CN110508231B - Continuous production system of azo reactive dye applying supergravity - Google Patents

Continuous production system of azo reactive dye applying supergravity Download PDF

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Publication number
CN110508231B
CN110508231B CN201910711393.XA CN201910711393A CN110508231B CN 110508231 B CN110508231 B CN 110508231B CN 201910711393 A CN201910711393 A CN 201910711393A CN 110508231 B CN110508231 B CN 110508231B
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reactor
spiral coil
reaction
supergravity
coil reactor
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CN110508231A (en
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邹海魁
肖振根
陈建峰
初广文
孙宝昌
罗勇
张亮亮
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BEIJING ZHONGCHAO HAIQI TECHNOLOGY CO LTD
Beijing University of Chemical Technology
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BEIJING ZHONGCHAO HAIQI TECHNOLOGY CO LTD
Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/82—Combinations of dissimilar mixers
    • 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
    • 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
    • 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
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • 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
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a continuous production system of azo reactive dye by using supergravity, which combines a spiral coil reactor with supergravity technology to distinguish diazotization reaction and coupling reaction, wherein the diazotization reaction is carried out in the spiral coil reactor, and the supergravity reactor is used for the coupling reaction and can improve the conversion rate and the quality of products 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 proceeding of 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 azo reactive dye in the same batch can be ensured to be close to or the same, and the industrial actual requirement can be met. Furthermore, the disturbance piece is arranged in the spiral coil pipe, so that the reaction solution in the spiral coil pipe reactor can be disturbed, the flowing and mixing of the reaction solution are accelerated, and the homogenization reaction is facilitated.

Description

Continuous production system of azo reactive dye applying supergravity
Technical Field
The invention relates to the technical field of azo reactive dye preparation. More particularly, it relates to a continuous production system of azo reactive dye using supergravity.
Background
Industrially, the production of reactive azo dyes is carried out in batch operation in stirred tank reactors. Due to the complexity of organic reaction and the large volume of the reactor of the stirring kettle, the temperature and the mixing effect of materials are difficult to reach uniformity in local areas, the production efficiency of the dye is low, and the difference between batches of the dye produced by the intermittent stirring kettle is large, thereby bringing inconvenience to the post-treatment of the dye and the application of the dye.
Therefore, it is desirable to provide a continuous production system for azo reactive dyes using supergravity.
Disclosure of Invention
In view of this, in order to solve the problem that an effective continuous production system for azo reactive dyes is lacking at present, the present invention provides a continuous production system for azo reactive dyes using supergravity.
In certain embodiments, a continuous production system for azo reactive dyes using supergravity, 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 azo reactive dye;
wherein, a disturbance piece with a fixed structure is arranged in an inner cavity of the spiral coil reactor for diazotization reaction, and the disturbance piece is used for disturbing the reaction solution in the spiral coil reactor.
In some embodiments, the disturbing element comprises a fixed part fixed on the surface of the inner cavity of the spiral coil reactor, and a free part fixed in combination with one end of the fixed part away from the surface of the inner cavity of the spiral coil reactor, wherein the free part comprises two free parts, and the two free parts and the fixed part form a Y-shaped structure or a T-shaped structure.
In some embodiments, the disturbance element is arranged perpendicular to the inner cavity surface of the spiral coil reactor or obliquely.
In some embodiments, the disturbing member includes a first portion which is reduced in diameter along the liquid inlet direction, and a second portion which is communicated with one end of the first portion with a smaller inner diameter, the second portion has an expanding diameter structure along the liquid inlet direction, and the first portion and the second portion are symmetrically arranged with a connecting surface thereof as a symmetry plane.
In certain embodiments, 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.
In certain embodiments, the premix assembly comprises a first fluid line and a second fluid line;
the first infusion tube is sleeved outside the second infusion tube, a gap is formed between the first infusion tube and the second infusion tube to allow one of the diazo component and the diazo reagent to flow through, and a cavity in the second infusion tube allows the other of the diazo component and the diazo reagent to flow through;
one end of the first liquid conveying pipe, which is close to the spiral coil reactor, forms a pre-mixing area for mixing the diazo component and the diazo reagent, and the second liquid conveying pipe extends to an inlet of the pre-mixing area and sprays the other one of the diazo component and the diazo reagent to the pre-mixing area.
In some embodiments, the premixing zone includes a reduced diameter portion adjacent its inlet and a straight portion in integral communication with the reduced diameter portion.
In certain embodiments, 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.
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 azo reactive dye by using supergravity, which combines a spiral coil reactor with supergravity technology to distinguish diazotization reaction and coupling reaction, wherein the diazotization reaction is carried out in the spiral coil reactor, and the supergravity reactor is used for the coupling reaction and can improve the conversion rate and the quality of products 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 proceeding of 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 azo reactive dye in the same batch can be ensured to be close to or the same, and the industrial actual requirement can be met. Furthermore, the disturbance piece is arranged in the spiral coil pipe, so that the reaction solution in the spiral coil pipe reactor can be disturbed, the flowing and mixing of the reaction solution are accelerated, and the homogenization reaction is facilitated.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic structural diagram of a continuous production system of azo-reactive dyes using supergravity in an embodiment of the present invention.
FIG. 2 shows a schematic of the construction of a premix assembly in an embodiment of the invention.
Fig. 3a shows one of the schematic structural diagrams of the disturbing member in the inner cavity of the spiral coil according to the embodiment of the present invention.
Fig. 3b shows a second schematic structural diagram of the disturbing element in the inner cavity of the spiral coil according to the embodiment of the present invention.
Fig. 3c shows a third schematic structural diagram of the disturbing element in the inner cavity of the spiral coil according to the embodiment of the present invention.
Fig. 3d shows a fourth schematic structural diagram of the disturbing element in the inner cavity of the spiral coil according to the embodiment 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.
In view of the above, the present invention firstly provides a continuous production system of azo reactive dye using supergravity, 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: the pre-mixing component is used for pre-mixing a heavy nitrogen component and a diazo reagent, and is communicated with the pre-mixing component, so that the pre-mixed reaction solution is subjected to diazo 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 azo reactive dye; wherein, a disturbance piece with a fixed structure is arranged in an inner cavity of the spiral coil reactor for diazotization reaction, and the disturbance piece is used for disturbing the reaction solution in the spiral coil reactor.
The continuous production system of azo reactive dye provided by the invention firstly adopts the spiral coil reactor to be applied to diazotization reaction, and 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 the jacket sleeved on the outer wall of the coil, the diameter of the pipe body of the spiral coil is small, and the side wall of the pipe body is thin, so that the jacket arranged on the outer side wall can directly conduct or remove heat out of the reaction system through the metal pipe wall in a very short time, the pipe diameter is small, and the heat conduction of the reaction solution in the pipe body is uniform, thereby achieving the purpose of precise temperature control, accurately controlling the rising and falling of the system temperature, and greatly reducing the decomposition of diazonium salt.
In addition, the invention further combines the spiral coil reactor with the hypergravity technology, and distinguishes the diazotization reaction and the coupling reaction, 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 the product 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 the two are combined together, and because the temperature control is accurate, the decomposition of the diazonium salt is extremely little, the subsequent coupling reaction can not be influenced, so that the concentration of the diazonium salt can be maintained in a higher range in the continuous production, and the performance of the azo reactive dye in the same batch can be ensured to be close to or the same, thereby being suitable for the actual requirements of the industry.
Thirdly, through setting up the disturbing piece, improve the mixture of reaction solution in the coil pipe for when the reaction rate, be favorable to the homogenization reaction.
In some embodiments, the supergravity reactor may be a supergravity rotating device such as a rotating packed bed, a stator and a rotor, a baffling type, a spiral channel, a rotating disk, 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 is used to cut the liquid into micro elements (liquid droplets or) with micro-nano dimensions, such as a wire mesh filler, and the like, which is not limited by the invention. 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.
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.
Because the disturbance piece makes reaction liquid form the vortex environment in the coil pipe, combine the supersound simultaneously, can mix the cooperation with the macro of vortex environment, further realize the micro-mixing through molecular vibration, and then go on simultaneously in macro and micro mixture, further reach the effect that the mass transfer was mixed, meanwhile, because the coil pipe diameter is less, to the higher reaction solution of viscosity or thick liquid, the setting of disturbance piece leads to the phenomenon of part jam easily, the cooperation supersound can pass through molecular vibration, make the molecule can not stop at fixed position, show and reduce blocking phenomenon, accelerate the flow of reaction solution or thick liquid.
In one particular embodiment, as shown in FIG. 1, FIG. 1 illustrates a continuous production system comprising: a diazo component mixing tank 1, a diazo reagent raw material tank 2, a pump 3, a pump 4, a premixing component 5, a spiral coil reactor 7, a coupling component raw material tank 9, a supergravity reactor 11 and a collection container 14. Wherein the diazo component mixing tank 1 is communicated with the premixing component 5 through the pump 3, so that the diazo component is introduced into the premixing component 5. The diazonium reagent head tank 2 is in communication with the pre-mix assembly 5 via pump 4 to pump diazonium reagent into the pre-mix assembly 5, which in turn mixes the diazonium component with the diazonium reagent within the pre-mix assembly 5. The premixing component 5 is communicated with the spiral coil reactor 7, the diazo component and the diazo reagent which are mixed together are introduced into the spiral coil reactor 7 for reaction, the diazo component and the diazo reagent enter the supergravity reactor 11 for coupling reaction after the diazo reaction, and the product after the coupling reaction enters the collecting container 14.
This embodiment includes a hypergravity reactor 11 that can be used for the continuous production of diazotization reaction-coupling reactions. For example, a red reactive azo dye reactive red M-3 BE.
In some embodiments, as shown in fig. 3a to 3d, the disturbing component includes a fixed portion fixed on the inner cavity surface of the spiral coil reactor, and two free portions fixed to an end of the fixed portion away from the inner cavity surface of the spiral coil reactor, and the two free portions and the fixed portion form a "Y" structure or a "T" structure.
Further, as can be seen from fig. 3a to 3d, the disturbing member is disposed perpendicular to the inner cavity surface of the spiral coil reactor, or disposed obliquely.
Specifically, with reference to the above illustration, the disturbing member includes a first portion that is reduced in diameter in the liquid inlet direction, and a second portion that is communicated with one end of the first portion having a smaller inner diameter, the second portion has an expanded diameter structure in the liquid inlet direction, and the first portion and the second portion are symmetrically disposed with a connection surface thereof as a symmetry plane.
In some embodiments, the system further comprises a heat exchange unit, which can heat or cool the tube body of the spiral coil reactor, for example, the outer wall of the tube body of the spiral 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.
In the above embodiment, the specific structure of the premixing component is shown in fig. 2, and the premixing component includes a first infusion tube 51 (outer infusion tube) and a second infusion tube 52 (inner infusion tube); the first infusion tube 51 is sleeved outside the second infusion tube 52, a gap is formed between the first infusion tube 51 and the second infusion tube 52 to allow one of the diazo component and the diazo reagent to flow through, and a cavity in the second infusion tube 52 allows the other of the diazo component and the diazo reagent to flow through; a pre-mixing area 53 for mixing the diazo component and the diazo reagent is formed at one end of the first liquid conveying pipe 51 close to the spiral coil reactor, the second liquid conveying pipe 52 extends to the inlet of the pre-mixing area 53, and the other one of the diazo component and the diazo reagent is sprayed to the pre-mixing area 53. In one embodiment, the space between the first infusion line 51 and the second infusion line 52 is filled with a diazo component and the second infusion line 52 is filled with a diazo reagent, although in other embodiments, the invention is not limited thereto.
The first infusion tube 51 is fed vertically, and a feed port is formed in the outer wall of the tube body, thereby avoiding a problem that the first infusion tube 51 and the second infusion tube 52 are fed from the same position (left position in the drawing) and the feeding is not possible.
Further, in order to enable a faster rate of solution flow through the pre-mix assembly, the pre-mix zone includes a reduced diameter portion adjacent to its inlet and a flat portion in integral communication with the reduced diameter portion. Therefore, the caliber of the liquid outlet is reduced during discharging, and the speed of flowing out the solution can be increased.
In some preferred embodiments, there is no gap between the heat exchange jacket and the outer wall of the tube body of the spiral coil reactor, so that the heat transfer effect of air with low heat transfer rate is avoided.
Diazotization reaction occurs in the spiral coil reactor to generate diazonium salt, and the temperature can be accurately controlled by the spiral coil reactor, so that the decomposition of the diazonium salt can be avoided, the diazonium salt can be 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.
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.
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 diazo component comprises 2-naphthylamine-1, 5 disulfonic acid, the diazotizing agent comprises nitrite and hydrochloric acid, and the coupling component comprises a condensation solution obtained by twice condensing H acid, para-ester and cyanuric chloride, so that the azo-reactive dye produced by the above-described system of the present invention is red reactive azo dye reactive red M-3 BE.
Of course, the continuous production system of the present invention is not limited to the two specific examples described above, and it should be understood that the present system can be applied to any azo-reactive dye that performs diazotization and coupling reactions, and the present invention is not intended to be exhaustive.
The following describes the continuous production system provided by the present invention in detail with reference to two specific examples.
Continuous generation of red reactive azo dye reactive red M-3BE
In this embodiment, the diazo component includes 2-naphthylamine-1, 5 disulfonic acid, the diazotizing agent includes hydrochloric acid and sodium nitrite, and the coupling component includes a condensation liquid obtained by twice condensation of H acid, para-ester and cyanuric chloride.
The diazotization reaction process comprises the following steps: pre-mixing a mixed solution of 2-naphthylamine-1, 5 disulfonic acid and nitrite with a hydrochloric acid solution through a pre-mixing component, as shown in figure 2, then respectively and continuously feeding the mixed solution into a spiral coil reactor through a pipeline, and then circularly returning the mixed solution to the inlet of a spiral pipe at an outlet to obtain a diazonium salt suspension, wherein the diazotization reaction is carried out at-10 ℃ to +40 ℃, preferably 0 ℃ to 12 ℃, the molar ratio of hydrogen ions of diazotization reaction hydrochloric acid to 2-naphthylamine-1, 5 disulfonic acid during feeding is 2.5-4: 1, preferably 3:1, the molar ratio of sodium nitrite to para-ester is 1-2: 1, preferably 1.01-1.1: 1, and the feeding flow rate is 0.08-0.8 m/s, preferably 0.25-0.7 m/s.
The condensation reaction process is as follows: introducing cyanuric chloride and H acid into a stirring kettle by a constant flow pump to perform primary condensation reaction at the temperature of 0-5 ℃ and the pH of 2.5-3.5, and introducing para-ester and the primary condensation liquid to perform secondary condensation at the temperature of 30-35 ℃ and the pH of 3-4 to obtain secondary condensation liquid, namely coupling raw material liquid.
The coupling reaction process is as follows: continuously feeding the diazonium salt and the coupling component into a supergravity rotating bed reactor respectively, and performing mixed reaction to generate an azo compound, wherein the reaction temperature is 0-45 ℃, and preferably 8-15 ℃; preferably, the pH value is 6-8.5; the rotating speed of the super-gravity reactor is 1200-3200 rpm, preferably 1600-1900 rpm.
The properties of the red reactive azo dye reactive red M-3BE produced by the continuous production method of the present invention will BE described below by taking some specific experimental parameters as examples.
(a) Preparation of 2-naphthylamine-1, 5-disulfonic acid diazonium salt (spiral coil reactor)
6.40g of 2-naphthylamine-1, 5-disulfonic acid is weighed, 90ml of water is added, 10% Na is added2CO3The solution was stirred and dissolved at room temperature until the pH became 6 to 6.5, and 1.1178g of nano2 was added and stirred and dissolved, and the amount of the mixed solution of 2-naphthylamine-1, 5-disulfonic acid and sodium nitrite was about 105 ml.
The mixed solution of 2-naphthylamine-1, 5 disulfonic acid and sodium nitrite and 45ml hydrochloric acid with the concentration of 1mol/L are pumped into a premixing component of a spiral coil reactor through a peristaltic pump. The temperature was controlled at 8 ℃ by a thermostatic bath jacket. A pale yellow suspension of 2-naphthylamine-1, 5 disulfonic acid diazonium salt is obtained.
(b) Preparation of the coupling component (stirred tank reactor)
Weighing 4.45g of para-ester powder, adding 30ml of water, and then adding 10% Na2CO3Stirring the solution, dissolving at room temperature until the pH value is 6-6.5, and performing suction filtration on the solution to obtain a para-ester sodium salt solution; weighing 5.63g H acid powder, adding water 30ml, adding 10% Na2CO3Stirring the solution, and dissolving at room temperature until the pH value is 6-6.5 to obtain a disodium H acid solution; weighing 2.83g of cyanuric chloride powder, directly pouring the cyanuric chloride powder into a stirred tank reactor, adding 72ml of ice water mixed solution, pulping cyanuric chloride at 0-5 ℃, introducing H acid into the stirred tank through a constant flow pump to perform primary condensation reaction, after the reaction is finished, introducing para-ester solution into the stirred tank through the constant flow pump, and performing secondary condensation at 30-35 ℃ to obtain secondary condensation solution, namely coupling raw material solution.
(c) Coupling reaction (hypergravity reactor)
Connecting the obtained secondary condensation liquid with one inlet of a coupling reaction rotating bed, connecting an outlet of a spiral coil reactor with the other inlet of the super-gravity rotating bed, dividing two materials into two parts, reacting in the super-gravity rotating bed, entering a stirring kettle reactor, and circularly returning to the super-gravity reactor, wherein the temperature is controlled to be about 10 ℃ by a constant temperature tank jacket, and the rotating speed of the rotating bed is 1700rpm, thus obtaining a red coupling product.
Salting out, drying, refining and drying the feed liquid to obtain the reactive red M-3BE dye, wherein the yield is up to 96 percent and the purity of the sample is up to 92 percent.
Obviously, the products in the experimental scene can achieve high yield and high purity samples, and the product performance of the same batch is almost the same, of course, although the invention takes the red reactive azo dye reactive red M-3BE as an example of continuous production, the invention does not mean that the invention can BE used for the above example, and from the inventive concept of the invention, the type of the azo reactive dye is not directly related to the main concept of the invention. It is to be understood that the invention as proposed by the present invention can be applied to any azo reactive dye by those skilled in the art, and the present invention is not exhaustive.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A system for the continuous production of azo reactive dyes using supergravity, said 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 azo reactive dye;
wherein, a disturbance piece with a fixed structure is arranged in an inner cavity of the spiral coil reactor for diazotization reaction, and the disturbance piece is used for disturbing the reaction solution in the spiral coil reactor.
2. The system according to claim 1, wherein the disturbing member comprises a fixed part fixed on the inner cavity surface of the spiral coil reactor and two free parts fixed with one end of the fixed part far away from the inner cavity surface of the spiral coil reactor, and the two free parts and the fixed part form a Y-shaped structure or a T-shaped structure.
3. The system of claim 2, wherein the disturbance element is disposed perpendicular to the inner cavity surface of the helical coil reactor or is disposed obliquely.
4. The system according to claim 1, wherein the disturbing member comprises a first portion which is reduced in diameter in the liquid inlet direction, and a second portion which is communicated with one end of the first portion having a smaller inner diameter, the second portion has an enlarged diameter structure in the liquid inlet direction, and the first portion and the second portion are symmetrically arranged with the connecting surface as a symmetrical plane.
5. The system of claim 1, further comprising:
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.
6. The system of claim 1, wherein the premix assembly comprises a first fluid line and a second fluid line;
the first infusion tube is sleeved outside the second infusion tube, a gap is formed between the first infusion tube and the second infusion tube to allow one of the diazo component and the diazo reagent to flow through, and a cavity in the second infusion tube allows the other of the diazo component and the diazo reagent to flow through;
one end of the first liquid conveying pipe, which is close to the spiral coil reactor, forms a pre-mixing area for mixing the diazo component and the diazo reagent, and the second liquid conveying pipe extends to an inlet of the pre-mixing area and sprays the other one of the diazo component and the diazo reagent to the pre-mixing area.
7. The system of claim 6, wherein the premixing zone comprises a reduced diameter portion adjacent to an inlet thereof and a flat portion in integral communication with the reduced diameter portion.
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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