CN112592602B - Continuous production system of nano disperse dye - Google Patents
Continuous production system of nano disperse dye Download PDFInfo
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- CN112592602B CN112592602B CN202011214572.1A CN202011214572A CN112592602B CN 112592602 B CN112592602 B CN 112592602B CN 202011214572 A CN202011214572 A CN 202011214572A CN 112592602 B CN112592602 B CN 112592602B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00081—Tubes
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Abstract
The invention provides a continuous production system of a nano disperse dye, aiming at the characteristics of easy blockage of disperse dye materials and the like, a pre-mixing vent pipeline of a feeding pipe and a vent pipeline at an inlet and an outlet of a spiral coil are designed, the vent pipeline is connected with a diazotization reaction raw material feeding port, and the outlet is connected with a supergravity coupling reactor. Because the release vent pipe is arranged at the local part of the vent pipe, the vent pipe can effectively solve the problem of material feeding blockage, and is favorable for the uniform feeding of materials into the spiral tube reactor to carry out diazotization reaction.
Description
Technical Field
The invention relates to the technical field of nano disperse dye preparation. And more particularly, to a continuous production system of nano disperse dyes.
Background
The disperse dye is a special dye for polyester fiber and acetate fiber, and is a dye with the largest yield in all the dye varieties in China at present. In industrial production, the azo disperse dyes are usually carried out in a stirred tank reactor in a batch operation mode, and due to the complexity of the synthesis process of the azo dyes and the limitation of the volume of the stirred tank, materials are difficult to uniformly mix, so that the production rate of the dyes is reduced, the difference between batches of the dyes is large, and the like, and the application of a post-treatment agent of the dyes is inconvenient. And the particle size of the dye particles synthesized in the stirred tank reactor is large, and the dye particles cannot be directly used for dyeing. The dye product needs to be post-treated, so that the particle size of the dye particles is reduced to about 1 mu m or even smaller, and the dye becomes a standardized commercial dye.
Therefore, it is highly desirable to provide a continuous production system for nano disperse dyes.
Disclosure of Invention
In view of this, in order to solve the problem that an effective continuous production system for azo disperse dyes is lacked at present, the invention provides a continuous production system for nano disperse dyes.
In certain embodiments, a system for continuous production of nanodispersed dyes, the system comprising:
a condensation reaction unit comprising a condensation reaction tank for generating a coupling component;
a diazotization reaction unit, the diazotization reaction unit comprising:
a pre-mix assembly for pre-mixing the heavy nitrogen component and the diazonium reagent, an
The spiral coil reactor is communicated with the premixing component so that the premixed reaction solution can perform diazotization reaction in the spiral coil reactor to generate diazonium salt;
the system further comprises:
the hypergravity coupling reaction unit is communicated with the diazotization reaction unit and the condensation reaction unit and is used for performing coupling reaction on diazonium salt and coupling components under a hypergravity environment to generate the nano disperse dye; and
a blowdown assembly connected to the inlet and outlet of the helical coil reactor, the blowdown assembly comprising a first blowdown conduit having a set height and opening upwardly;
The premixing assembly comprises two inlet pipelines and an outlet pipeline, a second emptying pipeline is arranged on the pipe wall of each inlet pipeline, and an opening of the second emptying pipeline is arranged upwards.
In a preferred embodiment, the second blow-down duct includes a plurality of root bases formed by respective duct walls extending outwardly, a connecting portion connected to each root base, and an extension portion connected to a free end of the uppermost root base and extending upwardly, the opening of the extension portion being disposed upwardly.
In a preferred embodiment, the root base comprises two, the two root bases, the connecting portion and the corresponding tube wall forming a parallelogram structure.
In a preferred embodiment, the root parts comprise at least two, and in two adjacent root parts, one end of the connecting part is connected with the free end of the next adjacent root part, and the other end is connected with the middle side wall of the last adjacent root part.
In a preferred embodiment, the root base is angled between 30-60 ° from the corresponding tube wall.
In a preferred embodiment, the first vent conduit and the second vent conduit have an inner diameter less than the minimum particle size of the reaction mass.
In a preferred embodiment, the height of the first vent pipe and the second vent pipe is greater than the height corresponding to the maximum pressure difference of the reaction liquid.
In certain embodiments, the hypergravity coupling reaction unit comprises:
the supergravity reactor is communicated with the spiral coil reactor;
a stirred tank reactor in series with the hypergravity reactor, an
A pump for pumping diazonium salt after diazonium reaction into the super-gravity rotating packed bed reactor and a pump for circularly pumping the diazonium salt back to the super-gravity reactor at the discharge hole of the stirred tank reactor.
In certain embodiments, the system further comprises a heat exchange unit for controlling the temperature within the spiral coil reactor reaction chamber and the temperature within the supergravity coupled reaction unit reaction chamber.
In certain embodiments, the heat exchange unit comprises:
the pipeline jacket is sleeved outside the pipeline of the spiral coil reactor and is provided with a cavity into which liquid can be introduced;
the shell jacket is sleeved on the outer side of a shell of the reaction cavity formed by the supergravity reactor and is provided with a cavity into which liquid can be introduced; and
and the heat exchange device is used for heating or cooling liquid introduced into the pipeline jacket and the shell jacket.
The invention has the following beneficial effects:
the invention provides a continuous production system of nano disperse dye, which combines a spiral coil reactor with a hypergravity technology to distinguish and treat diazotization reaction and coupling reaction, wherein the diazotization reaction is carried out in the spiral coil reactor, and the hypergravity reactor is used for the coupling reaction and can greatly improve the conversion rate and the quality of products. And the spiral coil reactor can accurately control the temperature, avoid the decomposition of the diazonium salt, and under the cooperation, because the temperature control is accurate, the decomposition of the diazonium salt is extremely little, can not influence the subsequent coupling reaction, so the concentration of the diazonium salt can be maintained in a higher range when the continuous production is ensured, thereby the performance of the nano disperse dye in the same batch is ensured to be close to or the same, and the industrial actual requirement is met. Furthermore, aiming at the characteristics of easy blockage of the disperse dye material and the like, a pre-mixing vent pipeline of a feed pipe and a vent pipeline of an inlet and an outlet of a spiral coil are designed, the vent pipeline is connected with a feed inlet of the diazotization reaction raw material, and the outlet of the vent pipeline is connected with a supergravity coupling reactor. Because the local part of the vent pipeline is provided with the pressure relief vent pipeline, the vent pipeline can effectively solve the problem of material feeding blockage and is beneficial to the uniform feeding of materials into the spiral tube reactor for diazotization reaction.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic diagram of a continuous structure of azo nanodispersed dye using supergravity in the practice of the present invention.
FIG. 2 shows a schematic of the construction of a vent valve in the practice of the invention.
FIG. 3 shows UV spectra of azo nanodispersed dye prepared in example 1 in accordance with the practice of the invention.
Fig. 4a shows a scanning electron micrograph of the nanodispersed dye prepared in example 2 according to the practice of the present invention. Fig. 4b shows a distribution of the average particle size of the nano-disperse dye prepared in example 2 in the practice of the present invention.
Fig. 5a shows a scanning electron micrograph of the nanodispersed dye prepared in example 3 in the practice of the present invention. Fig. 5b shows a distribution diagram of the average particle size of the nano-disperse dye prepared in example 3 in the practice of the present invention.
FIG. 6a shows a scanning electron micrograph of a disperse dye prepared in comparative example 1 in the practice of the present invention.
FIG. 6b is a graph showing the distribution of the average particle diameter of the disperse dye prepared in comparative example 1 in the practice of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The disperse dye is a special dye for polyester fiber and acetate fiber, and is a dye with the largest yield in all the dye varieties in China at present. In industrial production, the azo disperse dye is usually carried out in a stirred tank reactor in a batch operation mode, and due to the complexity of the synthesis process of the azo dye and the limitation of the volume of the stirred tank, materials are difficult to uniformly mix, so that the production efficiency of the dye is reduced, the difference among dye batches is large, and the like, and the application of a post-treatment agent of the dye is inconvenient. And the particle size of the dye particles synthesized in the stirred tank reactor is large, and the dye particles cannot be directly used for dyeing. The dye product needs to be post-treated, so that the particle size of the dye particles is reduced to about 1 mu m or even smaller, and the dye becomes a standardized commercial dye.
The synthesis process of the azo dye is complex, the heat release in the diazotization reaction process is severe, the local heat dissipation of the feed liquid is poor due to the poor mass transfer and heat transfer performance of the batch reactor in industrial production, the temperature is rapidly increased due to the diazotization reaction characteristics and industrial mass production, and the diazonium salt is extremely unstable at high temperature and has explosion danger. Moreover, the time period of the batch production of the disperse dye by the stirring kettle is long, the time of a single batch can be as long as 4-5 hours or even longer, the investment of manpower and material resources in industrial production is increased, the industrial production cost is increased, and the industrial economic benefit is reduced.
Most organic synthesis experiments have potential safety hazards such as toxicity, corrosivity and explosion, and a continuous synthesis disperse dye production system is introduced in order to reduce safety accidents in industrial production. The system effectively overcomes the defects caused by the production of the stirring kettle, and prepares the azo disperse dye with bright color, high purity and high yield through the continuous production system. Compared with an intermittent stirred tank operation mode, the method greatly reduces the reaction synthesis time, reduces the investment of manpower and material resources and potential safety hazards of industrial production, and brings huge benefits for industrial production.
In view of the above, the present invention firstly provides a continuous production system for nano disperse dyes, which comprises: a condensation reaction unit comprising a condensation reaction tank for generating a coupling component; a diazotization reaction unit, the diazotization reaction unit comprising: the pre-mixing component is used for pre-mixing a heavy nitrogen component and a diazo reagent, and the spiral coil reactor is communicated with the pre-mixing component so as to enable the pre-mixed reaction solution to carry out diazotization reaction in the spiral coil reactor to generate diazonium salt; the system further comprises: the hypergravity coupling reaction unit is communicated with the diazotization reaction unit and the condensation reaction unit and is used for performing coupling reaction on diazonium salt and coupling components under a hypergravity environment to generate the nano disperse dye; and a vent assembly connected to the inlet and outlet of the spiral coil reactor, the vent assembly comprising a first vent conduit having a set height and opening upwardly; the premixing assembly comprises two inlet pipelines and an outlet pipeline, a second emptying pipeline is arranged on the pipe wall of each inlet pipeline, and the opening of each emptying pipeline is arranged upwards.
The invention provides a continuous production system of nano disperse dyes, which combines a spiral coil reactor with a hypergravity technology to distinguish diazotization reaction and coupling reaction, wherein the diazotization reaction is carried out in the spiral coil reactor, and the hypergravity reactor is used for the coupling reaction, so that the conversion rate and the quality of products can be improved to a great extent. And the spiral coil reactor can accurately control the temperature, avoid the decomposition of the diazonium salt, and under the cooperation, because the temperature control is accurate, the decomposition of the diazonium salt is extremely little, can not influence the subsequent coupling reaction, so the concentration of the diazonium salt can be maintained in a higher range when the continuous production is ensured, thereby the performance of the nano disperse dye in the same batch is ensured to be close to or the same, and the industrial actual requirement is met. Furthermore, aiming at the characteristics of easy blockage of disperse dye materials and the like, a feed pipe premixing vent pipeline is designed, the vent pipeline is connected with a diazotization reaction raw material feed inlet, and an outlet is connected with a supergravity coupling reactor. Because the release vent pipe is arranged at the local part of the vent pipe, the vent pipe can effectively solve the problem of material feeding blockage, and is favorable for the uniform feeding of materials into the spiral tube reactor to carry out diazotization reaction.
In some embodiments, the supergravity reactor may be a supergravity machine such as a rotating packed bed, a stator and a rotor, where the rotating packed bed includes a housing and a rotating chamber, the rotating chamber is driven by a motor to rotate, and a filler is disposed in the rotating chamber, and the filler is used to cut the liquid into micro elements (liquid droplets or) with micro-nano dimensions such as a wire mesh filler, and the invention is not limited thereto. The difference between the stator and the rotor and the rotating packed bed is that the liquid is cut into micro-elements (liquid drops or liquid films) with micro-nano scale through cutting between the fixed stator column and the rotating rotor.
Further, in a preferred embodiment, the system further comprises: and the ultrasonic feeder is used for feeding ultrasonic waves into the spiral coil reactor and the hypergravity coupling reaction unit respectively, wherein the ultrasonic intensities fed into the spiral coil reactor and the hypergravity coupling reaction unit are the same or different.
The invention firstly adopts a spiral coil reactor which is locally provided with a blow-down valve component to be applied to diazotization reaction, because the reaction cavity of the spiral coil reactor is in a spiral coil shape, when temperature control is needed, a heating medium or a cooling medium can be introduced into a jacket which is sleeved on the outer wall of the coil, the diameter of the tube body of the spiral coil is small, and the side wall of the tube body is thin, so that the jacket arranged on the outer side wall can directly transmit or remove heat out of a reaction system through the wall of a metal tube in a very short time, the tube diameter is small, and the heat conduction of a reaction solution in the tube body is uniform, thereby achieving the purpose of accurately controlling the temperature, accurately controlling the temperature rise and fall of the system and greatly reducing the decomposition of diazonium salt.
In addition, aiming at the characteristics of easy blockage of the disperse dye material and the like, the invention designs the feed pipe premixing vent valve, the vent valve is connected with a diazotization reaction raw material feed inlet, and the outlet is connected with the supergravity coupling reactor. Because the local relief vent valve that is equipped with of blow-down valve, this blow-down valve can solve material feeding jam problem effectively, is favorable to the material evenly to get into the helical tube reactor and carries out diazotization reaction.
In one embodiment, as shown in FIG. 1, FIG. 1 shows a continuous azo disperse dye production system using supergravity, which comprises a diazo component mixing tank 1, a diazo reagent raw material tank 2, a pump 3, a pump 4, a regulating valve 5, a regulating valve 6, a vent valve assembly 7, a supergravity reactor 8, a diazo reagent raw material tank 9, a pump 10, a regulating valve 11, a vent valve assembly 12, a vent valve assembly 13, a spiral tube reactor 14, a vent valve assembly 15, a coupling component storage tank 16, a pump 17, a regulating valve 18, a supergravity reactor 19, a vent valve assembly 20, a pump 21, a stirring tank 22, a holding reaction tank 23, and a regulating valve 24. Wherein the diazo component mixing tank 1 is in communication with the supergravity assembly 8 via pump 3 to pass the diazo component to the vent valve assembly 12. The diazo reagent raw material tank 2 is communicated with the supergravity assembly 8 through a pump 4, so that the diazo reagent is introduced into an emptying valve assembly 12, and then the diazo reaction is carried out in a spiral tube reactor 14. The coupling component storage tank 16 is connected with the supergravity reactor 19 through a pump 17, the diazonium salt solution and the coupling component are pumped into the supergravity reactor 19 through the emptying valve assembly 15, the dye product flows into the stirring kettle 22 through the emptying valve assembly 19, the heat-preservation reaction is carried out through the heat-preservation stirring kettle 23, and finally the product is subjected to heat filtration, drying and grinding treatment to obtain the nano-scale disperse dye.
As shown in fig. 2, the second vent pipe includes a plurality of root bases formed by extending the corresponding pipe walls outward, a connecting portion connected to each root base, and an extending portion connected to the free end of the uppermost root base and extending upward, the opening of the extending portion being directed upward. In this way, the backflow of liquid can be avoided to the maximum extent,
in a preferred embodiment, the root base comprises two, the two root bases, the connecting portion and the corresponding tube wall forming a parallelogram structure.
The root base part comprises at least two root base parts, wherein in the two adjacent root base parts, one end of the connecting part is connected with the free end of the next adjacent base part, and the other end of the connecting part is connected with the side wall of the middle part of the last adjacent base part.
The root base and the corresponding pipe wall form an included angle of 30-60 degrees. For example, 45 degrees, the component is connected to a feeding pipe in a communicating mode, and the opening angle of the component is 45 degrees by adopting a parallelogram design, so that liquid backflow is facilitated.
The inner diameter of the first emptying pipeline and the inner diameter of the second emptying pipeline are smaller than the minimum particle size of the reaction materials. Thus avoiding the particle size from jumping out of the emptying pipeline.
The height of the first emptying pipeline and the height of the second emptying pipeline are larger than the height corresponding to the maximum pressure difference of the reaction liquid. To ensure that the liquid does not flow back.
Specifically, as shown in fig. 2, the vent valve includes an upper and a lower communicating exhaust valves, the interior of the vent valve is communicated to release pressure, the communicating interface is smaller than the average particle size of the material, and the material tends to be in a solution state after undergoing a diazotization reaction by the spiral tube.
In some embodiments, the rotating device in the supergravity reactor may be a rotating device such as a rotating packed bed, a rotating packed bed series micro reactor casing, a stator-rotor series micro reactor casing, and the like, where the rotating packed bed includes a housing and a rotating chamber, the rotating chamber is driven by a motor to rotate, and a filler is disposed in the rotating chamber, and the filler is used to cut liquid into micro elements (liquid droplets or liquid filaments) with micro-nano dimensions, such as a stainless steel wire mesh filler, a stainless steel structured filler, and the like. The difference between the stator and the rotor and the rotating packed bed is that the liquid is cut into micro-elements (liquid drops or liquid films) with micro-nano scale by cutting between the fixed stator column and the rotating rotor.
This embodiment includes a hypergravity reactor 12 that can be used for continuous production of diazotization-coupling reactions. For example, orange azo disperse orange 25 dye, the synthesis of which mainly comprises two steps, diazotization and coupling.
In some embodiments, the diazotization reaction equation is:
the coupling reaction equation is:
in some embodiments, the system further comprises a heat exchange unit, which can heat or cool the tube of the helical coil reactor, for example, the outer wall of the tube of the helical coil reactor is sleeved with a heat exchange jacket (not shown in the figure). Because the diameter of the tube body is small, the heat exchange jacket can quickly and uniformly diffuse heat energy or cold energy into the cavity in the whole tube body.
In some embodiments, the helical coils in the helical coil reactor are made of polyurethane. This prevents corrosion while having a small influence on heat conduction. Of course, as a different embodiment from this example, the inner surface of the helical coil in the helical coil reactor is lined with a layer of polyurethane material. Also, to avoid the effects of corrosion, the pump described above is a peristaltic pump, the feed tube chosen being of the polytetrafluoro type. In some preferred embodiments, the heat exchange unit comprises a pipe jacket sleeved outside the pipe of the spiral coil reactor, and the pipe jacket is provided with a cavity into which a liquid can be introduced and a heat exchange device for heating or cooling the liquid introduced into the pipe jacket. Namely, the tube body of the spiral coil reactor is heated or cooled by liquid so as to realize accurate control of the temperature. In addition, the heating or cooling medium in the pipe jacket may be water, alcohol, salt solution, or oil, which is not limited in the present invention.
In some embodiments, the system further comprises a heat exchange unit, which can heat or cool the tube of the helical coil reactor, for example, the outer wall of the tube of the helical coil reactor is sleeved with a heat exchange jacket (not shown in the figure). Because the diameter of the tube body is small, the heat exchange jacket can quickly and uniformly diffuse heat energy or cold energy into the cavity in the whole tube body.
In some embodiments, the helical coils in the helical coil reactor are made of polyurethane. This prevents corrosion while having a small influence on heat conduction.
Of course, as a different embodiment from this example, the inner surface of the helical coil in the helical coil reactor is lined with a layer of polyurethane material.
Similarly, to avoid the effects of corrosion, the pump described above is a teflon pump.
In some preferred embodiments, the heat exchange unit comprises a pipe jacket sleeved outside the pipe of the spiral coil reactor, and the pipe jacket is provided with a cavity into which liquid can be introduced; and a heat exchange device for heating or cooling medium to be introduced into the liquid in the pipe jacket. Namely, the tube body of the spiral coil reactor is heated or cooled by liquid so as to realize accurate control of the temperature.
In addition, the heating or cooling medium in the pipe jacket may be water, alcohol, salt solution, or oil, which is not limited in the present invention.
Diazotization reaction occurs in the spiral coil reactor to generate diazonium salt, and the spiral coil reactor can accurately control the temperature, so that the decomposition of the diazonium salt can be avoided, the diazonium salt is kept stable and unchanged in subsequent feeding concentration in the continuous production of the same batch, the product quality is stable, and the product performance of the same batch has small difference.
It should be noted that the liquid distributors of the supergravity reactor in this embodiment are two feeding streams in the figure, which are injected separately, but in other embodiments, the injection ports of the liquid distributors may also be provided with a premixing region, and further, before injection, the diazonium salt solution and the coupling component enter the supergravity reactor through the first liquid inlet and the second liquid inlet, and are premixed in the premixing region of the liquid distributors, and then injected into the reaction cavity, which is not further limited by the present invention.
It should be noted that, the coupling reaction also needs to ensure a certain temperature, but the coupling reaction has a lower temperature control requirement than the diazotization reaction, and experiments prove that the supergravity reactor is more advantageous to the coupling reaction than the spiral coil reactor.
In addition, as the coupling reaction needs to ensure a certain temperature, the shell of the hypergravity reactor can be heated or cooled by the heat exchange unit, so that the temperature can be controlled.
In some embodiments, the heat exchange unit further comprises a shell jacket sleeved on the reaction cavity formed by the supergravity reactor, and the shell jacket is provided with a cavity into which liquid can be introduced. Further, the heat exchange means may heat or cool the liquid in the pipe jacket and the shell jacket simultaneously. Furthermore, the pipe jacket is communicated with the shell jacket, and the heat exchange medium can flow into the shell jacket from the pipe jacket without limitation.
In some embodiments, the high-gravity reactor may be a high-gravity rotating bed reactor or a stator-rotor reactor, and it is understood by those skilled in the art that the specific type of the high-gravity reactor is not limited by the present invention, and any one of the high-gravity reactors in the prior art may be arbitrarily configured as required. It should be noted that the liquid distributors of the supergravity reactor in this embodiment are two feeding streams in the figure, which are injected separately, but in other embodiments, the injection ports of the liquid distributors may also be provided with a premixing region, and further, before injection, the diazonium salt solution and the coupling component enter the supergravity reactor through the first liquid inlet and the second liquid inlet, and are premixed in the premixing region of the liquid distributors, and then injected into the reaction cavity, which is not further limited by the present invention.
In some embodiments, the heat exchange unit further comprises an outer shell jacket sleeved on the reaction cavity formed in the supergravity reactor, and the outer shell jacket is provided with a cavity into which liquid can be introduced. Further, the heat exchange means may heat or cool the liquid in both the pipe jacket and the shell jacket. Furthermore, the pipe jacket is communicated with the shell jacket, and the heat exchange medium can flow into the shell jacket from the pipe jacket without limitation.
In some embodiments, the diazo components comprise p-nitroaniline and nitrite, the diazotizing agent comprises hydrochloric acid, and the coupling component comprises N-ethyl-N-cyanoethylaniline, acetic acid, and a dispersant, such that the azo disperse dye produced by the above-described system of the present invention is disperse orange 25.
In some specific examples, the dispersant consists essentially of: tween 20, tween 40, tween 60, tween 80, sodium dodecylbenzenesulfonate, hydroxymethyl cellulose, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, NNO, OP-10, sodium lignosulfonate, polyoxyethylene castor oil, and/or red oil, without limitation. If the selected dispersing agent is not suitable, serious agglomeration phenomenon can occur, so that the system is unstable, and better nano-scale disperse dye cannot be obtained.
Of course, the continuous production system of the present invention is not limited to the two specific examples, and it should be understood that the present system can be applied to any disperse azo dyes that undergo diazotization and coupling reactions, and the present invention is not exhaustive herein.
The continuous production of azo nano disperse dye provided by the invention is described in detail by combining two specific examples.
EXAMPLE 1 continuous production of azo nanodispersed dyes
In this example, the diazo components include paranitroaniline and nitrite, the diazotizing agent includes hydrochloric acid, and the coupling components include N-ethyl-N-cyanoethylaniline and acetic acid.
The diazotization reaction process comprises the following steps: pre-mixing the mixture of paranitroaniline and nitrite with hydrochloric acid solution by a pre-mixing component, as shown in figure 2, then respectively and continuously feeding into a spiral coil reactor by pipelines to obtain diazonium salt solution or suspension, carrying out diazotization reaction at-5 ℃ to 30 ℃, preferably at 5 ℃ to 10 ℃, wherein the molar ratio of hydrogen ions of diazotization reaction hydrochloric acid to paranitroaniline is
Preferably 2.8:1, wherein the molar ratio of the sodium nitrite to the paranitroaniline is 1-2: 1, preferably 1.07:1, and the feeding flow rate is 50-300 mL/min, preferably 50-120 mL/min.
The coupling reaction process is as follows: continuously pumping the diazonium salt and the coupling component into a supergravity reactor respectively, and generating a coupling product after high-speed rotation, wherein the reaction temperature is 0-30 ℃, and preferably 5-10 ℃; preferably at a pH of
Preference is given to
The rotational speed of the hypergravity reactor is
Preference is given to
The feeding speed is 50-300 mL/min, preferably 50-100 mL/min.
And (3) a heat preservation reaction stage: and pumping the feed liquid obtained by the supergravity coupling into a heat-preservation reaction kettle, and carrying out heat-preservation reaction to obtain the final disperse orange 25 dye. The reaction temperature is 50-150 ℃, and preferably 60-70 ℃; the reaction time is 0.5-2.5 h, preferably 0.5-1 h.
A continuous preparation method of disperse dye by using supergravity is characterized by comprising the following steps:
s11, the mixed solution of 0.02mol of paranitroaniline and 0.0214mol of nitrite and 0.056mol of hydrochloric acid are introduced into a vent valve assembly (figure two) for premixing.
S12: and respectively introducing the mixture of the paranitroaniline nitrite and hydrochloric acid into a spiral tube reactor to carry out diazotization reaction to generate light yellow paranitroaniline diazonium salt suspension.
S13 reaction of the above-mentioned p-nitroaniline diazonium salt with the coupling component (acetic acid) in a molar ratio of 1: and (3) introducing the mixture into a hypergravity coupling reaction unit in a proportion of 1.01 to perform coupling reaction, thereby obtaining the disperse orange 25 dye.
S14: and (3) introducing the dye liquid obtained by the coupling reaction into a heat-preservation reaction kettle, and carrying out heat preservation reaction for one hour at the temperature of 60-70 ℃ to obtain the final disperse orange 25 dye.
S15: the obtained feed liquid is filtered when the feed liquid is hot, washed to be neutral, refined and dried to obtain the disperse orange 25 dye, the yield can reach 99.5 percent, and the purity can reach 99.9 percent.
Compared with the supergravity continuous synthesis of disperse dyes, when the same yield and purity are achieved, the single-batch synthesis time of the stirred tank process is up to 4 hours, and the industrial energy consumption is too high.
EXAMPLE 2 continuous preparation of Nano-disperse dyes
In this example, the diazo components include paranitroaniline and nitrite, the diazotizing agent includes hydrochloric acid, and the coupling component includes N-ethyl-N-cyanoethylaniline, acetic acid, and a dispersant.
A method for continuously preparing a nano disperse dye by using supergravity is characterized by comprising the following steps:
the diazotization reaction process comprises the following steps: pre-mixing the mixed solution of paranitroaniline and nitrite with hydrochloric acid solution by a pre-mixing component as shown in figure 2, and then continuously and respectively mixing the mixed solution of paranitroaniline and nitrite with the hydrochloric acid solution by pipelinesFeeding into a spiral coil reactor to obtain a diazonium salt solution or suspension, wherein the diazotization reaction is carried out at a temperature of between 5 ℃ below zero and 30 ℃, preferably between 5 ℃ and 10 ℃, and the molar ratio of hydrogen ions of diazotization reaction hydrochloric acid to paranitroaniline is between 
Preferably 2.8:1, wherein the molar ratio of the sodium nitrite to the paranitroaniline is 1-2: 1, preferably 1.07:1, and the feeding flow rate is 50-300 mL/min, preferably 50-120 mL/min.
The coupling reaction process is as follows: weighing 0.004mol of dispersant NNO, dissolving in the coupling component to prepare a modified coupling component, respectively and continuously pumping the diazonium salt and the coupling component into a supergravity reactor, and generating a coupling product after high-speed rotation, wherein the reaction temperature is 0-30 ℃, and preferably 5-10 ℃; preferably at a pH of
Preference is given to
The rotational speed of the hypergravity reactor is
Preference is given to
The feeding speed is 50-300 mL/min, preferably 50-100 mL/min.
And (3) a heat preservation reaction stage: and pumping the feed liquid obtained by the supergravity coupling into a heat-preservation reaction kettle, and carrying out heat-preservation reaction to obtain the final disperse orange 25 dye. The reaction temperature is 50-150 ℃, and preferably 60-70 ℃; the reaction time is 0.5-2.5 h, preferably 0.5-1 h.
FIG. 4b shows a scanning electron micrograph of the nanodispersed dye prepared according to example 2 of the present invention, from which it can be seen that the average particle size of the nanodispersed dye prepared is 300 nm.
EXAMPLE 3 continuous preparation of a Nano-disperse dye
In this example, the diazo components include paranitroaniline and nitrite, the diazotizing agent includes hydrochloric acid, and the coupling component includes N-ethyl-N-cyanoethylaniline, acetic acid, and a dispersant.
A continuous preparation method of a nano disperse dye by using supergravity is characterized by comprising the following steps:
the diazotization reaction process comprises the following steps: pre-mixing the mixture of paranitroaniline and nitrite with hydrochloric acid solution by a pre-mixing component, as shown in figure 2, then respectively and continuously feeding into a spiral coil reactor by pipelines to obtain diazonium salt solution or suspension, carrying out diazotization reaction at-5 ℃ to +30 ℃, preferably at 5 ℃ to 10 ℃, wherein the molar ratio of hydrogen ions of the hydrochloric acid of the diazotization reaction to the paranitroaniline is
Preferably 2.8:1, wherein the molar ratio of the sodium nitrite to the paranitroaniline is 1-2: 1, preferably 1.07:1, and the feeding flow rate is 50-300 mL/min, preferably 50-120 mL/min.
The coupling reaction process is as follows: weighing 0.004mol of Tween serving as a dispersant and a sodium dodecyl benzene sulfonate compounded dispersant, dissolving the Tween and the sodium dodecyl benzene sulfonate compounded dispersant in a coupling component to prepare a modified coupling component, respectively and continuously pumping a diazonium salt and the coupling component into a supergravity reactor, and generating a coupling product after high-speed rotation, wherein the reaction temperature is 0-30 ℃, and preferably 5-10 ℃; preferably at a pH of
Preference is given to
The rotational speed of the hypergravity reactor is
Preference is given to
The feeding speed is 50-300 mL/min, preferably 50-100 mL/min.
And (3) a heat preservation reaction stage: pumping the feed liquid obtained by the supergravity coupling into a heat-preservation reaction kettle, and carrying out heat-preservation reaction to obtain the final disperse orange 25 dye. The reaction temperature is 50-150 ℃, and preferably 60-70 ℃; the reaction time is 0.5-2.5 h, preferably 0.5-1 h.
FIG. 5b shows a scanning electron microscope image of the nanodispersion dye prepared in example 3 of the present invention, from which it can be seen that the average particle size of the prepared nanodispersion dye is 80 nm.
Comparative example 1 preparation method of disperse dye synthesized by stirring kettle
In this example, the diazo components include paranitroaniline and nitrite, the diazotizing agent includes hydrochloric acid, and the coupling components include N-ethyl-N-cyanoethylaniline and acetic acid.
A continuous preparation method of disperse dye by using a stirring kettle is characterized by comprising the following steps:
the diazotization reaction process comprises the following steps: pre-mixing p-nitroaniline and hydrochloric acid solution in a stirring kettle, then dropwise adding sodium nitrite through a separating funnel to obtain diazonium salt solution or suspension, carrying out diazotization at-5 ℃ to 30 ℃, preferably at 5 ℃ to 10 ℃, wherein the molar ratio of hydrogen ions of diazotization hydrochloric acid to p-nitroaniline is 
Preferably 2.8:1, wherein the molar ratio of the sodium nitrite to the paranitroaniline is 1-2: 1, preferably 1.07:1, the stirring speed is in the range of 50-800 rpm, preferably 400-500 rpm, and the reaction time is 5-30 min, preferably 15-20 min.
The coupling reaction process is as follows: placing the coupling component into a dropping funnel, dropping the coupling component into the diazonium salt solution, and stirring to generate a coupling product, wherein the reaction temperature is 0-30 ℃, and preferably 5-10 ℃; preferably at a pH of
Preference is given to
The stirring speed is in the range of 50-800 rpm, preferably 400-500 rpm, and the reaction time is 30-180 min, preferably 100-120 min.
And (3) a heat preservation reaction stage: and pumping the feed liquid obtained by the supergravity coupling into a heat-preservation reaction kettle, and carrying out heat-preservation reaction to obtain the final disperse orange 25 dye. The reaction temperature is 50-150 ℃, and preferably 60-70 ℃; the reaction time is 0.5-2.5 h, preferably 0.5-1 h.
FIG. 6b is a scanning electron micrograph of the disperse dye prepared in the stirred tank of comparative example 1, and it can be seen that the average particle size of the nano disperse dye prepared is 480 nm.
Compared with the nano disperse dye prepared under the supergravity optimal condition, the disperse dye synthesized by the stirred tank process has large particles and obvious agglomeration, and brings certain difficulty to the dye post-treatment.
It should be understood that the above-described embodiments of the present invention are examples for clearly illustrating the invention, and are not to be construed as limiting the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications can be made on the basis of the above description, and it is not intended to exhaust all embodiments, and obvious changes and modifications can be made on the basis of the technical solutions of the present invention.
Claims (10)
1. A continuous production system for nano disperse dyes, which is characterized by comprising:
a condensation reaction unit comprising a condensation reaction tank for generating a coupling component;
a diazotization reaction unit, the diazotization reaction unit comprising:
a premixing assembly for premixing the diazo component and the diazo reagent, and
the spiral coil reactor is communicated with the premixing component so as to enable the premixed reaction solution to carry out diazotization reaction in the spiral coil reactor to generate diazonium salt;
the system further comprises:
the hypergravity coupling reaction unit is communicated with the diazotization reaction unit and the condensation reaction unit and is used for performing coupling reaction on diazonium salt and coupling components under a hypergravity environment to generate nano disperse dye; and
A vent assembly connected to the inlet and outlet of the spiral coil reactor, the vent assembly comprising a first vent conduit having a set height and opening upwardly;
the premixing assembly comprises two inlet pipelines and one outlet pipeline, a second emptying pipeline is formed on the pipe wall of each inlet pipeline, and the opening of each emptying pipeline is arranged upwards.
2. The system of claim 1 wherein the second vent pipe includes a plurality of root bases formed by corresponding pipe walls extending outwardly therefrom, a connecting portion connected to each root base, and an upwardly extending portion connected to a free end of an uppermost root base, the upwardly extending portion being open upwardly.
3. The system of claim 2, wherein the root base comprises two, the two root bases, the connecting portion, and the corresponding tube walls forming a parallelogram structure.
4. The system of claim 2, wherein the root bases comprise at least two, and in two adjacent root bases, the connecting portion has one end connected to the free end of the next adjacent base and the other end connected to the medial side wall of the previous adjacent base.
5. The system of claim 2, wherein the root base is angled between 30-60 ° from the corresponding tube wall.
6. The system of claim 1, wherein the first vent line and the second vent line have an inner diameter less than a minimum particle size of the reaction mass.
7. The system of claim 1, wherein the first vent conduit and the second vent conduit have a height that is greater than a height corresponding to a maximum pressure differential for the reaction liquid.
8. The system of claim 1, wherein the supergravity coupling reaction unit comprises:
the supergravity reactor is communicated with the spiral coil reactor;
a stirred tank reactor in series with the hypergravity reactor, an
And the pump is used for pumping diazonium salt after diazo reaction into the hypergravity rotating packed bed reactor and the pump of the discharge port of the stirred tank reactor to circularly pump back to the hypergravity reactor.
9. The system of claim 1, further comprising a heat exchange unit for controlling the temperature within the helical coil reactor reaction chamber and the temperature within the supergravity coupled reaction unit reaction chamber.
10. The system of claim 9, wherein the heat exchange unit comprises:
the pipeline jacket is sleeved outside the pipeline of the spiral coil reactor and is provided with a cavity into which liquid can be introduced;
the shell jacket is sleeved on the outer side of a shell of the reaction cavity formed by the supergravity reactor and is provided with a cavity into which liquid can be introduced; and
and the heat exchange device is used for heating or cooling liquid introduced into the pipeline jacket and the shell jacket.
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| EP3057938A1 (en) * | 2013-10-18 | 2016-08-24 | Henkel AG & Co. KGaA | Method for ageing the reaction mixture in a sulfonation process |
| CN109651843A (en) * | 2019-01-21 | 2019-04-19 | 北京化工大学 | The continuous production system of the azo active dyestuff of hypergravity |
| CN110508231A (en) * | 2019-08-02 | 2019-11-29 | 北京化工大学 | The continuous production system of the azo active dyestuff of hypergravity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3057938A1 (en) * | 2013-10-18 | 2016-08-24 | Henkel AG & Co. KGaA | Method for ageing the reaction mixture in a sulfonation process |
| CN109651843A (en) * | 2019-01-21 | 2019-04-19 | 北京化工大学 | The continuous production system of the azo active dyestuff of hypergravity |
| CN110508231A (en) * | 2019-08-02 | 2019-11-29 | 北京化工大学 | The continuous production system of the azo active dyestuff of hypergravity |
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