at the gel time control unit 54. The method 100 can also include updating at least one of a flasher gel time, a finisher gel time, and a transfer line gel time in response to receiving the at least one parameter. In one example, each of the flasher gel time, the finisher gel time, and the transfer line gel time can be substantially similar. In another example, at least two of the flasher gel time, the finisher gel time, and the transfer line gel time are different.

Method 100 can include comparing at least one gel time value to a threshold value. For example, the flasher gel time, the finisher gel time, and the transfer line gel time can be compared to the threshold. In one example, an alarm, such as alarm 62, is generated when either of the flasher gel time, the finisher gel time, and the transfer line gel time is below the threshold. The method 100 can include displaying, via the interface 60, a gel time of at least one of a flasher gel time, a finisher gel time, and a transfer line gel time.

At 108, method 100 includes switching reactor 20 of the polyamine synthesis system from a first mode of operation to a second mode. For example, switching the reactor 20 of the polyamine synthesis system from the first mode of operation to the second mode can include shutting off the outlet valve 66 of the reactor 20. Additionally, switching the reactor 20 of the polyamine synthesis system from the first mode of operation to the second mode can include directing the partially polymerized polyamine mixture stream to a reservoir other than the flasher 30. In one example, if reactor 20 is a baffle reactor, switching the reactor 20 of the polyamine synthesis system from the first mode of operation to the second mode includes reducing the concentration of the partially polymerized mixture within reactor 20. The concentration can be lowered by opening the water inlet valve 70 and introducing water from the water source 68 to the reactor 20.

As described herein, the gel time is counted down to the time when the material in the device gels. When the gel time expires, the device cannot switch from the second mode of operation to the first mode of operation without performing burnout to remove the gel. The method 100 can include switching the flasher feed pump 38, the transfer line pump 46, and the finisher pump 44 from the second mode of operation to the first mode of operation prior to expiration of the gel time. In the case of the method 100, the method 100 can include deactivating the gel time control unit 54. When the gel time expires, the method 100 can include shutting down the entire process, such as when the second mode is the idle mode, and burns out the entire back end process, including, for example, the flasher 30, the finisher 36, and the transfer line 40.

FIG. 5 is a flow diagram of an example system 200 for making polyamines, and in particular for making nylon 6,6. System 200 can include a reservoir 202. The reservoir 202 can contain a dicarboxylic acid, a diamine, and an aqueous solution of a solvent (e.g., water) in a liquid or substantially liquid phase. Dicarboxylic acid and diamine An ammonium carboxylate salt is formed. In one example, if system 200 is configured for nylon 6,6, then reservoir 202 can include a hexamethylene diammonium adipate salt that is soluble in the water in reservoir 202. The reservoir 202 can be used to mix or store an aqueous solution of an ammonium carboxylate salt.

In one example, the dicarboxylic acid and diamine can be added to the reservoir 202 at substantially equal molar ratios. The resulting ammonium carboxylate salt solution may have a pH of about 7.5, such as from about 7.4 to about 7.6. Each molecule of the ammonium carboxylate salt may include a diamine molecule and a dicarboxylic acid molecule. The aqueous solution in reservoir 202 can be heated with a preheater or vapor, such as a vapor formed in another portion of system 200.

A solution comprising a dicarboxylic acid and a diamine (e.g., an aqueous solution of an ammonium carboxylate salt) can be transferred from the reservoir 202 to the evaporator 208 via line 204. The evaporator 208 can be configured to convert a portion of the water in the aqueous solution from a substantially liquid phase to a substantially gaseous phase in the form of a water vapor stream 206. In one example, the evaporator 208 is heated by heating the aqueous solution to a temperature of from about 100 ° C to about 230 ° C, such as from about 100 ° C to about 150 ° C, such as about 110 ° C, about 120 ° C, about 130 ° C, about 140 ° C, about 150. The water vapor stream 206 is formed at a temperature of °C, about 160 °C, about 170 °C, about 180 °C, about 190 °C, about 200 °C, about 210 °C, about 220 °C, or about 230 °C. The evaporator 208 can increase the concentration of the ammonium carboxylate solution. In one example, the concentration of the ammonium carboxylate solution leaving the reservoir 202 and fed to the evaporator 208 is from about 40% to about 80% by weight salt in water or from about 52% to about 65% by weight in water. , such as about 63% by weight of salt. Evaporator 208 can increase the concentration of the ammonium carboxylate solution to, for example, about 72% by weight salt in water.

Removal of water by evaporation of evaporator 208 may also react at least a portion of the dicarboxylic acid and diamine present in the solution to form a polyamido prepolymer which may comprise a relatively short polymer chain of dicarboxylic acid and diamine. . In other words, removal of water can initiate a condensation reaction between the dicarboxylic acid and the diamine to form an oligomer, which can be the first stage of the final polyamine chain. The evaporator 208 can be reduced, for example, by a water concentration of the solution produced by the evaporator 208 to, for example, from about 5% by weight to about 50% by weight water, such as from about 25% by weight to about 35% by weight water, such as about 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 The aqueous solution is concentrated by a water concentration of %, about 32% by weight, about 33% by weight, about 34% by weight or about 35% by weight of water.

An aqueous mixture comprising water, unreacted dicarboxylic acid, and a diamine (e.g., in the form of an unreacted ammonium carboxylate salt and, if present, a polyamidamine prepolymer) can be transferred from evaporator 208 to reactor 212 via line 210. In the example illustrated in Figure 5, reactor 212 is an autoclave. In reactor 212, the unreacted dicarboxylic acid and diamine can be reacted with each other, or with a polyamidoprepolymer, or both to form a polyamidamine product. Reactor 212 can provide for further removal of water such that the polyamide precursor is subjected to further polymerization to form a final polyamine polymer having a final desired molecular weight or molecular weight range. Water may exit the reactor via line 214, which may optionally be connected to the rectification column. The final desired molecular weight or molecular weight range selected may depend on the final desired properties of the polyamine product.

Reactor 212 produces a final polyamine polymer having a water concentration of from about 0.0001% to about 20% by weight water, such as from about 0.001% to about 15% by weight water, such as from about 0.01% to about 15% by weight water. , for example, 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% by weight, and 2% by weight 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 % by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, or about 20% by weight water.

The final polyamine polymer can exit reactor 212 via transfer line 216. Transfer line 216 can be fed to final processing system 228 where the final polyamine polymer can be further machined, such as one or more of spinning, extrusion, and granulation.

System 200 can also include an inductor 230 coupled to gel time control unit 218. The gel time control unit 218 can determine the number of gels in a single batch and the number of gels in a continuous batch. single Both the batch gel number and the continuous batch gel number can be based on at least one of the temperature of the reactor 212 being above the threshold temperature. In an example, the sensor 230 can include a temperature sensor or other component configured to provide parameters for the gel time control unit 218 to determine the number of gels per individual and the number of consecutive gels.

In the example shown in FIG. 2, gel time control unit 218 includes processor 220, memory 222, interface 224, and notification 226. Gel time control unit 218 and sensor 230 may form or may be part of one or more computers. Memory 222, interface 224, sensor 230, and notification 226 are in communication with processor 220 as illustrated in the examples. Processor 220 can be configured to execute instructions for estimating the number of individual batch gels and the number of consecutive gels.

The number of gels in a single batch is related to each batch in reactor 212 (e.g., autoclave). In one example, during each batch process, when the temperature in reactor 212 is greater than 265 °C, the number of gels per batch remains increased. In one example, when the temperature of reactor 212 is greater than a threshold temperature (eg, 265 °C), the number of gels in a single batch begins at zero and ends in an equivalent minute. After the subsequent batch is introduced from the evaporator 208, the individual batch gel number is reset to zero. The individual batch gel numbers for each batch of the polyamine product can be stored in memory 222 and plotted via interface 224. The individual batch gel number can identify when a particular batch within the reactor 212 has been degraded higher than the other batches. The identification of when a particular batch has a higher degradation (eg, the higher the number of gels per batch, the higher the degradation) can identify operational issues that can be investigated before reactor 212 fails or produces low quality products. For example, a particular reactor 212 may have problems that cause high degradation (eg, an error set point).

The number of continuous gels is related to reactor 212 and continues to accumulate until reactor 212 is overhauled. In one example, when the temperature of the reactor is greater than the threshold temperature (e.g., 265 ° C), the number of consecutive gels starts at zero and ends in an equivalent minute. When the temperature of the reactor 212 is greater than 265 ° C, the number of consecutive gels of the plurality of batches continues to increase. That is, the number of continuous gels of each batch continues to increase until reactor 212 is removed from manufacture and cleaned to remove gel formation. The number of continuous gels provides the amount of time for a particular reactor (eg, reactor 212) to be close to overhaul. News. In one example, reactor 212 will require servicing when the number of consecutive gels reaches a maximum or exceeds the threshold for continuous gelation. The gel time control unit 218 can compare the continuous gel number to the continuous gel number maximum. The gel time control unit 218 can display the notification 226 via the interface 224 when the number of consecutive gels is greater than the number of consecutive gels. The notification 226 can signal an alarm condition or provide a notification or a specific detection condition.

Memory 222 provides instructions relating to gel time and storage of data. Interface 224 may include a keyboard, trackpad, screen, printer, network interface, or configured to allow a user to observe and monitor the countdown gel time (eg, 19:00:00, 18:59:59) , 18:59:58, etc.) or control the heat transfer medium at flasher 30, the heat transfer medium at finisher 36, or other components of the temperature of the heat transfer medium at transfer line 40.

Figure 6 illustrates a method 300 of monitoring gel formation in a polyamine synthesis system, according to one example. At step 302, method 300 includes feeding a first batch comprising one or more starting materials to the reactor. At 304, method 300 includes activating a gelation control unit configured to generate a first single batch gel number and a continuous batch gel number. As described herein, the first individual batch gel number and the continuous batch gel number are based on at least one of the reactor temperature being above the threshold temperature. At 306, method 300 includes converting one or more starting materials to a first polyamine product in a reactor. At 308, method 300 includes transferring the first polyamine product from the reactor. At 310, method 300 includes feeding a second batch comprising one or more starting materials to the reactor. At 312, the method can include initiating a gelation control unit configured to generate a second individual batch gel number and update a continuous batch gel number.

Instance General System of Example 1 to Example 2

In a continuous nylon 6,6 process, adipic acid and hexamethylenediamine are combined in water at approximately equal molar ratios to form an aqueous mixture containing nylon 6,6 salt and having about 50% by weight water. The brine solution was transferred to the evaporator at about 90 L/min. The evaporator heats the brine solution to about 125-135 ° C (130 ° C) and removes water from the heated brine solution to achieve a water concentration of Up to about 30% by weight. The evaporated salt mixture was transferred to a tubular reactor at about 75 L/min. The reactor raises the temperature of the evaporated salt mixture to about 218-250 ° C (235 ° C), allowing the reactor to further remove water from the heated evaporated salt mixture to a water concentration of about 10% by weight, and to make the salt Further polymerization. The reaction mixture was transferred to a flasher at about 60 L/min. The flasher heats the reaction mixture to about 270-290 ° C (280 ° C), further removes water from the reacted mixture to a water concentration of about 0.5% by weight, and further polymerizes the reaction mixture. The flasher includes a tube having a varying cross-sectional area that begins at a small area at the front end of the tube and at a pressure of about 2 MPa, and gradually expands to a larger cross-sectional area at the rear end and has a pressure of about 34 KPa. The flashed mixture having a relative viscosity of about 13 is transferred to the finishing machine at about 54 L/min, and the polymerization mixture is subjected to a vacuum to further remove water so that the water concentration reaches about 0.1% by weight and the relative viscosity reaches about 60, so that the The polydecylamine reached a range suitable for the final degree of polymerization before the finishing polymerization mixture was transferred to the extruder and granulator at about 54 L/min.

Example 1. Comparative example. Failure of the flasher pump without the gel time control unit.

The flasher feeds the pump fault. In response, the flasher feed pump, finisher pump, and transfer line pump are switched from active mode to idle mode. The flasher, finisher and transfer line temperatures were maintained at 285 ° C, the flasher was maintained at approximately 138 KPa, and the flasher feed pump was repaired for 33 hours. After the finishing machine pump repair is completed, the temperature and pressure of the flasher, the transfer line and the finishing machine are raised to prepare to switch the flasher feed pump, the finishing machine pump and the transfer line pump from the idle mode to the active mode. After the flasher feed pump, finisher pump, and transfer line pump are switched to active operating conditions; however, the flasher pump cannot pump material through the flasher.

During the idle mode, the flasher was subjected to 33 hours at 285 ° C and 138 KPa and the flasher was fully gelled. The system is placed in idle mode, the flasher pump and flasher are taken offline, and the flasher is burned out to remove the gel. After the burnout, the flasher pump and flasher are restarted and the flasher feed pump is capable of pumping material through the flasher. Separate the flasher and associated equipment It is expensive to perform the burnout and the manufacturing cost is increased.

Example 2. Failure of a flasher pump utilizing a gel time control unit in a system utilizing a baffle reactor.

The flasher feeds the pump fault. In response, the flasher feed pump, finisher pump, and transfer line pump were switched from active mode to idle mode, maintaining the temperature at 285 ° C and maintaining the flasher pressure at 138 KPa. In response to the flasher feed pump, the finisher pump, and the transfer line pump being switched to the idle mode, the gel time control unit is activated. In response to the initiation of the gel time control unit, a gel time is generated. The gel time is indicated as 6 hours. The baffle reactor was switched to the idle mode where the outlet of the reactor to the flasher was closed and about 500 L of water was introduced into the baffle reactor to reduce the polyamine concentration. The material temperature in the flasher, finisher and transfer line is communicated to the gel time control unit and the gel time is continuously updated based on the current temperature of 285 °C. It is estimated that the repair of the flasher feed pump will take 30-35 hours of work. The 6 hour estimated gel time indicated by the gel time control unit shows the operator the conditions necessary to change the idle mode to prevent wasted time and expensive gelation events in the flasher and other components of the system. The temperature of the flasher, finisher and transfer line was lowered to 240 ° C (via adjusting the temperature and pressure of the heat transfer medium). The gel time control unit indicates a gel time of 40 hours. Repair work was performed on the flasher feed pump for 33 hours.

Complete the flasher feed pump repair before the gel time expires. Material temperature adjustment (heat transfer medium temperature and pressure) in the flasher, transfer line and finishing machine to standard operating conditions, in preparation for switching the flasher feed pump, finishing pump and transfer line pump from idle mode to Activity mode. Open the reactor outlet. After the flasher feed pump, finisher pump, and transfer line pump are switched to active mode, material is pumped through the system.

Compared to Example 1, no gelation event occurred. The gel time control unit provides a warning indicating that gelation will occur during the estimated repair time of the flasher pump, resulting in adjustment of idle conditions in the system.

General System of Example 3 and Example 4

In the batch nylon 6,6 process, adipic acid and hexamethylenediamine are combined in water at approximately equal molar ratios to form an aqueous mixture containing nylon 6,6 salt and having about 50% by weight water. The brine solution was transferred to the evaporator at about 90 L/min. The evaporator heats the brine solution to about 125-135 ° C (130 ° C) and removes water from the heated brine solution to a water concentration of about 30% by weight. The evaporated salt mixture was transferred to an autoclave at about 75 L/min such that about 10,000 L of the autoclaved mixture was filled with the evaporated salt mixture. The autoclave heats the material to 270-290 ° C (280 ° C) to a water concentration of about 0.1% by weight and a relative viscosity of about 60, so that the finishing polymerization mixture is transferred to the extruder and granulation at about 60 L/min. Polyamines are suitable for the final degree of polymerization before the machine. After the polyamine product was extruded from the autoclave, the temperature in the autoclave was lowered to 160 °C. Another evaporated salt solution from the evaporator was passed to the autoclave and the autoclave cycle was started again.

Example 3. Comparative example. Failure of the autoclave failure of the gel time control unit.

After a plurality of batches, the autoclave unexpectedly failed due to the accumulation of gel in the autoclave. In response to autoclave failure, the autoclave was removed from manufacturing and overhauled, where all surfaces were cleaned and gel formation removed.

Example 4. Autoclave failure including gel time control unit.

After a number of batches, the individual batch gel number indicates that the autoclave set point is 285 ° C, which is 5 ° C higher than the past performance. The set point was readjusted to 280 ° C and the individual batches of gel in the autoclave were monitored. After a number of batches, the number of continuous gels received into the autoclave has increased to exceed the continuous gel number threshold (over 260 ° C, over 10,000 hours of operation), indicating that the autoclave may be malfunctioning and in the next five Overhaul is required in ten batches. The plan is closed on a regular basis, minimizing time, money and product losses. After the autoclave is overhauled, the continuous gel number is set to zero.

The presently described examples of the present invention are not limited to the specific examples disclosed herein, as such examples are intended to be illustrative of several aspects of the present invention. Any equivalent examples are intended to be within the scope of this creation. In fact, those who are familiar with this technology will Numerous modifications to the examples in addition to the examples shown and described herein are readily apparent. Such amendments are also intended to be within the scope of the accompanying patent application.

All publications referred to in this specification include non-patent literature (e.g., scientific journal literature), patent application publications, and patents, which are hereby incorporated by reference in their entirety as if individually and individually The way to incorporate the same.

Additional statement.

The present disclosure provides the following statement, the numbering of which is not to be construed as indicating the level of importance: Embodiment 1 may include subject matter (such as a device, device, method, or one or more means for performing an action), such as may be included in polyamine synthesis A method of monitoring gel formation in the system. The method can include directing a partially polymerized polyamine mixture through a flasher feed pump, a finishing pump, and a transfer line pump, feeding the flasher to a pump, the finishing pump, and the transfer line pump from a first operation Switching the mode to the second mode of operation, activating a gel time control unit configured to estimate a gel time of at least one of the flasher, the finisher, and the transfer line, wherein the gel time is based on the flasher And at least one temperature of the partially polymerized polyamine mixture in at least one of the finishing machine and the transfer line and a parameter related to a time when the temperature is greater than a threshold temperature, and reacting the polyamine synthesis system The device switches from the first reactor mode of operation to the second reactor mode of operation.

Embodiment 2 may include or be combined with the subject matter of Example 1 as appropriate, including where the gel time control unit includes a graphical interface, the method further comprising displaying the gel time via the graphical interface.

Embodiment 3 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 and 2, optionally including comparing at least one gel time value to a threshold value.

Embodiment 4 may include or may be combined with the subject matter of one or any combination of Embodiments 1 through 3, as appropriate, including generating an alert based on the comparison.

Embodiment 5 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 3, optionally including where the gel time control unit determines the flasher gelation Time, gelling time of the finishing machine and gelling time of the transfer line.

Embodiment 6 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 5, optionally including wherein the flasher gel time is based on at least one temperature of the heat transfer medium at the flasher Determination.

Embodiment 7 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 6, including optionally wherein the transfer line gel time is based on at least one temperature of the heat transfer medium at the transfer line Determination.

Embodiment 8 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 7 to optionally include wherein the finishing machine gel time is based on at least the heat transfer medium at the finishing machine A temperature measurement.

Embodiment 9 may include or optionally combine with the subject matter of one or any combination of Embodiments 1-8, optionally including receiving the flasher, the finishing machine, and the transfer at the gel time control unit At least one thermal transfer medium parameter of at least one of the pipelines, and each of the flasher gel time, the finisher gel time, and the transfer line gel time is updated in response to receiving the at least one parameter.

Embodiment 10 may include or optionally combine with the subject matter of one or any combination of embodiments 1 to 9 to optionally include wherein the first mode of operation and the first reactor mode of operation are active modes and the The second mode of operation and the second reactor mode of operation are idle modes.

Embodiment 11 may include or optionally combine with one or any combination of the embodiments 1 to 10 to optionally feed the flasher into the pump, the finishing pump, and the transfer line pump. Switching from the first mode of operation to the second mode of operation includes reducing the flow rate of the partially polymerized polyamine mixture through the flasher feed pump, the finisher pump, and the transfer line pump to less than 1 L/min .

Embodiment 12 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 11 to optionally feed the flasher into the pump, the finishing machine pump, and Switching the transfer line pump from the first mode of operation to the second mode of operation includes reducing the flow rate of the partially polymerized polyamine mixture through the flasher feed pump, the finisher pump, and the transfer line pump to 0L/min.

Embodiment 13 can include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 12, optionally including wherein the reactor is switched from the first reactor mode of operation to the second reactor The mode of operation includes closing the outlet valve of the reactor.

Embodiment 14 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 13 to optionally include wherein the reactor is switched from the first reactor mode of operation to the second reactor The mode of operation includes directing an output stream of the partially polymerized polyamine mixture from the reactor to a reservoir.

Embodiment 15 may include or optionally combine with the subject matter of one or any combination of Examples 1 to 14 to optionally include wherein the reactor is a baffle reactor and the reactor is from the first reactor Switching the mode of operation to the second reactor mode of operation includes reducing the concentration of the partially polymerized polyamine mixture in the reactor.

Embodiment 16 may comprise or optionally combine with one or any combination of the embodiments 1 to 15 to optionally include wherein the concentration of the partially polymerized polyamine mixture is reduced to include introduction into the reactor Demineralized water.

Embodiment 17 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 16 to optionally include feeding the flasher to the pump, the transfer line pump, and the finishing machine pump The first operation mode is switched to detect the event before the second operation mode.

Embodiment 18 may include or may be combined with the subject matter of one or any combination of Embodiments 1 to 17, optionally including wherein detecting the event includes detecting a flasher feed pump failure, a finisher pump failure At least one of a transfer line pump failure, a power interruption, and combinations thereof.

Embodiment 19 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 18, optionally including feeding the flasher before the gel time expires The intake pump, the transfer line pump, and the finishing machine pump are switched from the second mode of operation to the second mode of operation.

Embodiment 20 may include or may be combined with the subject matter of one or any combination of embodiments 1 through 19, as appropriate, including when the flasher feed pump, the transfer line pump, and the finishing machine pump When the second operation mode is switched to the second operation mode, the gel time control unit is activated.

Embodiment 21 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 19, optionally including burning the flasher, the finisher, and the time when the gel time has elapsed Transfer pipeline.

Embodiment 22 may comprise or optionally combine with the subject matter of one or any combination of Examples 1 to 21, optionally including wherein the gel time is the time prior to gel formation in the polyamide synthesis system .

Embodiment 23 may comprise or optionally combine with the subject matter of one or any combination of Examples 1 to 22, optionally including wherein the polyamine synthesis system is comprised of or consists of a linear dicarboxylic acid and a linear diamine Polyamines are synthesized from oligomers of linear dicarboxylic acids and linear diamines.

Embodiment 24 may include or be combined with the subject matter of one or any combination of Embodiments 1 to 35, as appropriate, to include the subject matter (such as a device, device, method, or one or more means for performing an action), such as Systems for monitoring gel formation in the manufacture of polyamine products can be included. The system can include a polymerization reactor configured to react one or more starting materials to form a polyamine; a downstream processing system downstream of the polymerization reactor, the subsequent processing system configured to increase the polyamine a molecular weight forming the polyamine product; and a gelation time control unit operatively coupled to the back end process system and configured to estimate a gel time of the back end process system, the back end process system being first The mode of operation is switched to a second mode of operation, wherein the gel time is based on a parameter relating to at least one temperature of the polyamine in the back-end process and a time at which the temperature is greater than the threshold temperature.

Embodiment 25 may include or may be combined with one or any combination of embodiments 1 to 24 as appropriate The subject matter combination includes, where appropriate, the gel time control unit including a processor coupled to the memory, wherein the processor is configured to execute instructions stored in the memory.

Embodiment 26 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 25, as the case may be, where the gel time control unit includes a graphical interface configured to display gel time.

Embodiment 27 can include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 26, as the case may be, wherein the gel time control unit includes configured to have a gel time value below The alarm that is activated when the limit is reached.

Embodiment 28 can include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 27, optionally including a preheater and evaporator positioned upstream of the polymerization reactor.

Embodiment 29 can include or optionally combine with one or any combination of the embodiments 1 to 28, including wherever the polymerization reactor includes an autoclave, the outlet valve being configured to be in the subsequent stage of the process The system is turned off in this second mode of operation.

Embodiment 30 can include or optionally be combined with the subject matter of one or any combination of Embodiments 1 through 29, as the case may be, where the polymerization reactor includes a baffle reactor.

Embodiment 31 may include or optionally combine with the subject matter of one or any combination of embodiments 1 to 30, including where the polymerization reactor is coupled to an inlet line, the inlet line being coupled to the positioning An evaporator upstream of the polymerization reactor, wherein the inlet line includes a water inlet port.

Embodiment 32 may include or be combined with the subject matter of one or any combination of Embodiments 1 through 31, as the case may be, where the first mode of operation is an active mode and the second mode of operation is an idle mode.

Embodiment 33 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 32, including, where appropriate, the flow of the polyamide when the back-end processing system is in the second mode of operation The rate is less than 1 L/s.

Embodiment 34 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 33, including where appropriate, wherein the back end process system includes: a flasher positioned downstream of the polymerization reactor, wherein exiting The polyamine of the flasher has a water percentage of about 1% by weight; a finishing machine positioned downstream of the flasher, wherein the percentage of water leaving the polyamine of the finishing machine is about 0.1% by weight; Downstream of the finishing machine, the polyamine product is transferred from the finishing machine to a transfer line of an extruder, the extruder being configured to extrude the polyamine product to form one or more polyamines Strands.

Embodiment 35 may include, or may be combined with, the subject matter of one or any combination of embodiments 1 to 34, as the case may be, where the rear stage process system includes: a flasher feed pump coupled to the flasher, A finishing machine pump coupled to the finishing machine and a transfer line pump coupled to the transfer line.

Embodiment 36 can include or optionally combine with the subject matter of one or any combination of Embodiments 1 through 35, including wherever the flasher includes a flasher operatively coupled to the gel time control unit Temperature sensor.

Embodiment 37 can include or optionally combine with one or any combination of the embodiments 1 to 36, including optionally wherein the finishing machine includes an operatively operatively coupled to the gel time control unit The whole machine temperature sensor.

Embodiment 38 may include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 37, including where the transfer line includes a transfer line operatively coupled to the gel time control unit, as appropriate Temperature sensor.

Embodiment 39 can include or optionally combine with the subject matter of one or any combination of Embodiments 1 to 38, optionally including wherein the polymerization reactor is configured to receive the one or more starting materials, the one Or a plurality of starting materials include linear dicarboxylic acids and linear diamines or oligomers formed from linear dicarboxylic acids and linear diamines.

Embodiment 40 can include or optionally combine with one or any combination of the embodiments 1 to 39, optionally including wherein the polymerization reactor is configured to receive the one or A plurality of starting materials, the one or more starting materials comprising a mixture of adipic acid and hexamethylenediamine or an oligomer formed from a mixture of adipic acid and hexamethylenediamine.

Embodiment 41 may comprise or optionally combine with the subject matter of one or any combination of embodiments 1 to 40, optionally including polymerizing one or more monomers, including converting one or more monomers to a first polyfluorene. amine.

Embodiment 42 may include or be combined with the subject matter of one or any combination of embodiments 1 to 35, as appropriate, to include the subject matter (such as a device, device, method, or one or more means for performing an action), such as The method of gel formation is monitored in a polyamine synthesis system. The method includes feeding a first batch comprising one or more starting materials to a reactor, and initiating a gelation control unit configured to produce a first individual batch gel number and a continuous batch gel number, wherein The first individual batch gel number and the continuous batch gel number are based on the reactor temperature being at least one time above a threshold temperature, wherein the one or more starting materials are converted to the first a polyamine product, transferring the first polyamine product from the reactor, feeding a second batch comprising the one or more starting materials to the reactor, and initiating a gelation control unit configured To generate a second individual batch of gel number and update the continuous batch gel number.

20‧‧‧Reactor

22‧‧‧ Pipes

26‧‧‧ Pipes

30‧‧‧Flasher

32‧‧‧ Pipes

34‧‧‧Export pipeline

36‧‧‧ Finishing machine

38‧‧‧Flasher feed pump

40‧‧‧Transfer pipeline

42‧‧‧Final processing system

44‧‧‧ Finishing machine pump

46‧‧‧Transfer line pump

50‧‧‧ part of the system

52A‧‧‧ sensor

52B‧‧‧ sensor

52C‧‧‧ sensor

54A‧‧‧gel time control unit

54B‧‧‧gel time control unit

54C‧‧‧gel time control unit

56A‧‧‧ processor

56B‧‧‧ processor

56C‧‧‧ processor

58A‧‧‧ memory

58B‧‧‧ memory

58C‧‧‧ memory

60A‧‧ interface

60B‧‧ interface

60C‧‧ interface

62A‧‧‧Announcer

62B‧‧‧Announcer

62C‧‧‧Announcer

64A‧‧‧ channel

64B‧‧‧ channel

64C‧‧‧ channel

66‧‧‧Export valve

68‧‧‧Water source

70‧‧‧Water inlet valve

72‧‧‧ Pipes

Claims (17)

A system for monitoring gel formation in the manufacture of a polyamidamine product, the system comprising: a polymerization reactor configured to react one or more starting materials to form a polyamine; after downstream of the polymerization reactor a stage process system configured to increase the molecular weight of the polyamide to form the polyamide product; and a gel time control unit operatively coupled to the back end process system and configured to Estimating the gel time of the back-end process system, wherein the back-end process system is switched from the first mode of operation to the second mode of operation, wherein the gel time is based on at least one temperature and the temperature of the polyamide in the back-end process Time-related parameters greater than the threshold temperature. The system of claim 1, wherein the gel time control unit comprises a processor coupled to the memory, wherein the processor is configured to execute instructions stored in the memory. A system as claimed in claim 1, wherein the gel time control unit comprises a graphical interface configured to display the gel time. The system of claim 1, wherein the gel time control unit includes an alarm configured to initiate when the gel time value is below a threshold. The system of claim 1 further comprising a preheater and an evaporator positioned upstream of the polymerization reactor. The system of claim 1, wherein the polymerization reactor includes an outlet valve configured to close when the rear stage process system is in the second mode of operation. The system of claim 1 wherein the polymerization reactor comprises a baffle reactor. The system of claim 1, wherein the polymerization reactor is coupled to an inlet line, the inlet The port line is coupled to an evaporator positioned upstream of the polymerization reactor, wherein the inlet line includes a water inlet port. The system of claim 1, wherein the first mode of operation is an active mode and the second mode of operation is an idle mode. The system of claim 1, wherein the polyamine has a flow rate of less than 1 L/s when the back-end process system is in the second mode of operation. The system of claim 1, wherein the back-end processing system comprises: a flasher positioned downstream of the polymerization reactor, wherein the polyamine has a percentage of water leaving the flasher of 1% by weight; positioned downstream of the flasher a finishing machine, wherein the percentage of water leaving the polyamine of the finishing machine is 0.1% by weight; and a transfer positioned downstream of the finishing machine to transfer the polyamidamine product from the finishing machine to the extruder A line that is configured to extrude the polyamine product to form one or more polyamine strands. The system of claim 11, wherein the rear stage processing system comprises: a flasher feed pump coupled to the flasher; a finishing machine pump coupled to the finishing machine; and a transfer line pump coupled To the transfer line. The system of claim 12, wherein the flasher comprises a flasher temperature sensor operatively coupled to the gel time control unit. The system of claim 12, wherein the finishing machine comprises a finisher temperature sensor operatively coupled to the gel time control unit. The system of claim 12, wherein the transfer line includes a transfer line temperature sensor operatively coupled to the gel time control unit. The system of claim 1, wherein the polymerization reactor is configured to receive the one or more starting materials, the one or more starting materials comprising a linear dicarboxylic acid and a linear diamine Or an oligomer formed from a linear dicarboxylic acid and a linear diamine. The system of claim 1, wherein the polymerization reactor is configured to receive the one or more starting materials, the one or more starting materials comprising a mixture of adipic acid and hexamethylenediamine or from adipic acid An oligomer formed with a mixture of hexamethylenediamine.