TWM499416U - Apparatus and systems for the recovery of water from a polyamide synthesis process - Google Patents

Abstract

The present disclosure relates to an apparatus and a system for recovering water from a condensation reaction of at least one carboxylic acid and at least one diamine to make polyamide. The apparatus and the system can include a tubular reactor configured to further polymerize a partially polymerized polyamide, thereby producing water having a substantially gaseous phase; a rectification column, in fluid communication with the tubular reactor, configured to remove one or more of a diamine, a carboxylic acid and polyamide to provide purified water having a substantially gaseous phase; a condensation assembly, in fluid communication with the rectification column, configured to receive the water having a substantially gaseous phase and transform the water having a substantially gaseous phase into water having a substantially liquid phase; and a conduit network configured to return the water having a substantially liquid phase to at least one component of a polyamide production system.

Description

Device and system for recovering water from polyamido synthesis process Cross-reference to related applications

The present application claims priority to U.S. Provisional Patent Application Serial No. 61/818,048, filed on

Polyamine is obtained by polymerizing a diamine (for example, hexamethylene-1,6-diamine) with a dicarboxylic acid (for example, adipic acid) under polycondensation conditions (for example, a temperature of from 180 ° C to 300 ° C). It is sometimes in the form of an aqueous solution of the ammonium carboxylate salt of the two components. The condensation reaction produces polyamines (e.g., nylon 6,6) and water as a by-product. Water by-products are produced at various stages in the polyamine synthesis process.

Polyamine synthesis processes sometimes involve the use of tubular reactors. The tubular reactors include vents disposed along the length of the reactor to allow water (in the form of water vapor) generated during the polyamide synthesis process to escape. After passing through the scrubber system, the vented water vapor is typically allowed to escape to the atmosphere or condense in the scrubber and pass to a wastewater treatment process.

Water treatment may have little or no jurisdictional consequences in jurisdictions where there is no limit to the amount of water that can be disposed of to the local sewage system or where the treatment of water to the sewage system is relatively inexpensive. However, there are jurisdictions that limit the amount of water that can be discarded and that there are significant cost consequences over the limits. In addition, there may be significant costs associated with the use of large amounts of demineralized water. Therefore, there is a current need for methods and systems for recovering water from polyamine production facilities, particularly in jurisdictions that impose significant cost consequences over water treatment constraints.

Discarding of water produced during the polyamine synthesis process is problematic when the water is in liquid form and can be recovered in purified form (eg, as a purified liquid) and in liquid form (eg, as a diamine/dicarboxylic acid solution) or as a gas (i.e., in vapor form, steam can be used to transfer heat to one or more components of the polyamide synthesis process), especially when reused in the process.

This creation is directed to systems and methods for solving the problem of recovering water from a tubular reactor used in a purified form from a polyamine synthesis process. The systems and methods described herein re-use purified water in liquid form recovered from a tubular reactor used in a polyamine synthesis process, or water in the form of a vapor produced in a tubular reactor used in a polyamide synthesis process, Transfer heat from one or more components of the vapor to the polyamido synthesis process.

10‧‧‧Reservoir

12‧‧‧ pipeline

14‧‧‧Valve

16‧‧‧ pipeline

18‧‧‧Evaporator

22‧‧‧ pipeline

24‧‧‧ valve

26‧‧‧Exhaust line

28‧‧‧ pipeline

30‧‧‧ valve

32‧‧‧ pipeline

34‧‧‧ tubular reactor

36‧‧‧ pipeline

38‧‧‧Valves

40‧‧‧ pipeline

42‧‧‧flasher

44‧‧‧ pipeline

46‧‧‧Valves

48‧‧‧ pipeline

50‧‧‧ Finishing machine

54‧‧‧ pipeline

56‧‧‧ valve

58‧‧‧ pipeline

62‧‧‧Exhaust port

64‧‧‧ pipeline

66‧‧‧Management

68‧‧‧ pipeline

70‧‧‧Reservoir

72‧‧‧ pipeline

74‧‧‧Exhaust line

76‧‧‧Valves

78‧‧‧ pipeline

80‧‧‧Rectifier

81‧‧‧Rectification zone

82‧‧‧Partial condenser-preheater

83‧‧‧Condenser

84‧‧‧ pipeline

86‧‧‧ valve

88‧‧‧ pipeline

90‧‧‧Filter or adsorption assembly

92‧‧‧ pipeline

94‧‧‧Valve

96‧‧‧ pipeline

98‧‧‧Unit/pipeline

100‧‧‧ storage container

T1‧‧‧Tray

T2‧‧‧Tray

T3‧‧‧Tray

T4‧‧‧Tray

T5‧‧‧Tray

T6‧‧‧Tray

T7‧‧‧Tray

T8‧‧‧Tray

In the drawings, like elements may be used in the various figures. The drawings are generally described by way of example, and not of limitation

Figure 1 is a schematic illustration of a system for making polyamine.

Figure 2 is a schematic view (top view) of a tubular reactor.

This creation describes a system and method for recovering water from the condensation reaction of at least one carboxylic acid from at least one diamine from the preparation of polyamine, comprising: obtaining an aqueous mixture from an evaporator comprising partially polymerized polyamine and carboxy At least one of an acid and a diamine; passing the aqueous mixture through a tubular reactor while subjecting the aqueous mixture to a temperature and pressure sufficient to further polymerize the partially polymerized polyamine by condensation of the carboxylic acid with a diamine. This produces water having a substantially gaseous phase; passing the substantially gaseous phase water to the rectification column, thereby removing one or more of the diamine, carboxylic acid, and polyamine to provide substantial gas Purifying the water; and condensing the purified water having a substantially gaseous phase into purified water having a substantially liquid phase.

Referring to Figure 1, the reservoir 10 (sometimes referred to as a "salt trigger") may contain a dicarboxyl group. An acid, a diamine, and an aqueous solution having substantially liquid phase water. In some examples, the dicarboxylic acid and the diamine form a salt of a diamine and a dicarboxylic acid, such as an ammonium salt or a diammonium salt, which is soluble in the reservoir 10 having water. The reservoir 10 can be used to mix or store aqueous solutions. The type of reservoir encompassed by the reservoir 10 is not limited and can be any suitable reservoir.

In one example, the aqueous solution can be passed to line 18 via line 12, valve 14 and line 16, wherein a portion of the water having a substantially liquid phase can be utilized (e.g., by a temperature of from about 100 ° C to about 300 ° C) The lower heating) is converted into water having a substantially gaseous phase to concentrate the aqueous solution.

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 "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.

In the evaporator 18, the dicarboxylic acid can be concentrated by converting a portion of the water having a substantially liquid phase (for example, by heating at a temperature of from about 100 ° C to about 300 ° C) to water having a substantially gaseous phase. An aqueous solution of an acid and a diamine. In evaporator 18, the dicarboxylic acid and diamine may also be partially reacted to form an aqueous mixture comprising a polyamidamine prepolymer (e.g., a polyamine which is not substantially fully polymerized).

In some cases, the exhaust line 26 can receive at least some of the water having a substantially gaseous phase transferred by the line 22 and the valve 24. The vent line 26 can be in fluid communication with a scrubber system (not shown) or a suitable condenser (not shown) that can convert water having a substantially gaseous phase into water having a substantially liquid phase. A portion of the water having a substantially liquid phase can be transferred to a storage vessel (not shown) for use, for example, in a sewage system (not shown) that is subsequently used or discarded to the polyamine production facility. In one embodiment, a portion of the water having a substantially liquid phase can be transferred to a storage container (not shown) for subsequent use, for example, a portion of the sewage system (not shown) that can be disposed of to the polyamine production facility; It can be reused (e.g., reused in reservoir 10 or tubular reactor 34). Reuse in a tubular reactor can include reuse in the form of a vapor, such as for a heat exchanger.

As used herein, the term "polyamido prepolymer" generally refers to unreacted dicarboxylic acid and diamine; polyamines (eg, oligomers) that are not substantially fully polymerized; and unreacted dicarboxylic acids and A mixture of amines and a polyamine (eg, an oligomer) that is not substantially fully polymerized. The polyamido prepolymer may consist essentially or entirely of a diamine/diacid salt or may consist essentially or entirely of polyamine, and need not include any substantial portion or any of the diacids and diamines in pure form.

The aqueous mixture comprising the polyamidene prepolymer can be transferred via line 28, valve 30 and line 32 to tubular reactor 34 (side view shown in Figure 1 and top view shown in Figure 2), wherein unreacted two The carboxylic acid and diamine can be further reacted to form an additional polyamidamine prepolymer.

In various examples, the reactor can heat the reaction mixture and evaporate water therefrom, further pushing the equilibrium toward the polyamine product. The reaction mixture can be heated in the reactor to any suitable temperature, such as about 150-400 ° C, or about 250-350 ° C, or about 250-310 ° C, or about 200 ° C or less, or about 210 ° C, 220. 230, 240, 250, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 320, 330, 340 ° C, or about 350 ° C or more. The reaction mixture leaving the reactor and leading to the flasher can have any suitable weight percentage of water, such as from about 0.0001% to 20% by weight, from 0.001 to 15% by weight, or from about 0.01 to 15% by weight, or from about 0.0001% by weight or 0.0001% by weight or less, or about 0.001% by weight, 0.01% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 3%, 4 % by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight 17% by weight, 18% by weight, 19% by weight, or about 20% by weight or more.

Referring to Figure 2, tubular reactor 34 can be any suitable tubular reactor that can be used to further polymerize unreacted dicarboxylic acid, diamine, and polyamidamine prepolymer to form additional polyamidamine prepolymer. The tubular reactor 34 can have any suitable shape and design. The tubular reactor 34 can include a cylindrical tube having a jacket disposed outside the cylindrical tube.

The tubular reactor 34 can have any suitable length, such as the length between the inlet and the outlet along a straight section or a curved section. The tubular reactor 34 can have from about 50 to about 300 m, from about 75 to about 125 m, or from about 90 to about 110 m, or from about 50 m or less, or from about 60 m, 70 m, 80 m, 85 m, 90 m, 95 m, 100 m, 105 m, 110m, 115m, 120m, 130m, 140m, 150m, 160m, 170m, 180m, 190m, 200m, 225m, 250m, 275m, or a length of about 300m or more.

The tubular reactor 34 can have any suitable inner diameter, such as a straight section and a curved section. The inner diameter of one end of the reactor to the other end may vary, or the inner diameter may be constant. For example, the inner diameter can extend from the tubular reactor inlet end to the tubular reactor exit end. The tubular reactor 34 can have from about 10 cm to 80 cm, or from about 25 cm to about 60 cm, or from about 35 cm to 50 cm, or from about 10 cm or less, or from about 15 cm, 20 cm, 25 cm, 30 cm, 35 cm, 36 cm, 37 cm, 38 cm, 39 cm. An inner diameter of 40 cm, 41 cm, 42 cm, 43 cm, 44 cm, 45 cm, 46 cm, 47 cm, 48 cm, 49 cm, 50 cm, 55 cm, 60 cm, 65 cm, 70 cm, 75 cm, or about 80 cm or more. If the tubular reactor 34 includes a jacket, the jacket may have any suitable outer diameter, in some cases consistent with the outer diameter of the tubular reactor 34, such as about 1-50 cm above the inner diameter, or about 1 inner diameter. Up to 25 cm, or about 1 cm or less, or more than about 2 cm, 4 cm, 6 cm, 8 cm, 10 cm, 12 cm, 14 cm, 16 cm, 18 cm, 20 cm, 22 cm, 24 cm, 26 cm, 28 cm, 30 cm, 32 cm, 34 cm, 36 cm. 38 cm, 40 cm, 42 cm, 44 cm, 46 cm, 48 cm or about 50 cm or more.

The tubular reactor can have a constant inner diameter, or the diameter can extend from the entry end to the exit end of the reactor, such as linear expansion or non-linear expansion. The diameter can be sufficiently expanded such that as the reactor is used, a substantially constant pressure is maintained from the inlet end to the exit end of the reactor. The diameter is expandable such that as the reactor is used, the pressure decreases from the entry end to the exit end. The expansion rate of the tubular reactor is sufficient, the amount of heat applied to the reaction mixture, the amount of water removed from the reaction mixture by evaporation and venting, and the pressure of the reaction mixture at a predetermined location along the length help to maintain the reaction mixture leaving the reactor. The end flows and reduces or minimizes the build up or accumulation of gel or other impurities. The inner diameter of the reactor may extend about 2.5 cm per length from about 6.25 m to about 750 m, may extend about 2.5 cm per length from about 22.5 m to about 550 m, may extend about 2.5 cm per length from about 22.5 m to about 110 m, or about about every cm. 6m or less in length, or about 8m, 10m, 15m, 20m, 25m, 30m, 35m, 40m, 45m, 50m, 55m, 60m, 65m, 70m, 75m, 80m, 85m, 90 m, 95, 100, 105, 110, 120, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 550, 550, 650m, 700m or about 750m in length can be extended by about 2.5cm.

The tubular reactor 34 can have any suitable length/inner diameter (L/ID, such as the length of the tubular reactor divided by the inner diameter). For example, the L/ID of the tubular reactor 34 can be from about 50 to 2500, or from about 100 to 500, or from about 230 to 270, or from about 50 or less, or from about 75, 100, 125, 150, 175, 200, 210, 220, 230, 235, 240, 245, 250, 255, 260, 265, 270, 280, 290, 300, 400, 500, 600, 700, 800, 900, 1000, 1250, 1500, 1750, 2000, 2250, or about 2500 or more.

Referring to Figures 1 and 2, the tubular reactor 34 includes one or more exhaust ports 62 along its length. The tubular reactor 34 can include any suitable number and type of vents 62 such that vapor can be released from the vent 62. The tubular reactor 34 can include any suitable number of vents 62 along its length. For example, the tubular reactor 34 can have from about 5 to 50 exhaust ports 62 along its length, or about 10 to 25 exhaust ports 62 along its length, or about 5 or less exhaust ports 62, Or about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, about 45 rows Port 62, or about 50 or more exhaust ports 62.

Exhaust port 62 may be present in tubular reactor 34 at any suitable distance from adjacent exhaust ports 62. For example, tubular reactor 34 may have an average of from about 2 m to about 15 m per tubular reactor 34, from about 3 m to about 9 m, or about 1 row per about 5 to about 8 m along the length of tubular reactor 34. The gas port 62, or about every 2 m or less, or about 3 m, 4 m, 5 m, 6 m, 7 m, 8 m, 9 m, 10 m, 11 m, 12 m, 13 m, 14 m or about 15 m or 15 m along the length of the tubular reactor 34. About one exhaust port 62 above.

The tubular reactor 34 may have any suitable amount of flat between the exhaust ports 62 along its length. With an average spacing, for example, the vents 62 may be spaced from about 2 m to about 15 m, from about 3 m to about 9 m, along the length of the tubular reactor 34, or may be equally spaced from about 5 to about 8 m along the length of the tubular reactor 34, Or along the length of the tubular reactor 34, the average interval is about 2m or less, or an average of about 3m, 4m, 5m, 6m, 7m, 8m, 9m, 10m, 11m, 12m, 13m, 14m, or an average of about 15m or more. .

The number and distribution of the vents 62 of the tubular reactor 34 may be such that the velocity of the substantially gaseous phase water within the tubular reactor 34 does not exceed any suitable maximum. For example, the number and distribution of vents 62 may be sufficient such that the vapor velocity in tubular reactor 34 does not exceed about 0.5 m/s to about 400 m/s, 1-200 m/s, 2-100 m/s, 4- 50 m/s, or about 0.5 m/s or less, or about 1 m/s, 2 m/s, 3 m/s, 4 m/s, 5 m/s, 15 m/s, 10 m/s, 20 m/s 25m/s, 30m/s, 35m/s, 40m/s, 45m/s, 50m/s, 55m/s, 60m/s, 65m/s, 70m/s, 75m/s, 80m/s, 85m / s, 90 m / s, 95 m / s, 100 m / s, 125 m / s, 150 m / s, 175 m / s, 200 m / s, 250 m / s, 300 m / s, or about 400 m / s or more than 400 m / s.

The tubular reactor can have any suitable flow rate of polymeric material therethrough. For example, the flow rate can be from 1 L/min to about 1,000,000 L/min, or from about 10 L/min to about 100,000 L/min, or about 1 L/min or less, 10 L/min, 20 L/min, 30 L /min, 40L/min, 50L/min, 60L/min, 70L/min, 80L/min, 90L/min, 100L/min, 125L/min, 150L/min, 175L/min, 200L/min, 225L/min 250L/min, 275L/min, 300L/min, 350L/min, 400L/min, 450L/min, 500L/min, 600L/min, 700L/min, 800L/min, 900L/min, 1,000L/min, 2,500 L/min, 5,000 L/min, 10,000 L/min, 50,000 L/min, 100,000 L/min, 500,000 L/min, or about 1,000,000 L/min or 1,000,000 L/min or more. The polymerization system comprising a tubular reactor can produce a polymer at any suitable rate, such as from about 1 L/min to about 1,000,000 L/min, or from about 10 L/min to about 100,000 L/min, or about 1 L/min or less. 10 L/min, 20L/min, 30L/min, 40L/min, 50L/min, 60L/min, 70L/min, 80L/min, 90L/min, 100L/min, 125L/min, 150L/min, 175L/ Min, 200L/min, 225L/min, 250L/min, 275L/min, 300L/min, 350L/min, 400L/min, 450L/min, 500L/min, 600L/min, 700L/min, 800L/min, 900 L/min, 1,000 L/min, 2,500 L/min, 5,000 L/min, 10,000 L/min, 50,000 L/min, 100,000 L/min, 500,000 L/min, or about 1,000,000 L/min or 1,000,000 L/min the above.

The number and distribution of the vents 62 of the tubular reactor 34 can be such that the tubular reactor 34 has any suitable F factor. The exhaust port 62 can be connected to a suitable exhaust line. The method can include injecting water into the exhaust line. Water can be injected into each vent at any suitable rate.

The tubular reactor of the present invention can be operated for any suitable time between shutdown and cleaning to remove gel or other contaminants. For example, the method can be performed for at least about 1 to 7 years, 2 to 5 years, or about 2.3 to 3 years, or about 3 years, without shutting down the tubular reactor for cleaning.

The reaction mixture and vapor in the tubular reactor can have any suitable flow regime. For example, a tubular reactor can have primarily an annular flow (eg, most of the liquid is in contact with the interior of the reactor tube, while the gas and vapor travel primarily down the middle of the reactor tube). In some examples, the tubular reactor can have a plug flow (eg, a substantially continuous gas and vapor cylinder in a substantially continuous liquid cylindrical passage tube in the tube), and other flow regimes (eg, the liquid stays at the bottom of the tube to form about half of the cylinder, and Gas and vapor stay at the top of the tube). Any suitable combination of annular flow, plug flow, and other flow regimes may be present in the tubular reactor.

In the non-limiting example shown in FIG. 1, the vent 62 on the tubular reactor 34 is coupled to one or more lines 64, which may be part of the manifold 66 in communication with one or more lines 68. One or more lines 68 may be coupled to one or more rectification columns 80 (only one shown in Figure 1) comprising one or more rectification zones 81. In an embodiment, each of the one or more lines 64 may be directly connected to line 68 (configuration not shown in Figure 1). In an embodiment, line 68 may be absent and each of one or more lines 64 may be directly connected to rectification column 80 (Configuration not shown in Figure 1).

Rectification column 80 can be any suitable rectification column. See, for example, U.S. Patent No. 3,900,450, which is incorporated herein in its entirety by reference. Water having a substantially gaseous phase can flow into the rectification column 80, which in the non-limiting example shown in Figure 1, comprises eight trays T1-T8. The trays T1-T8 can be, for example, bubble cap trays or sieve trays and can be larger or smaller than eight. Those skilled in the art will appreciate that the trays T1-T8 can be replaced with any suitable column packing, including glass wool, Raschig rings, glass beads, structured packing, or any suitable column packing material. The column can have any suitable height, such as from about 1 M to about 500 M, or from about 1 M to about 20 M, or about 1 M or less, or about 2 M, 3 M, 4 M, 5 M, 6 M, 7 M, 8 M, 9 M, 10 M, 12 M, 14M, 16M, 18M, 20M, 25M, 30M, 35M, 40M, 45M, 50M, 100M, 150M, or about 200M or more. The column can have any suitable diameter, such as from about 0.1 M to about 30 M, or from about 0.1 M to about 10 M, or about 0.1 M or less, or about 0.5 M, 1 M, 2 M, 3 M, 4 M, 5 M, 6 M, 7 M. , 8M, 9M, 10M, 12M, 14M, 16M, 18M, 20M, 22M, 24M, 26M, 28M or about 30M.

Water having a substantially gaseous phase rises from the bottom of the rectification column 80 and passes through the rectification zone 81. Water having a substantially gaseous phase rising from the top tray (here indicated as T8) is in contact with a portion of the condenser-preheater 82 and may be partially condensed to produce reflux. The return flow from the partial condenser-preheater 82 to the rectification column 80 may be in particular from at least a portion of the condenser-preheater 82 fluid (eg, comprising a dicarboxylic acid, a diamine, and a water having a substantially liquid phase) The amount, concentration and temperature of the aqueous solution, which can flow through the condenser-preheater coil for preheating; and the pressure control in the rectification zone 81. In one example, the heat transfer zone of the partial condenser-preheater 82 can be configured such that as the flow of fluid therein increases, the amount of water having a substantially gaseous phase condensed in reflux form increases. In some examples, water having a substantially liquid phase that can be collected at the bottom of rectification column 80 can be heated using any suitable means to convert it into water having a substantially gaseous phase, thereby producing at least some reflux.

As water having substantially gaseous phase passes through the rectification zone 81, one or more of the diamine, carboxylic acid, and polyamine is collected in the reservoir 70 in the form of its substantially aqueous solution. In some examples, a substantially aqueous solution comprising one or more of a diamine, a carboxylic acid, and a polyamidamine can then be recycled to tubular reactor 34 via line 72, valve 30, and line 32 for reuse in the polymerization. In the indole synthesis process. In one example, one or more of the diamine, carboxylic acid, and polyamine can be collected in the reservoir 70 as a substantially aqueous solution. The solution can be transferred to one or more components of the polyamine synthesis process via a line or valve network (not shown in Figure 1) including, but not limited to, reservoir 10 or evaporator 18. In some cases, the reservoir 70 can be located where T2, T4, or T6 is located (configuration not shown in Figure 1). In some cases, more than one reservoir 70 may be present in the rectification column. In some cases, the dicarboxylic acid can be added (eg, injected) to a higher plate in the reservoir 70 or column, and reacted, for example, with a diamine such as hexamethylenediamine. The resulting material from the reaction of the dicarboxylic acid with a diamine (e.g., a polyamidamide prepolymer) can be recycled via line 72, valve 30, and line 32, for example, back to reactor 34.

Uncondensed water having a substantially gaseous phase discharged from the top of the rectification column 80 via the exhaust line 74 and the valve 76 may constitute purified water having a substantially gaseous phase. Purified water having a substantially gaseous phase can be transferred via line 78 to condenser 83 where it can be condensed into water having a substantially liquid phase. Water having a substantially liquid phase can then be transferred via line 84, valve 86, and line 88. In some embodiments, as shown in FIG. 1, water can be transferred to the filter or adsorption assembly 90. In some embodiments, water having a substantially liquid phase can be used directly in the vapor or can be recycled upstream without further purification (not shown in Figure 1). Water exiting column 80 at line 74 can include at least one of water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof. The water present in line 74 can be substantially demineralized, and if it is directed back to the process, fresh demineralized water consumption can be reduced and cost can be saved.

In addition to removing one or more of the diamine, carboxylic acid, and polyamine, the rectification column can remove one or more impurities from the water having substantially gaseous phase, such as a material that causes gelation and degradation of the polyamine. At least one of the materials. The separated impurities may be solid (undissolved) impurities, such as heavy gold. Genus. The heavy metal is insoluble in water or slightly soluble in water, and can flow into the circulation device in the form of water droplets containing the suspended material together with water having a substantially gaseous phase. Certain heavy metals (such as iron, cobalt, manganese, magnesium, and titanium) and inorganic materials (such as ceria) can catalyze gel formation, including catalyzing the formation of bis(hexamethylene)triamine. The boiling point of the separated impurities may be different from water, such as cyclopentanone (BP = 131 ° C), hexamethyleneimine (BP = 138 ° C) or bis (hexamethylene) triamine (BP = 163-164 ° C ). Cyclopentanone, hexamethyleneimine, bis(hexamethylene)triamine can be used as a blocking agent (for example, premature end-capped polymerization at one or more ends of the polymer), a branching agent (for example The polymer strands are loosely linear, which can form a gel) and linear units in the final polyamine product (eg, which can reverse the regular repeating unit of polyamine, regardless of product quality). The water present from the rectification column can suitably remove one or more gelling-inducing materials or polyamine degradation materials such that a high water circulation ratio can be achieved without accumulating the gelling-inducing material or the polyamine degradation material.

The filtration or adsorption assembly 90 can purify water having a substantially liquid phase by removing impurities from water having a substantially liquid phase, such as a gelling-inducing material or a polyamine degradation material. The representative filter or adsorption assembly 90 can be any suitable configuration and can include a coarse filter (e.g., 200 [mu]m) and optionally a heat exchanger that can be aligned with the first fine filter (e.g., 50 [mu]m). The first fine filter can be of any suitable configuration, including in line with at least one activated carbon adsorbent bed. Water having a substantially liquid phase can then pass through a second fine filter (e.g., 5 [mu]m) to remove particulate matter, including activated carbon adsorbents, that may leave the adsorbent bed. Examples of impurities that may be removed using a filter or adsorption assembly 90 include heavy metals such as iron, cobalt, manganese, magnesium, and titanium, and may include organic materials such as cyclopentanone, hexamethyleneimine, bis (six Methylene) triamine, and inorganic materials such as cerium oxide.

In various embodiments, line 74 can be a side cut of rectification column 80 rather than the overhead stream illustrated in FIG. The side fraction may carry water having substantially gaseous phase, purified water having a substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof. Materials with a boiling point lower than water can appear from the top of the column. In some embodiments, the column may have a bottoms stream exiting the lower portion of the column, which may contain materials having a boiling point higher than water (eg, adipic acid, hexamethylenediamine, cyclopentanone, At least one of hexamethyleneimine and bis(hexamethylene)triamine). The bottom stream can carry solid impurities such as iron, cobalt, titanium, manganese, magnesium and cerium oxide. In some embodiments, the bottoms stream can return the reactants to reactor 34 or evaporator 18, optionally removing solid impurities by a filter assembly similar to unit 98. In some embodiments, the column may have a side cut below the height of the line 74 from the column (as the top or side fraction) and above the bottom of the column such that the material having an intermediate boiling point can be removed from the system. For example, in some embodiments, the column can include a bottoms stream comprising materials such as solid impurities, adipic acid, and hexamethylenediamine; including cyclopentanone, hexamethyleneimine And a first side fraction of at least one of the bis(hexamethylene)triamine; and a top fraction or a second side fraction above the first side fraction, which carries water having substantially gaseous phase, At least one of purified water having substantially gaseous phase and purified water having a substantially liquid phase.

Reusing with one or more components (including, but not limited to, returning to reservoir 10 via line 92, valve 94, and line 96) with purified liquid having a substantially liquid phase returned to the polyamine synthesis process Substantially liquid water. In one embodiment, purified water having a substantially liquid phase can be transferred to storage vessel 100 via line 92, valve 94, and line 98 for, for example, subsequent use. In one embodiment, water having a substantially liquid phase can be transferred from the condenser 83 or the filter or adsorption assembly 90 to a sewage system (not shown) of the polyamine production facility. In one example, a portion of the water having a substantially liquid phase can be transferred to the storage vessel 100 for, for example, subsequent use; a portion can be disposed of to the sewage system of the polyamine production facility (not shown); and a portion can be passed by Re-use of one or more components to the polyamide synthesis process (eg, in one or more of reservoir 10, evaporator 18, reactor 34, flasher 42, finisher 50, or storage vessel 100) use). In various embodiments, reusing water having a substantially liquid phase can include converting water to vapor and using vapor in one or more components of the polyamide synthesis process.

In some examples, the material from line 75 that appears in rectification column 80 (eg, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or The combination thereof or the material leaving the adsorption or filtration device is sufficiently pure to be used as a source of vapor in the polyamine synthesis process, for example at least about 90% by weight pure, or about 91% by weight, 92% by weight, 93% by weight, 94% by weight. %, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight, 99.999% by weight, 99.9999% by weight, 99.99999% by weight or about 99.999999% by weight or 99.999999% by weight Above pure. In some embodiments, the vapor is of sufficient purity to drive the vacuum vapor ejector, and the downstream finisher is evacuated using a reliable operation.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable heavy metal concentration (eg, elemental heavy metals or compounds including heavy metals), such as about 1% by weight or less, or about 0.5%, 0.1%, 0.05%, 0.01%, or 0.01% by weight, From about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb , 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have a reduction in the total amount of any suitable heavy metals, such as from about 1% to about 100% reduction, or about 50, as compared to water leaving the reactor and entering the recycle assembly. Up to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96% by weight %, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable iron concentration (eg elemental iron or a compound comprising iron), such as about 1% by weight or less, or about 0.5% by weight, 0.1% by weight, 0.05 % by weight, 0.01% by weight or less, from about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total iron, such as from about 1% to about 100% reduction, or about 50, compared to water leaving the reactor and entering the recycle assembly. Up to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96% by weight %, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable cobalt concentration (eg, elemental cobalt or a compound including cobalt), such as about 1% by weight or less, or about 0.5%, 0.1%, 0.05%, 0.01%, or 0.01% by weight, From about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb , 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total cobalt, such as from about 1% to about 100% reduction, or about 50, compared to water leaving the reactor and entering the recycle assembly. Up to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96% by weight %, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (eg, water with substantially gas phase, purified water with substantial gas phase, purified water with a substantially liquid phase, or a combination thereof) or self-filter or total adsorption The substance to be present may have any suitable manganese concentration (eg, elemental manganese or a compound including manganese), such as about 1% by weight or less, or about 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight or less, about 1 ppb to about 10,000 ppm, about 10 ppb to about 1,000 ppm, about 100 ppb to about 100 ppm, or about 5,000 ppm or more, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total manganese, such as from about 1% to about 100% reduction, or about 50, compared to water leaving the reactor and entering the recycle assembly. Up to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96% by weight %, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable magnesium concentration (eg, elemental magnesium or a compound including magnesium), such as about 1% by weight or less, or about 0.5%, 0.1%, 0.05%, 0.01%, or 0.01% by weight, From about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb , 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total magnesium, such as from about 1% to about 100% reduction, or about 50, compared to water leaving the reactor and entering the recycle assembly. Up to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96% by weight %, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable titanium concentration (eg, elemental titanium or a compound including titanium), such as about 1% by weight or less, or about 0.5%, 0.1%, 0.05%, 0.01%, or 0.01% by weight, From about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb , 10 ppb, 5 ppb or about 1 ppb or less. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total titanium, such as from about 1% to about 100% reduction, or about, as compared to water leaving the reactor and entering the recycle assembly. 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96 % by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable concentration of cerium oxide, such as about 1% by weight or less, or about 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or less, and about 1 ppb to about 10,000 ppm, From about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or from about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb Or below 1ppb. The water present from the rectification column or filter or adsorption assembly may have any suitable reduction in total cerium oxide, such as from about 1% to about 100%, as compared to water leaving the reactor and entering the recycle assembly. Or about 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% A decrease in the amount of %, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or 99.999% by weight or more.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable concentration of cyclopentanone, such as about 10% by weight or less, or about 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight or less, about 1 ppb to about 10,000 ppm, about 10 ppb to about 1,000 ppm, about 100 ppb to about 100 ppm, or About 5,000 ppm or more, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the filter or adsorption assembly or the water present from the rectification column may have any suitable reduction in the amount of cyclopentanone, such as from about 1% to about 100%, as compared to the water leaving the reactor and entering the recycle assembly. Decrease, or about 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95 A decrease in weight %, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or 99.999% by weight or more.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable hexamethyleneimine concentration, such as about 10% by weight or less, or about 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight %, 1.5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight or less, from about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm Or about 5,000 ppm or more, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the filter or adsorption assembly or the water present from the rectification column may have any suitable reduction in the amount of hexamethyleneimine, such as about 1% to the water leaving the reactor and entering the recycle assembly. About 100% reduction, or about 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% by weight %, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable bis(hexamethylene)triamine concentration, such as about 10% by weight or less, or about 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight 2% by weight, 1.5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight or less, about 1 ppb to about 10,000 ppm, about 10 ppb to about 1,000 ppm, about 100 ppb To about 100 ppm, or about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the filter or adsorption assembly or the water present from the rectification column may have any suitable reduction in the amount of bis(hexamethylene)triamine, such as about the water leaving the reactor and entering the recycle assembly. 1% to about 100% reduction, or about 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% by weight 90% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (eg, water with substantially gas phase, purified water with substantial gas phase, purified water with a substantially liquid phase, or a combination thereof) or self-filter or total adsorption The substance to be present may have any suitable hexamethylenediamine concentration, such as about 10% by weight or less, or about 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5. % by weight, 2% by weight, 1.5% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight, from about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, From about 100 ppb to about 100 ppm, or about 5,000 ppm or more than 5,000 ppm, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the filter or adsorption assembly or the water present from the rectification column may have any suitable reduction in the amount of hexamethylenediamine, such as about 1% to the water leaving the reactor and entering the recycle assembly. About 100% reduction, or about 50 to about 99% reduction, or about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% by weight %, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Water from the rectification column (for example, water having substantially gaseous phase, purified water having substantially gaseous phase, purified water having a substantially liquid phase, or a combination thereof) or a substance emerging from a filter or an adsorption assembly Having any suitable adipic acid concentration, such as about 10% by weight or less, or about 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5 % by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight or 0.01% by weight, from about 1 ppb to about 10,000 ppm, from about 10 ppb to about 1,000 ppm, from about 100 ppb to about 100 ppm, or about 5,000 ppm or more, about 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 500 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb or about 1 ppb or less. The water present from the filter or adsorption assembly or the water present from the rectification column may have any suitable reduction in the amount of adipic acid, such as from about 1% to about 100%, as compared to water leaving the reactor and entering the recycle assembly. Decrease, or about 50 to about 99% reduction, or about 10% by weight, 20 % by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight , 99.9% by weight, 99.99% by weight or about 99.999% by weight or more than 99.999% by weight.

Whether the water having a substantially liquid phase or water having a substantially gaseous phase is ultimately reused (eg, for reuse in the reservoir 10, the tubular reactor 34, or stored in the storage vessel 100), the methods and systems described herein will At least 80% or less of the purified water leaving the rectification column 80 has a substantially gaseous phase of purified water condensed into water having a substantially liquid phase. In some cases, at least 85%, at least 90%, at least 95%, at least 99%, from about 80% to about 100%, from about 80% to about 90%, from about 85% to about 95% of the rectification column 80 From about 90% to about 99% or about 100% of the water having substantially gaseous phase can be condensed into water having a substantially liquid phase.

In some examples, the methods and systems described herein further comprise operating at a water recycle ratio of at least 0.2:1 v/v. As used herein, the term "cycle ratio" generally refers to the re-use/circulation of liquid water to a reservoir relative to "fresh" liquid water (ie, from the condensation of water from a substantially gaseous phase to have substantial The "fresh" water is used in particular for preparing the aqueous solution contained in the reservoir 10 by the volume ratio of the volume of the water outside the water source. In some examples, the water circulation ratio can be at least 0.2:1 or 0.2:1 or less, or about 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1 : 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2: 1, 2.2: 1, 2.4: 1 2.6:1, 2.8:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 20:1, 50 : 1, 100:1 or about 200:1 or more than 200:1. In other examples, the water recycle ratio is in the range of from about 1:1 to about 200:1, such as from about 10:1 to about 100:1 or from about 25:1 to about 100:1.

In some examples, one or more of the lines and valves described herein include water for transferring water having a substantially gaseous phase (eg, line 74, valve 76, and line 78) and water having a substantially liquid phase. (eg, line 84, valve 86, line 88, line 92, valve 94, line 96 and Line 98) is made of stainless steel or other material that helps maintain, reduce, or minimize the level of impurities in substantially purified water having at least a substantial liquid phase, such as materials that cause gelation and polyamine degradation materials.

As used herein, the term "iron" generally refers to iron ions (eg, Fe ³⁺ and Fe ²⁺ ions in solution), elemental iron and iron oxides (eg, FeO, Fe ₂ O _{3 ,} and Fe ₃ O ₄ ), and A compound of iron.

As used herein, the term "cobalt" generally refers to cobalt ions (eg, Co ³⁺ and Co ²⁺ ions in solution), elemental cobalt, and cobalt compounds used as gelling catalysts.

As used herein, the term "manganese" generally refers to manganese ions, elemental manganese, and manganese compounds used as gelling catalysts.

As used herein, the term "magnesium" generally refers to magnesium ions, elemental magnesium, and magnesium compounds used as gelling catalysts.

As used herein, the term "titanium" generally refers to titanium ions, elemental titanium, and titanium compounds used as gelling catalysts.

The polyamidamide prepolymer formed in tubular reactor 34 can be passed to flasher 42 via line 36, valve 38, and line 40. Flasher 42 is in turn in fluid communication with finisher 50 via line 44, valve 46, and line 48. Finisher 50, in turn, can be in fluid communication with line 54, valve 56, and line 58, through which substantially polymerized polyamine can be transferred for further processing (e.g., spinning or granulation).

Instance

Continuous polymerization process. The following process is performed in the example. In the continuous nylon 6,6 process, adipic acid and hexamethylenediamine are combined in a salt trigger at approximately equimolar ratio to form a water containing nylon 6,6 salt and having about 50% by weight water. mixture. The brine solution was transferred to the evaporator at about 105 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 a tubular reactor at about 75 L/min. The length of the tubular reactor is about 100 m and the average inner diameter is about 40.6 cm. The expansion of the inner diameter from the entry end to the exit end is about 2.5 cm per 50 m length, the L/D ratio is about 246, and there are 17 rows along the length. Air port. 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 (285 ° 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 flashed mixture having a relative viscosity of about 13 was transferred to the finishing machine at about 59 L/min. In the transfer conduit between the flasher and the finisher, the polymer mixture is maintained at a temperature of about 285 °C. The finishing machine subjects the polymerization mixture to a vacuum to further remove water to a water concentration of about 0.1% by weight and a relative viscosity of about 60, such that the finishing polymerization mixture is transferred to the extruder and granulation at about 59 L/min. Prior to the machine, the polyamine reached a range suitable for the final degree of polymerization.

A general method for determining the gelation rate. The gelation rates described in the examples were determined by averaging the gelation rates determined by the two methods. In the first method, when the reaction mixture is hot, the system discharges the liquid reaction mixture, the system is cooled, disassembled, and the gel volume therein is visually evaluated. In the second method, when the reaction mixture is hot, the system discharges the liquid reaction mixture, cools, fills with water, and drains water. The gel volume in the system is measured from the gel-free volume of the system minus the volume of water discharged from the system. In order to determine the gelation rate of one or more particular types of equipment or downstream of a particular location, only special types of equipment or systems downstream of a particular location are filled with water. In both methods, the gel density was estimated to be 0.9 g/cm ³ .

The variable X is a constant value in all instances. The side or bottom fraction of the rectification column at least partially separates solid impurities and materials having a lower boiling point than water.

Example 1. Comparison, no impurities removed from circulating water, no thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and condenses without further purification. Condensation of 18.5 Kg/min 235 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 48 MJ/min. From the reaction The approximately 18.5 L/min of the condensed unpurified water was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 10,000 ppm cyclopentanone, about 8,000 ppm hexamethyleneimine, about 5,000 ppm bis(hexamethylene). Diamine, about 100,000 ppm hexamethylenediamine and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 4. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 1 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about X per day, plus a daily steam condensation cost of about 15.5*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 2. Comparison, no impurities removed from circulating water, carbon steel evaporator circulation unit, no heat integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and condenses without further purification. Condensation of 18.5 Kg/min 235 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 48 MJ/min. Approximately 18.5 L/min of condensed unpurified water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily carbon steel. After 3 months on line, the purified water recycled to the salt trigger contains about 10,000 ppm iron, about 5,000 ppm cobalt, about 20,000 ppm cyclopentanone, about 16,000 ppm hexamethyleneimine, about 10,000 ppm double (hexamethylene a diamine, about 100,000 ppm hexamethylenediamine, and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 2 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about X per day, plus a daily steam condensation cost of about 15.5*X. Compared to not having an evaporator The corresponding process of the cycle, avoiding excessive sewage pipe discharge fines and using less demineralized fresh water to save about 30*X per day.

Example 3. Comparison, carbon dioxide evaporator circulation device without removing impurities from circulating water, anti-corrosion treatment, no heat integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and condenses without further purification. Condensation of 18.5 Kg/min 235 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 48 MJ/min. Approximately 18.5 L/min of condensed unpurified water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily carbon steel which has been treated with a combination of sodium dihydrogen phosphate, sodium benzoate, sodium nitrite and sodium nitrate. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 10,000 ppm cyclopentanone, about 8,000 ppm hexamethyleneimine, about 5,000 ppm bis(hexamethylene). Diamine, about 100,000 ppm hexamethylenediamine and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 4. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 1 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about X per day, plus a daily steam condensation cost of about 15.5*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

However, over a period of about six months, the corrosion resistant material leached from the carbon steel, partially losing its corrosion resistance and contaminating the polyamine product. After six months on the line, the purified water recycled to the salt trigger contains about 10,000 ppm iron, about 5,000 ppm cobalt, about 20,000 ppm cyclopentanone, about 16,000 ppm hexamethyleneimine, about 10,000 ppm double (hexamethylene a diamine, about 100,000 ppm hexamethylenediamine, and about 1,000 ppm adipic acid. The yellowness coefficient of the refined polyamidamide particles produced by the system according to ASTM D1925 is about 5. After 6 months, the system The gel formation rate is about 1.5 Kg per day.

Example 4. Comparison, filtration from the circulating water selectivity but insufficient removal of some impurities, no thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and condenses. Condensation of 18.5 Kg/min 235 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 48 MJ/min. The condensed water was cleaned by a filter assembly containing a rough filter (200 μm) in line with the first fine filter (50 μm). The first fine filter is in line with the activated carbon adsorbent bed containing about 50 Kg of activated carbon adsorbent. The water then passed through a second fine filter (5 μm). Approximately 18.5 L/min of condensed clean water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 50 ppm iron, about 25 ppm cobalt, about 8,000 ppm cyclopentanone, about 7,000 ppm hexamethyleneimine, about 4,000 ppm bis(hexamethylene). Diamine, about 100,000 ppm hexamethylenediamine and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 3.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 1 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 3*X per day, plus a daily steam condensation cost of about 15.5*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 5. Comparison, rectification from circulating water selective but insufficient removal of impurities, no thermal integration

Perform a continuous aggregation process. The vapor material evaporating from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 1M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. Tubular reactor circulation device and The relevant transfer conduit is primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 35 ppm iron, about 15 ppm cobalt, about 5,000 ppm cyclopentanone, about 4,000 ppm hexamethyleneimine, about 2,000 ppm bis(hexamethylene). Diamine, about 50,000 ppm hexamethylenediamine and about 500 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 3.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.6 Kg gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 3*X per day, plus a daily steam condensation cost of about 14*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 6. Selective removal of impurities by recirculating from 1:1 cycle ratio of circulating water, without thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. About 9.5 L/min of purified water from the evaporator and free of impurities (e.g., about 30% by weight of the total amount of water removed from the reaction mixture in the evaporator) is also recycled back to the salt trigger. The total amount of circulating water entering the salt trigger was 28 L/min, which was combined with 28 L/min demineralized fresh water at a cycle ratio of 1:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day, plus a daily steam condensation cost of about 14*X. Compared to not having evaporation The corresponding process of the cycle, avoiding excessive sewage pipe discharge fines and using less demineralized fresh water to save about 3*X per day.

Example 7. Selective removal of impurities from recirculating water by rectification without thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day, plus a daily steam condensation cost of about 14*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 8. Selective removal of impurities from recirculating water by rectification, without thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 10M high 0.5M diameter rectification column packed with Raschig rings. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 1 ppm iron, about 0.5 ppm cobalt, about 10 ppm cyclopentanone, about 8 ppm six Asia. Methylimine, about 5 ppm bis(hexamethylene)diamine, about 100 ppm hexamethylenediamine, and about 1 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 1.4. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.35 Kg gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 16*X per day, plus a daily steam condensation cost of about 14*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 9. Refining and Filtration Selective Removal of Impurities from Circulating Water, No Thermal Integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. The condensed liquid was cleaned by a filter assembly containing a rough filter (200 μm) in line with the first fine filter (50 μm). The first fine filter is in line with the activated carbon adsorbent bed containing about 50 Kg of activated carbon adsorbent. The water then passed through a second fine filter (5 μm). Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 5 ppm iron, about 2 ppm cobalt, about 50 ppm cyclopentanone, about 40 ppm hexamethyleneimine, about 25 ppm bis(hexamethylene)diamine, About 2,500 ppm of hexamethylenediamine and about 25 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.35 Kg gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 5*X per day, plus a daily steam condensation cost of about 14*X. Avoid excessive sewage pipe discharge fines and use less demineralized material than the corresponding process without evaporator cycle Fresh water saves about 30*X per day.

Example 10. Selective removal of impurities from a circulating water ratio of 4:1 cycle, no thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. About 26.3 L/min of purified water from the evaporator and free of impurities (e.g., about 82% by weight of all water removed from the reaction mixture in the evaporator) is also recycled back to the salt trigger. The total amount of circulating water entering the salt trigger was 44.8 L/min, which was combined with 11.2 L/min demineralized fresh water at a cycle ratio of 4:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 5*X per day, plus a daily steam condensation cost of about 14*X. Compared to a process that does not have an evaporator cycle, avoiding excessive sewer discharge penalties and using less demineralized fresh water saves about 50*X per day.

Example 11. Selective removal of impurities from a circulating water ratio of 14.1:1 cycle, no thermal integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily stainless steel. After 3 months on the line, cycle to the purification of the salt trigger Water contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, about 5,000 ppm hexamethylenediamine, and about 50 ppm. Diacid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. Approximately 32 L/min of purified water from the evaporator and free of impurities (eg, 100% by weight water removed from the reaction mixture in the evaporator) is also recycled back to the salt trigger. The total amount of circulating water entering the salt trigger was 50.5 L/min, which was combined with 3.5 L/min demineralized fresh water at a cycle ratio of 14.4:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 5*X per day, plus a daily steam condensation cost of about 14*X. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 60*X per day.

Example 12. Selective removal of impurities by rectification from circulating water, carbon steel evaporator circulation unit, no heat integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily carbon steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 500 ppm cyclopentanone, about 220 ppm hexamethyleneimine, about 200 ppm bis(hexamethylene)diamine, About 1,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 1.8. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.5 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day, plus a daily steam condensation cost of about 14*X. Compared to not having evaporation The corresponding process of the cycle, avoiding excessive sewage pipe discharge fines and using less demineralized fresh water to save about 30*X per day.

Example 13. Selective removal of impurities by rectification from recycled water, treated carbon steel evaporator circulation unit, without heat integration

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column condenses into a liquid for circulation. Condensation of 18.5 Kg/min 100 ° C vapor to 18.5 L/min 90 ° C aqueous liquid requires about 43 MJ/min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit and associated transfer conduits are primarily carbon steel which has been treated with a combination of sodium dihydrogen phosphate, sodium benzoate, sodium nitrite and sodium nitrate. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day, plus a daily steam condensation cost of about 14*X. However, over a period of about six months, the corrosion resistant material leached from the carbon steel, partially losing its corrosion resistance and contaminating the polyamine product. After six months, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 500 ppm cyclopentanone, about 220 ppm hexamethyleneimine, about 200 ppm bis(hexamethylene)diamine, about 1,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 1.8. After six months, the gel formation rate was about 0.5 Kg per day. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 14. Comparison, thermal integration with evaporator, no rectification

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is charged to a heat transfer unit to partially heat the evaporator. At about 130 ° C (under pressure), 18.5 Kg / min 235 ° C vapor was condensed to 18.5 L / min aqueous liquid transferred to the evaporator about 47 MJ / min. The condensed water was circulated back to the salt trigger at a rate of about 18.5 L/min. The tubular reactor circulation unit, associated transfer conduit, and evaporator heat transfer unit are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 10,000 ppm cyclopentanone, about 8,000 ppm hexamethyleneimine, about 5,000 ppm bis(hexamethylene). Diamine, about 100,000 ppm hexamethylenediamine and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 4. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 1 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about X per day. The transfer of heat to the evaporator saves about 15.5*X per day compared to a corresponding process that does not transfer heat to the evaporator. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 15. Comparison, heat integration with the evaporator and steam for the finishing machine, no rectification

Perform a continuous aggregation process. The vapor material evaporating from the reaction mixture in the reactor exits the vent of the reactor and is used to at least partially drive a vacuum vapor ejector that evacuates the downstream finisher. The vapor leaving the finishing machine is charged to a heat transfer unit to partially heat the evaporator. At about 130 ° C (under pressure), 18.5 Kg / min 235 ° C vapor was condensed to 18.5 L / min aqueous liquid transferred to the evaporator about 47 MJ / min. The condensed water was circulated back to the salt trigger at a rate of about 18.5 L/min. The tubular reactor circulation unit, associated transfer conduit, and evaporator heat transfer unit are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 10,000 ppm cyclopentanone, about 8,000 ppm hexamethyleneimine, about 5,000 ppm bis(hexamethylene). Diamine, about 100,000 Ppm hexamethylenediamine and about 1,000 ppm adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 4. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 1 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about X per day. The transfer of heat to the evaporator saves about 15.5*X per day compared to a corresponding process that does not transfer heat to the evaporator. Providing 18.5 Kg/min of steam to the finishing machine saves about 20*X per day compared to the corresponding process in which the steam does not circulate back to the finishing machine. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 16. Rectification, thermal integration with evaporator

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column is charged to a heat transfer unit to partially heat the evaporator. At 130 ° C (under pressure), 18.5 Kg / min 130 ° C vapor was condensed to 18.5 L / min aqueous liquid under pressure to transfer to the evaporator about 43 MJ / min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit, associated transfer conduit, and evaporator heat transfer unit are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day. The transfer of heat to the evaporator saves about 15*X per day compared to a corresponding process that does not transfer heat to the evaporator. Compared to a corresponding process without an evaporator cycle, Avoid excessive sewer discharge penalties and use less demineralized fresh water to save about 30*X per day.

Example 17. Rectification, heat integration with the evaporator and steam for the finishing machine

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the column is used to at least partially drive a vacuum vapor ejector that evacuates the downstream corrector. The vapor leaving the finishing machine is charged to a heat transfer unit to partially heat the evaporator. At 130 ° C (under pressure), 18.5 Kg / min 130 ° C vapor was condensed to 18.5 L / min aqueous liquid under pressure to transfer to the evaporator about 43 MJ / min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit, associated transfer conduit, and evaporator heat transfer unit are primarily stainless steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 10 ppm iron, about 5 ppm cobalt, about 100 ppm cyclopentanone, about 80 ppm hexamethyleneimine, about 50 ppm bis(hexamethylene)diamine, About 5,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness coefficient of about 1.5. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day. The transfer of heat to the evaporator saves about 15*X per day compared to a corresponding process that does not transfer heat to the evaporator. Providing 18.5 Kg/min of steam to the finishing machine saves about 20*X per day compared to the corresponding process in which the steam does not circulate back to the finishing machine. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 18. Comparison, rectification, thermal integration with evaporator, carbon steel unit

Perform a continuous aggregation process. The vapor material evaporating from the reaction mixture in the reactor leaves the vent of the reactor and is directed to a 3M high 0.5M diameter packed with Raschig rings. Distillation tower. The vapor leaving the top of the column is charged to a heat transfer unit to partially heat the evaporator. At 130 ° C (under pressure), 18.5 Kg / min 130 ° C vapor was condensed to 18.5 L / min aqueous liquid under pressure to transfer to the evaporator about 43 MJ / min. Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. The tubular reactor circulation unit, associated transfer conduit, and evaporator heat transfer unit are primarily carbon steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 100 ppm iron, about 50 ppm cobalt, about 500 ppm cyclopentanone, about 220 ppm hexamethyleneimine, about 200 ppm bis(hexamethylene)diamine, About 1,000 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 1.8. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 3 Kg of gel is produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day. The transfer of heat to the evaporator saves about 15*X per day compared to a corresponding process that does not transfer heat to the evaporator. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

Example 19. Distillation, heat integration with an evaporator and filtration, carbon steel unit

Perform a continuous aggregation process. The vapor material evaporated from the reaction mixture in the reactor exits the vent of the reactor and is directed to a 3M high 0.5M diameter rectification column packed with a Raschig ring. The vapor leaving the top of the column is charged to a heat transfer unit to partially heat the evaporator. At 130 ° C (under pressure), 18.5 Kg / min 130 ° C vapor was condensed to 18.5 L / min aqueous liquid under pressure to transfer to the evaporator about 43 MJ / min. The condensed water was cleaned by a filter assembly containing a rough filter (200 μm) in line with the first fine filter (50 μm). The first fine filter is in line with the activated carbon adsorbent bed containing about 50 Kg of activated carbon adsorbent. The water then passed through a second fine filter (5 μm). Approximately 18.5 L/min of condensed water from the reactor was recycled back to the salt trigger. Tubular reactor circulation unit, associated transfer The transfer conduit and evaporator heat transfer device is mainly carbon steel. After 3 months on the line, the purified water recycled to the salt trigger contains about 60 ppm iron, about 70 ppm cobalt, about 300 ppm cyclopentanone, about 150 ppm hexamethyleneimine, about 60 ppm bis(hexamethylene)diamine, About 500 ppm of hexamethylenediamine and about 50 ppm of adipic acid. The fine polyamide particles produced by the system according to ASTM D1925 have a yellowness factor of about 1.6. The total amount of circulating water entering the salt trigger was 18.5 L/min, which was combined with 37.5 L/min demineralized fresh water at a cycle ratio of 0.5:1.

Approximately 0.4 Kg of gel was produced per day in a continuous polymerization system. The reactor cycle unit operates at a cost of about 4*X per day. The transfer of heat to the evaporator saves about 15*X per day compared to a corresponding process that does not transfer heat to the evaporator. Compared to the corresponding process without the evaporator cycle, avoid excessive sewage pipe discharge fines and use less demineralized fresh water to save about 30*X per day.

The presently described embodiments of the present invention are not limited to the specific embodiments disclosed herein, as such embodiments are intended to be illustrative of several aspects of the present invention. Any equivalent embodiment is intended to be within the scope of this creation. In fact, it will be apparent to those skilled in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Such amendments are also intended to be within the scope of the accompanying patent application.

This work has been summarized and generally described. The narrower categories and subsets within the scope of this creation also form part of this creation. This includes general descriptions of the creations under the restrictions or negative restrictions of the removal of the subject matter from the category, whether or not a specific statement is made herein. In addition, if the characteristics or aspects of the creation are described in terms of the Markush group, those skilled in the art should understand that the creation is also based on any individual member or subgroup of the Marcus group. .

The singular forms "a", "the", "the" and "the" are meant to include the plural. Thus, for example, reference to "a reactor" includes a plurality of reactors, such as a series of reactors. In this document, the term "or" is used to mean non unless otherwise indicated. Exclusivity or such that "A or B" includes "A but not B", "B but not A" and "A and B".

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 the 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 permit a variability 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.

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.

This creation provides the following examples, the numbers of which are not to be construed as indicating the level of importance: Statement 1 provides a self-prepared polyamine and at least one carboxylic acid A method of recovering water by a condensation reaction, comprising: obtaining an aqueous mixture from an evaporator comprising a partially polymerized polyamine and at least one of a carboxylic acid and a diamine; passing the aqueous mixture through a tubular reactor, comprising the aqueous mixture Subjecting to a temperature and pressure sufficient to further polymerize the partially polymerized polyamine by condensation of the carboxylic acid with a diamine, thereby producing water having a substantially gaseous phase; and passing the substantially gaseous phase water to the rectification a column, whereby one or more of a diamine, a carboxylic acid, and a polyamidamine are removed to provide purified water having a substantially gaseous phase; and the purified water having a substantially gaseous phase is condensed to have a substantially liquid phase Purified water.

Statement 2 provides the method of claim 1, further comprising removing at least one impurity from the purified water having substantially liquid phase and at least one of the water having a substantially gaseous phase, wherein the impurity comprises a material that causes gelation and agglomerates At least one of the guanamine degradation materials.

Statement 3 provides the method of claim 2, wherein the impurity comprises iron.

Statement 4 provides the method of claim 2, wherein the impurity comprises at least one selected from the group consisting of iron, cobalt, titanium, manganese, magnesium, cerium oxide, cyclopentanone, hexamethyleneimine, and bis (hexamethylene) Base) triamine.

The method of any one of statements 1 to 4, further comprising returning the substantially liquid phase water to the reservoir or the polyamine generating reactor.

Statement 6 provides the method of claim 5, wherein the method further comprises operating at a water circulation ratio of at least 0.2:1.

The method of any one of statements 1 to 6, further comprising reusing the purified water having a substantially liquid phase.

Statement 8 provides the method of claim 7, wherein reusing the purified water having a substantially liquid phase comprises returning the purified water having a substantially liquid phase to one or more components of the polyamide synthesis process.

The method of any one of statements 1 to 8, wherein the rectification column comprises a rectification zone.

The method of any one of statements 1 to 9, wherein the rectification column comprises one or Multiple condensers.

Statement 11 provides the method of claim 10, wherein the one or more condensers transfer heat to one or more components of the polyamide synthesis process.

The method of any one of statements 1 to 11, wherein the condensing of the purified water having a substantially gaseous phase into purified water having a substantially liquid phase comprises condensing at least 80% of the water having a substantially gaseous phase.

The method of any one of statements 1 to 12, further comprising: passing the purified water having a substantially liquid phase through a filter or an adsorption assembly comprising at least one activated carbon adsorbent bed, providing a substantially liquid phase Substantially purified water.

Statement 14 provides the method of claim 13, wherein the substantially purified water having a substantially liquid phase is of sufficient purity to be converted and used as a vapor source in the polyamide synthesis process.

The method of any one of statements 1 to 14, wherein the substantially gaseous phase water is of sufficient purity to be used as a vapor source in the polyamine synthesis process.

The method of any one of statements 1 to 15, further comprising reusing one or more of a diamine, a carboxylic acid or a polyamine removed in the rectification column.

Statement 17 provides the method of claim 16, wherein the one or more of the diamine, carboxylic acid or polyamine removed in the rectification column comprises a diamine that is removed in the rectification column, The one or more of the carboxylic acid or polyamine is returned to one or more components of the polyamine synthesis process.

The method of claim 17, wherein the one or more components of the polyamine synthesis process comprise at least one of an evaporator, the tubular reactor, and a salt trigger.

The method of any one of statements 1 to 18, wherein the tubular reactor has a length of from about 50 to about 300 m.

The method of any one of statements 1 to 18, wherein the tubular reactor has a length of from about 75 to about 125 m.

The method of any one of statements 1 to 20, wherein the tubular reactor is The diameter is from about 10 cm to about 80 cm.

The method of any one of statements 1 to 21, wherein the tubular reactor further comprises a jacket.

Statement 23. The method of claim 1, wherein the tubular reactor has a length to diameter ratio of from about 50 to about 2,500.

The method of any one of statements 1 to 23, wherein the tubular reactor has a length to diameter ratio of from about 100 to about 500.

The method of any one of statements 1 to 24, wherein the tubular reactor further comprises an exhaust port along its length.

Statement 26 provides the method of claim 25, wherein the tubular reactor comprises from about 5 to about 50 vents.

Statement 27 provides the method of claim 25, wherein the tubular reactor comprises from about 10 to about 25 vents.

The method of any one of statements 25 to 27, wherein the tubular reactor comprises about 1 venting port on average from about 2 m to about 15 m along the length of the tubular reactor.

The method of any one of statements 25 to 28, wherein the tubular reactor comprises about 1 venting port on average from about 3 m to about 9 m along the length of the tubular reactor.

The method of any one of statements 25 to 29, wherein the tubular reactor comprises an average spacing of between about 2 m and about 15 m between the vents along the length of the tubular reactor.

The method of any one of statements 25 to 30, wherein the tubular reactor comprises an average spacing of between about 3 m and about 9 m between the vents along the length of the tubular reactor.

The method of any one of statements 1 to 31, wherein the tubular reactor comprises a length of from about 75 to about 125 m, the tubular reactor comprises an inner diameter of from about 25 cm to about 60 cm, and the tubular reactor comprises from about 100 to A length/diameter (L/ID) of about 500, and wherein the tubular reactor comprises from about 10 to about 25 vents along its length.

The method of any one of statements 1 to 32, wherein the aqueous mixture and the partially polymerized polyamine comprises a monomer of a C ₄ -C ₁₈ α,ω-dicarboxylic acid.

Statement 34 provides the method of claim 33, wherein the dicarboxylic acid is a C ₄ -C ₁₀ α,ω-dicarboxylic acid.

The method of any one of statements 33 to 34, wherein the dicarboxylic acid is a C ₄ -C ₈ α,ω-dicarboxylic acid.

The method of any one of statements 33 to 35, wherein the dicarboxylic acid is adipic acid.

The method of any one of statements 1 to 36, wherein the aqueous mixture and the partially polymerized polyamine comprises a C ₄ -C ₁₈ α,ω-diamine monomer.

Statement 38 provides the method of claim 37, wherein the diamine is a C ₄ -C ₁₀ α,ω-diamine.

Statement 39 provides the method of any of statements 37 to 38, wherein the diamine is C ₄ -C ₈ α, ω- diamine.

The method of any one of statements 37 to 39, wherein the diamine is hexamethylenediamine.

The method of any one of statements 1 to 40, wherein the polyamine is nylon 6,6.

Statement 43 provides a method of recovering water from a nylon 6,6 synthetic process comprising: obtaining an aqueous mixture comprising partially polymerized nylon 6,6 and hexamethylenediamine from an evaporator; passing the aqueous mixture through a tubular reactor While subjecting the aqueous mixture to a temperature and pressure sufficient to further polymerize the partially polymerized nylon 6,6, thereby producing water having a substantially gaseous phase; passing the substantially gaseous phase water to the rectification column, Thereby removing at least a portion of any hexamethylenediamine present in the water having substantially gaseous phase, providing purified water having a substantially gaseous phase; and condensing the purified water having a substantially gaseous phase to have substantially Purified water in the liquid phase.

Statement 44 provides a method for recovering water from a condensation reaction of at least one carboxylic acid of a polyamine and at least one diamine, comprising: obtaining an aqueous mixture from an evaporator comprising a partially polymerized polyamine and a carboxylic acid and At least one of the amines; the aqueous mixture is in the tube The reaction in the reactor comprises subjecting the aqueous mixture to a temperature and a pressure sufficient to further polymerize the partially polymerized polyamine by condensation of the carboxylic acid with a diamine, thereby producing water having a substantially gaseous phase; Refining the substantially vapor phase water in the rectification column of the rectification zone, thereby removing one or more of the diamine, the carboxylic acid and the diamine to provide purified water having a substantially gaseous phase; Determining whether the water having a substantially gas phase contains an excess amount of a carboxylic acid or a diamine or a stoichiometric balance, and injecting a carboxylic acid or a diamine into the rectification zone; and condensing the purified water having a substantially gaseous phase into Purified water having a substantially liquid phase.

Statement 45 provides a system comprising: a tubular reactor configured to further polymerize a partially polymerized polyamine to thereby produce water having a substantially gaseous phase; a rectification column in fluid communication with the tubular reactor Provided to remove one or more of a diamine, a carboxylic acid, and a polyamidamine to provide purified water having a substantially gaseous phase; a condensing assembly in fluid communication with the rectification column, configured to Receiving water having substantially gaseous phase and converting water having a substantially gaseous phase into water having a substantially liquid phase; and a network of pipes configured to return the substantially liquid phase water to the poly At least one component of the guanamine production system.

Statement 46 provides an apparatus for making polyamine, comprising: a tubular reactor configured to further polymerize a partially polymerized polyamine, thereby producing water having a substantially gaseous phase; and reacting with the tubular a rectifying column in fluid communication, configured to remove one or more of a diamine, a carboxylic acid, and a polyamidamine to provide purified water having a substantially gaseous phase; a total amount of condensation in fluid communication with the rectification column Forming to receive the water having substantially gaseous phase and converting water having a substantially gaseous phase into water having a substantially liquid phase; and a network of pipes configured to substantially The liquid phase water is returned to at least one component of the polyamine production system.

Statement 47 provides the apparatus of claim 44, wherein the apparatus is configured to remove at least one impurity from at least one of the purified liquid having substantially liquid phase and the water having substantially a gaseous phase, wherein the impurity comprises causing gelation At least one of a material and a polyamide degradation material.

Statement 48 provides the apparatus of claim 47, wherein the impurity comprises iron.

The apparatus of any one of statements 46 to 48, wherein the impurity comprises at least one selected from the group consisting of iron, cobalt, manganese, magnesium, titanium, cerium oxide, cyclopentanone, hexamethyleneimine And bis(hexamethylene)triamine.

The apparatus of any one of statements 44 to 49, wherein the apparatus is configured to return the substantially liquid phase water to the reservoir or the tubular reactor.

Statement 51 provides a device of claim 50, wherein the device operates at a water circulation ratio of at least 0.2:1.

The statement 52 provides the device of any one of statements 44 to 51, wherein the device is configured to reuse the purified water having a substantially liquid phase.

Statement 53 provides the apparatus of claim 52, wherein reusing the purified water having a substantially liquid phase comprises returning the purified water having a substantially liquid phase to one or more components of the polyamide synthesis process.

The statement 54 provides the apparatus of any one of statements 44 to 53, wherein the rectification column comprises a rectification zone.

Statement 55 provides the apparatus of claim 54, wherein the rectification column comprises one or more condensers.

Statement 56 provides the apparatus of claim 55, wherein the one or more condensers are configured to transfer heat to one or more components of the polyamide synthesis process.

The apparatus of any one of statements 44 to 56, wherein the condensation assembly is configured to convert at least 80% of the water having substantially gaseous phase into water having a substantially liquid phase.

The apparatus of any one of statements 44 to 57, further comprising a filter or adsorption assembly having substantially liquid phase water passing therethrough, wherein the filter or adsorption assembly comprises at least one activated carbon adsorbent bed And the filter or adsorption assembly provides substantially purified water having a substantially liquid phase.

Statement 59 provides the apparatus of claim 58, wherein the substantially purified liquid having a substantially liquid phase is of sufficient purity to be converted and used as a vapor source in the polyamide synthesis process.

The invention of claim 60, wherein the substantially gas phase water is of sufficient purity to be used as a vapor source in the polyamide synthesis process.

The statement 61 provides the apparatus of any one of statements 44 to 60, wherein one or more of the diamine, carboxylic acid or polyamine removed in the rectification column is reused.

Statement 62 provides the apparatus of claim 61, wherein the one or more of the diamine, carboxylic acid or polyamine removed in the rectification column comprises a diamine that is removed in the rectification column, The one or more of the carboxylic acid or polyamine is returned to one or more components of the polyamine synthesis process.

Statement 63 provides the apparatus of claim 62, wherein the one or more components of the polyamine production process comprise at least one of an evaporator, the tubular reactor, and a salt trigger.

The statement 64 provides the apparatus of any one of statements 44 to 63, wherein the tubular reactor has a length of from about 50 to about 300 m.

The apparatus of any one of statements 44 to 64, wherein the tubular reactor has a length of from about 75 to about 125 m.

The apparatus of any one of statements 44 to 65, wherein the tubular reactor has an inner diameter of from about 10 cm to about 80 cm.

The apparatus of any one of statements 44 to 66, wherein the tubular reactor further comprises a jacket.

The apparatus of any one of statements 44 to 67, wherein the tubular reactor has a length to diameter ratio of from about 50 to about 2,500.

The apparatus of any one of statements 44 to 68, wherein the tubular reactor has a length to diameter ratio of from about 100 to about 500.

The apparatus of any one of statements 44 to 69, wherein the tubular reactor further comprises an exhaust port along its length.

Statement 71 provides the apparatus of claim 70, wherein the tubular reactor comprises from about 5 to about 50 vents.

Statement 72 provides the apparatus of claim 70, wherein the tubular reactor comprises from about 10 to about 25 vents.

The apparatus of any one of statements 69 to 72, wherein the tubular reactor comprises about 1 venting port on average from about 2 m to about 15 m along the length of the tubular reactor.

The apparatus of any one of statements 69 to 73, wherein the tubular reactor comprises about 1 venting port on average from about 3 m to about 9 m along the length of the tubular reactor.

The apparatus of any one of statements 69 to 74, wherein the tubular reactor comprises an average spacing of between about 2 m and about 15 m between the vents along the length of the tubular reactor.

The apparatus of any one of statements 69 to 75, wherein the tubular reactor comprises an average spacing of between about 3 m and about 9 m between the exhaust ports along the length of the tubular reactor.

The apparatus of any one of statements 44 to 76, wherein the tubular reactor comprises a length of from about 75 to about 125 m, the tubular reactor comprises an inner diameter of from about 25 cm to about 60 cm, and the tubular reactor comprises from about 100 to A length/diameter (L/ID) of about 500, and wherein the tubular reactor comprises from about 10 to about 25 vents along its length.

The apparatus of any one of statements 44 to 77, wherein the partially polymerized polyamine comprises a monomer of a C ₄ -C ₁₈ α,ω-dicarboxylic acid.

Statement 79 provides the apparatus of claim 78, wherein the dicarboxylic acid is a C ₄ -C ₁₀ α,ω-dicarboxylic acid.

The apparatus of any one of statements 78 to 79, wherein the dicarboxylic acid is a C ₄ -C ₈ α,ω-dicarboxylic acid.

The apparatus of any one of statements 78 to 79, wherein the dicarboxylic acid is adipic acid.

The apparatus of any one of statements 44 to 81, wherein the partially polymerized polyamine comprises a monomer of a C ₄ -C ₁₈ α,ω-diamine.

Statement 83 provides the apparatus of claim 82, wherein the diamine is a C ₄ -C ₁₀ α,ω-diamine.

The apparatus of any one of statements 82 to 83, wherein the diamine is a C ₄ -C ₈ α,ω-diamine.

The apparatus of any one of statements 82 to 84, wherein the diamine is hexamethylenediamine.

The device of any one of claims 44 to 85, wherein the polyamine is nylon 6,6.

10‧‧‧Reservoir

12‧‧‧ pipeline

14‧‧‧Valve

16‧‧‧ pipeline

18‧‧‧Evaporator

22‧‧‧ pipeline

24‧‧‧ valve

26‧‧‧Exhaust line

28‧‧‧ pipeline

30‧‧‧ valve

32‧‧‧ pipeline

34‧‧‧ tubular reactor

36‧‧‧ pipeline

38‧‧‧Valves

40‧‧‧ pipeline

42‧‧‧flasher

44‧‧‧ pipeline

46‧‧‧Valves

48‧‧‧ pipeline

50‧‧‧ Finishing machine

54‧‧‧ pipeline

56‧‧‧ valve

58‧‧‧ pipeline

62‧‧‧Exhaust port

64‧‧‧ pipeline

66‧‧‧Management

68‧‧‧ pipeline

70‧‧‧Reservoir

72‧‧‧ pipeline

74‧‧‧Exhaust line

76‧‧‧Valves

78‧‧‧ pipeline

80‧‧‧Rectifier

81‧‧‧Rectification zone

82‧‧‧Partial condenser-preheater

83‧‧‧Condenser

84‧‧‧ pipeline

86‧‧‧ valve

88‧‧‧ pipeline

90‧‧‧Filter or adsorption assembly

92‧‧‧ pipeline

94‧‧‧Valve

96‧‧‧ pipeline

98‧‧‧Unit/pipeline

100‧‧‧ storage container

T1‧‧‧Tray

T2‧‧‧Tray

T3‧‧‧Tray

T4‧‧‧Tray

T5‧‧‧Tray

T6‧‧‧Tray

T7‧‧‧Tray

T8‧‧‧Tray

Claims (42)

An apparatus for making polyamine, comprising: a tubular reactor configured to further polymerize a partially polymerized polyamine to thereby produce water having a substantially gaseous phase; in fluid communication with the tubular reactor a rectification column configured to remove one or more of a diamine, a carboxylic acid, and a polyamidamine to provide purified water having a substantially gaseous phase; a condensing assembly in fluid communication with the rectification column Configuring to receive the water having substantially gaseous phase and converting the water having substantially gaseous phase into water having a substantially liquid phase; and a network of pipes configured to have substantially The liquid phase water is returned to at least one component of the polyamine production system. The device of claim 1, wherein the device is configured to remove at least one impurity from at least one of the purified water having a substantially liquid phase and the water having a substantially gaseous phase, wherein the impurity comprises causing gelation At least one of a material and a polyamide degradation material. The device of claim 2, wherein the impurity comprises at least one selected from the group consisting of iron, cobalt, manganese, magnesium, titanium, cerium oxide, cyclopentanone, hexamethyleneimine, and bis(hexamethylene) ) Triamine. The device of claim 3, wherein the impurity comprises iron. The device of claim 1, wherein the device is configured to return water having a substantially liquid phase to the reservoir or the tubular reactor. The device of claim 5, wherein the device is operated at a water circulation ratio of at least 0.2:1. The device of claim 1, wherein the device is configured to reuse the substance Purified water in the upper liquid phase. The apparatus of claim 7, wherein reusing the purified water having a substantially liquid phase comprises returning the purified water having a substantially liquid phase to one or more components of the polyamide synthesis process. The apparatus of claim 1, wherein the rectification column comprises a rectification zone. The apparatus of claim 9, wherein the rectification column comprises one or more condensers. The device of claim 10, wherein the one or more condensers are configured to transfer heat to one or more components of the polyamide synthesis process. The apparatus of claim 1 wherein the condensing assembly is configured to convert at least 80% of the water having substantially gaseous phase to water having a substantially liquid phase. The device of claim 1, further comprising a filter or adsorption assembly having water passing through the substantially liquid phase, wherein the filter or adsorption assembly comprises at least one activated carbon adsorbent bed, and the filter or adsorption The assembly provides substantially purified water having a substantially liquid phase. The apparatus of claim 13 wherein the substantially purified liquid having a substantially liquid phase is of sufficient purity to be converted and used as a vapor source in the polyamido synthesis process. The apparatus of claim 1 wherein the substantially gaseous phase water is of sufficient purity to be used as a vapor source in the polyamide synthesis process. The apparatus of claim 1, wherein the one or more of the diamine, carboxylic acid or polyamine removed in the rectification column is reused. The apparatus of claim 16, wherein the one or more of the diamine, carboxylic acid or polyamine removed in the rectification column comprises a diamine, a carboxy group which is removed in the rectification column. The one or more of the acid or polyamine is returned to one or more components of the polyamine production system. The device of claim 17, wherein the one or more components of the polyamine generating system comprise at least one of an evaporator, the tubular reactor, and a salt trigger. The apparatus of claim 1 wherein the tubular reactor has a length of from about 50 to about 300 m. The device of claim 1 wherein the tubular reactor has a length of from about 75 to about 125 m. The device of claim 1, wherein the tubular reactor has an inner diameter of from about 10 cm to about 80 cm. The device of claim 1 wherein the tubular reactor further comprises a jacket. The apparatus of claim 1 wherein the tubular reactor has a length to diameter ratio of from about 50 to about 2,500. The apparatus of claim 1 wherein the tubular reactor has a length to diameter ratio of from about 100 to about 500. The device of claim 1 wherein the tubular reactor further comprises an exhaust port along its length. The device of claim 25, wherein the tubular reactor comprises from about 5 to about 50 vents. The device of claim 25, wherein the tubular reactor comprises from about 10 to about 25 vents. The apparatus of claim 24, wherein the tubular reactor comprises about one venting port on average from about 2 m to about 15 m along the length of the tubular reactor. The apparatus of claim 24, wherein the tubular reactor comprises about 1 venting port on average from about 3 m to about 9 m along the length of the tubular reactor. The apparatus of claim 24, wherein the tubular reactor comprises an average spacing between the vents of between about 2 m and about 15 m along the length of the tubular reactor. The apparatus of claim 24, the tubular reactor comprising an average spacing between the vents of between about 3 m and about 9 m along the length of the tubular reactor. The device of claim 1 wherein the tubular reactor comprises from about 75 to about 125 m long The tubular reactor comprises an inner diameter of from about 25 cm to about 60 cm, the tubular reactor comprises a length/diameter (L/ID) of from about 100 to about 500, and wherein the tubular reactor comprises from about 10 to about about along its length. 25 exhaust ports. The device of claim 1, wherein the partially polymerized polyamine comprises a monomer of a C ₄ -C ₁₈ α,ω-dicarboxylic acid. The device of claim 33, wherein the dicarboxylic acid is a C ₄ -C ₁₀ α,ω-dicarboxylic acid. The device of claim 33, wherein the dicarboxylic acid is a C ₄ -C ₈ α,ω-dicarboxylic acid. The device of claim 33, wherein the dicarboxylic acid is adipic acid. The device of claim 1, wherein the partially polymerized polyamine comprises a monomer of a C ₄ -C ₁₈ α,ω-diamine. The device of claim 37, wherein the diamine is a C ₄ -C ₁₀ α,ω-diamine. The device of claim 37, wherein the diamine is a C ₄ -C ₈ α,ω-diamine. The device of claim 37, wherein the diamine is hexamethylenediamine. The device of claim 1, wherein the polyamine is nylon 6,6. A system comprising: a tubular reactor configured to further polymerize a partially polymerized polyamine to thereby produce water having a substantially gaseous phase; a rectification column in fluid communication with the tubular reactor, Configuring to remove one or more of a diamine, a carboxylic acid, and a polyamine to provide purified water having a substantially gaseous phase; a condensing assembly in fluid communication with the rectification column configured to receive The water having substantially gaseous phase and converting the water having substantially gaseous phase into water having a substantially liquid phase; and a network of pipes configured to return water having a substantially liquid phase to the poly At least one component of the guanamine production system.