CN109651843A - The continuous production system of the azo active dyestuff of hypergravity - Google Patents
The continuous production system of the azo active dyestuff of hypergravity Download PDFInfo
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- CN109651843A CN109651843A CN201910053415.8A CN201910053415A CN109651843A CN 109651843 A CN109651843 A CN 109651843A CN 201910053415 A CN201910053415 A CN 201910053415A CN 109651843 A CN109651843 A CN 109651843A
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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
- 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
- C09B62/513—Disazo or polyazo dyes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of continuous production system of the azo active dyestuff of hypergravity, supergravity reactor is applied to coupling reaction first, the quality of reaction conversion ratio and product can largely be improved, simultaneously using spiral coil reactor produced in diazo-reaction, compared at present using stirred tank reactor progress diazo-reaction, the temperature rise of system temperature can be accurately controlled, it is significant to shorten the diazo-reaction time, the decomposition for largely reducing diazonium salt, can be realized industrialization continuous production.
Description
Technical field
The present invention relates to azo active dyestuff preparation technical fields.More particularly, to a kind of azo of hypergravity
The continuous production system of reactive dye.
Background technique
Industrially, the production of reactive azo dyes is to be carried out in stirred tank reactor with andnon-continuous operation manner.By
Too big in the complexity and stirred tank reactor volume of organic reaction, the temperature and mixed effect for leading to material are in partial zones
Domain is difficult to reach uniformly, and the production efficiency of dyestuff is low, and difference is larger between the dyestuff each batch of batch agitator kettle production, right
The post-processing of dyestuff and the application of dyestuff all bring inconvenience.
Therefore, it is urgent to provide a kind of continuous production systems of the azo active dyestuff of hypergravity.
Summary of the invention
In view of this, in order to solve the continuous production system for lacking effective azo active dyestuff at present, the present invention is mentioned
For a kind of continuous production system of the azo active dyestuff of hypergravity.
In certain embodiments, a kind of continuous production system of the azo active dyestuff of hypergravity, the system
Include:
Diazo-reaction unit, the diazo-reaction unit include:
Component is premixed, diazo component and diazo reagent are premixed, and
Spiral coil reactor is connected to the premix component, so that the reaction solution after premix is in the spiral coil
Diazo-reaction is carried out in reactor generates diazonium salt；
The system further comprises the hypergravity coupling reaction unit being connected with the diazo-reaction, described overweight
It is living for making diazonium salt and coupling component carry out the coupling reaction generation azo under Elevated Gravity that couple closes reaction member
Property dyestuff.
In certain embodiments, the premix component includes the first perfusion tube and the second perfusion tube；
First perfusion tube is sheathed on the outside of second perfusion tube, and first perfusion tube and described second
Cavity with gap for one of circulation of diazo component and diazo reagent between perfusion tube, in second perfusion tube
It circulates for the another one of diazo component and diazo reagent；
First perfusion tube forms mixed for diazo component and diazo reagent close to one end of the spiral coil reactor
The pre-mix zone of conjunction, second perfusion tube extends to the inlet of the pre-mix zone, and sprays the diazonium to the pre-mix zone
The another one of component and diazo reagent.
In certain embodiments, the pre-mix zone includes closing on the reducing diameter part of its inlet and integrally connecting with the reducing diameter part
Logical flat part.
In certain embodiments, the hypergravity coupling reaction unit includes:
Supergravity reactor is connected to the spiral coil reactor, and
For the diazonium salt after diazo reaction to be pumped into the circulating pump of the high gravity rotating packed bed reactor.
In certain embodiments, the pump is polytetrafluoro constant-flux pump.
In certain embodiments, the spiral coil in the spiral coil reactor is made of polyurethane.
In certain embodiments, the inner surface of the spiral coil in the spiral coil reactor is combined with polyurethane material
Layer.
In certain embodiments, the azo active dyestuff is Reactive dye red M-3BE dyestuff or active yellow M-5G dyestuff.
In certain embodiments, the system further comprises heat exchange unit, and the heat exchange unit is for controlling the spiral shell
The intracorporal temperature of capstan pipe reactor reaction chamber and the intracorporal temperature of the hypergravity coupling reaction unit process chamber.
In certain embodiments, the heat exchange unit includes:
It is set in the pipeline collet of the pipeline external of the spiral coil reactor, the pipeline collet has and can be passed through liquid
The cavity of body；
It is set in the shell collet that the supergravity reactor forms the outer side of shell of reaction cavity, the shell collet tool
There is the cavity that can be passed through liquid；And
For the heat-exchanger rig for being passed through liquid in the pipeline collet and the shell collet to be heated or cooled.
Beneficial effects of the present invention are as follows:
The present invention provides the continuous production system of the azo active dyestuff of hypergravity, first by using helical disk
Pipe reactor is applied to diazo-reaction, since the reaction cavity of spiral coil reactor is helical disk tubulose, when needing temperature
When control, heat exchange jacket etc. can be directly set in coil pipe outer wall, since the pipe diameter of spiral coil is small, tube wall compared with
It is thin, therefore the heat exchange jacket being arranged on outer side wall in a very short period of time can directly be passed thermal energy or cold energy by metal pipe-wall
It leads in reaction system, and since caliber is small, it is uniform to manage intracorporal reaction solution heat transfer, to reach the mesh of accurate temperature controlling
, the lifting of system temperature can be accurately controlled, the decomposition of diazonium salt is largely reduced.In addition, the present invention further will
Spiral coil reactor is treated diazo-reaction and coupling reaction differentiation, diazo-reaction exists in conjunction with high-gravity technology
It is carried out in spiral coil reactor, supergravity reactor can largely improve conversion ratio and product for coupling reaction
Quality.And spiral coil reactor can accurate temperature controlling, the decomposition of diazonium salt is avoided, under cooperating in this way, since temperature controls
Accurately, diazonium salt decomposes few, will not influence the progress of subsequent coupling reaction, therefore can guarantee diazonium salt when continuous production
Concentration maintain higher range, it is close or identical with a batch of azo active dyestuff performance so as to guarantee, adapt to
The actual demand of industry.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 a shows the continuous production system structure of the azo active dyestuff of the hypergravity in the embodiment of the present invention
One of schematic diagram.
Fig. 1 b shows the continuous production system structure of the azo active dyestuff of the hypergravity in the embodiment of the present invention
One of schematic diagram.
Fig. 2 shows the structural schematic diagrams of the premix component in the embodiment of the present invention.
Fig. 3 shows the continuous production method process signal of the azo active dyestuff of hypergravity in the embodiment of the present invention
Figure.
Fig. 4 shows the idiographic flow schematic diagram of continuous production Reactive dye red M-3BE dyestuff of the embodiment of the present invention.
Fig. 5 shows the idiographic flow schematic diagram of step S11 in Fig. 4.
Fig. 6 shows the idiographic flow schematic diagram of step S12 in Fig. 4.
Fig. 7 shows the idiographic flow schematic diagram of step S13 in Fig. 4.
Fig. 8 shows the idiographic flow schematic diagram of continuous production active yellow M-5G dyestuff of the embodiment of the present invention.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Industrially, reactive azo dyes are to be carried out in stirred tank reactor with andnon-continuous operation manner.Due to organic
The complexity and stirred tank reactor size of reaction are too big, and the temperature of material and mixed effect is caused to be difficult in regional area
Reaching uniformly, the conversion ratio and production efficiency of dyestuff are low, and difference is larger between the dyestuff each batch of batch agitator kettle production,
The application of post-processing and dyestuff to dyestuff all brings inconvenience.Therefore not yet occurring one kind at present being capable of continuous production idol
The production system of nitrogen reactive dye.
In view of this, present invention firstly provides a kind of continuous production system of the azo active dyestuff of hypergravity,
The system includes: diazo-reaction unit, and the diazo-reaction unit includes: premix component, is tried diazo component and diazonium
Agent is premixed and spiral coil reactor, is connected to the premix component, so that the reaction solution after premix is in the spiral
Diazo-reaction is carried out in coil reactor generates diazonium salt；The system further comprises being connected with the diazo-reaction
Hypergravity coupling reaction unit, the hypergravity coupling reaction unit under Elevated Gravity for making diazonium salt and coupling group
Divide and carries out the coupling reaction generation azo active dyestuff.
The continuous production system of above-mentioned azo active dyestuff provided by the invention is answered using spiral coil reactor first
It,, can be with when needing temperature to control since the reaction chamber of coil reactor is helical disk tubulose for diazo-reaction
Heat medium or cooling medium are passed through in the collet for being set in coil pipe outer wall, the pipe diameter of spiral coil is small, tube wall
It is relatively thin, therefore heat directly can be conducted or be removed by metal pipe-wall in a very short period of time by the collet being arranged on outer side wall
Reaction system, and caliber is small, and it is uniform to manage intracorporal reaction solution heat transfer, thus achieve the purpose that accurate temperature controlling, Neng Gouzhun
The lifting of true control system temperature, largely reduces the decomposition of diazonium salt.
In addition, the present invention is further by spiral coil reactor in conjunction with high-gravity technology, for diazo-reaction and idol
It closes reaction differentiation to treat, diazo-reaction carries out in spiral coil reactor, and supergravity reactor can for coupling reaction
Largely improve the quality of conversion ratio and product.And spiral coil reactor can accurate temperature controlling, avoid diazonium salt
It decomposes, the two combines, and since temperature control is accurate, diazonium salt is decomposed seldom, it will not influence the progress of subsequent coupling reaction,
Therefore it can guarantee that the concentration of diazonium salt when continuous production maintains higher range, so as to guarantee with a batch of azo
Reactive dye performance is close or identical, adapts to the actual demand of industry.
In a specific embodiment, as shown in Figure 1a, Fig. 1 a shows a kind of continuous process system, the continuous production system
System includes: that diazo component blending tank 11, diazo reagent head tank 12, pump 13, pump 14, pump 18, premix component 15, spiral coil are anti-
Answer device 16, coupling component head tank 17, supergravity reactor 19, collection container 10.Wherein, diazo component blending tank 1 passes through pump
13 are connected to premix component 15, so that diazo component is passed through premix component 15.Diazo reagent head tank 12 is by pump 14 and in advance
Mixed component 15 is connected to, so that diazo reagent is passed through premix component 15, and then in premix component 15, diazo component and diazonium examination
Agent mixing.Premix component 15 is connected to spiral coil reactor 16, and the diazo component mixed and diazo reagent are passed through
It is reacted in spiral coil reactor 16, supergravity reactor 19 is entered after diazo reaction and carries out coupling reaction, coupling
Product after reaction enters in collection container 10.
Include supergravity reactor 19 in the embodiment, can be used for diazo-reaction-coupling reaction continuous production.Example
Such as active yellow M-5G dyestuff.
In further embodiments, as shown in Figure 1 b, Fig. 1 b shows another continuous process system, the continuous production system
System include: diazo component blending tank 21, diazo reagent head tank 22, pump 20, pump 23, pump 24, pump 28, pump 32, premix component 25,
Spiral coil reactor 26, alkaline coupling component raw material tank 31, supergravity reactor 29, surpasses acid coupling component raw material tank 27
Gravity reactor 33 and collection container 34.Wherein, diazo component blending tank 21 is connected to by pump 23 with premix component 25, thus
Diazo component is passed through premix component 25.Diazo reagent head tank 22 is connected to by pump 24 with premix component 25, thus by diazonium
Reagent is passed through premix component 25, and then in premix component 25, diazo component and diazo reagent mixing.Premix component 25 and spiral
Coil reactor 26 is connected to, and the diazo component mixed and diazo reagent are passed through in spiral coil reactor 26 and carried out instead
It answers, the acid coupling component raw material in supergravity reactor 29 and acid coupling component raw material tank 27 is entered after diazo reaction
Carry out acid coupling reaction, then acid coupling product is pumped into supergravity reactor 33 by pump 20, and then with alkaline coupling group
The alkaline coupling component raw material divided in head tank carries out alkaline coupling reaction, and the product of alkaline coupling reaction enters collection container 10
In.
Include supergravity reactor 29 and supergravity reactor 33 in the embodiment, can be used for diazo-reaction-acidity
Coupling reaction-alkaline coupling reaction continuous production.Such as Reactive dye red M-3BE dyestuff.
In some embodiments, above system further comprises heat exchange unit, and spiral can be heated or cooled in heat exchange unit
The tube body of coil reactor, such as the tube wall of spiral coil reactor are arranged with heat exchange jacket (not shown).Due to
Pipe diameter is small, therefore thermal energy or cold energy rapidly can be diffused to equably and entirely be managed in intracorporal cavity by heat exchange jacket.
In some embodiments, the spiral coil in the spiral coil reactor is made of polyurethane.It in this way can be with
It prevents from corroding, while heat transfer is influenced smaller.
Certainly, as embodiment unlike this embodiment, spiral coil in the spiral coil reactor it is interior
Surface is lined with urethane material.
Equally, in order to avoid the influence of corrosion, above-mentioned pump is polytetrafluoro constant-flux pump.
In some preferred embodiments, the heat exchange unit includes being set in outside the pipeline of the spiral coil reactor
The pipeline collet in portion, the pipeline collet have the cavity that can be passed through liquid；The pipe is passed through with for heating or cooling medium
The heat-exchanger rig of liquid in road collet,.Spiral coil reactor tube body is heated or cooled by liquid to realize temperature
It is precisely controlled.
In addition, the heating or cooling medium in pipeline collet can be water, alcohol, salting liquid, or oil, the present invention
It is without limitation.
In the above-described embodiments, the specific structure of component is premixed as shown in Fig. 2, the premix component includes the first perfusion tube
51 (outer layer perfusion tubes) and the second perfusion tube 52 (internal layer perfusion tube)；First perfusion tube 51 is sheathed on second perfusion tube
52 outside, and have gap for diazo component and diazonium between first perfusion tube 51 and second perfusion tube 52
One of circulation of reagent, the another one stream of cavity in second perfusion tube 52 for diazo component and diazo reagent
It is logical；First perfusion tube 51 is mixed close to the formation of one end of the spiral coil reactor for diazo component and diazo reagent
Pre-mix zone 53, second perfusion tube 52 extend to the inlet of the pre-mix zone 53, and spray to the pre-mix zone 53 described
The another one of diazo component and diazo reagent.When it is implemented, the sky between the first perfusion tube 51 and the second perfusion tube 52
Clearance flow leads to diazo component, and circulate diazo reagent in the second perfusion tube 52, and certainly, in other embodiments, vice versa, the present invention
It is without limitation.
It should be noted that the charging of the first perfusion tube 51 is feeding vertical, feed inlet is formed in tube wall, and then keep away
Exempt from the first perfusion tube 51 and the second perfusion tube 52 and leads to not asking for charging from same position (left position in diagram) charging
Topic.
Further, in order to make by premix component outflow solution have faster speed, the pre-mix zone
Including the flat part for closing on the reducing diameter part of its inlet and being integrally connected to the reducing diameter part.In this way discharging when liquid outlet
Bore becomes smaller, and can accelerate the speed for flowing out solution.
It is very close to each other between heat exchange jacket and the tube wall of spiral coil reactor in some preferred embodiments,
This avoid the air of low heat transfer rate to have an impact to heat transfer.
Diazo-reaction occurs in spiral coil reactor, diazonium salt is generated, since spiral coil reactor can be accurate
Control temperature, therefore can be avoided the decomposition of diazonium salt so that in a batch of continuous production diazonium salt it is subsequent into
Material concentration holding is stablized constant, so that stable product quality, differs smaller with a batch of properties of product.
In some embodiments, supergravity reactor can be rotating packed bed reactor or rotor reactor,
Those skilled in the art are illustrated, and the present invention with no restrictions, as needed, can arbitrarily set the concrete type of supergravity reactor
Set the one of which of all supergravity reactors in the prior art.
It should be noted that the liquid distribution trough of supergravity reactor is two bursts of chargings in diagram in the present embodiment, point
It does not spray, but in other embodiments, pre-mix zone can also be set at liquid distribution trough jet port, and then before ejecting,
Diazonium salt solution and coupling component enter supergravity reactor first in liquid each by the first liquid-inlet and second liquid import
The pre-mix zone of body distributor is premixed, and then into reaction inner cavity, the present invention does not do further limitation to this for injection.
It should be noted that coupling reaction also needs to guarantee certain temperature, but compared to diazo-reaction for, it is even
It is not high to the demand for control of temperature to close reaction, is experimentally confirmed, for coupling reaction using supergravity reactor compared to spiral shell
Capstan pipe reactor has more advantage.
In addition, since coupling reaction needs to guarantee certain temperature, it can be anti-to hypergravity by above-mentioned heat exchange unit
The shell of device is answered to be heated or cooled, to realize the control to temperature.
In certain embodiments, heat exchange unit further comprises being set in the supergravity reactor to form reaction chamber
The shell collet of body, shell collet have the cavity that can be passed through liquid.Further, heat-exchanger rig can be heated or cooled simultaneously
Liquid in pipeline collet and shell collet.Further, pipeline collet is connected to shell collet, and heat transferring medium can be from pipe
Road collet flows into shell collet, without limitation.
In certain embodiments, the diazo component includes para-ester and nitrite, the diazo reagent packet
Hydrochloric acid is included, the coupling component includes H acid and sodium carbonate, the azo activity generated in this way by above system of the invention
Dyestuff is Reactive dye red M-3BE dyestuff.
In other specific embodiment, the diazo component includes para-ester and nitrite, the diazotising examination
Agent includes hydrochloric acid, and the coupling component includes 1- (2,5- bis- chloro- 4- sulfonic acid) -3- methyl -5- pyrazolone and sodium carbonate, described
Azo active dyestuff is active yellow M-5G dyestuff.
Certainly, continuous process system of the invention is not limited to above two specific embodiment, it is to be understood that this system
It can be suitable for any azo active dyestuff for carrying out diazo-reaction and coupling reaction, the present invention does not do exhaustion herein.
Obviously, detailed description through the foregoing embodiment, those skilled in the art could be aware that the present invention adopts first
It is applied to diazo-reaction with spiral coil reactor, since the reaction chamber of coil reactor is helical disk tubulose, when
When temperature being needed to control, heat medium or cooling medium can be passed through in the collet for being set in coil pipe outer wall, spiral coil
Pipe diameter is small, and tube wall is relatively thin, therefore heat can be passed through gold in a very short period of time by the collet being arranged on outer side wall
Belong to tube wall directly to conduct or remove reaction system, and caliber is small, and it is uniform to manage intracorporal reaction solution heat transfer, to reach essence
The purpose of true temperature control, can accurately control the lifting of system temperature, largely reduce the decomposition of diazonium salt.In addition, this hair
It is bright that diazo-reaction and coupling reaction differentiation are treated further by spiral coil reactor in conjunction with high-gravity technology, it is heavy
Nitridation reaction carries out in spiral coil reactor, and supergravity reactor can largely improve conversion for coupling reaction
The quality of rate and product.And spiral coil reactor can accurate temperature controlling, avoid the decomposition of diazonium salt, the two combines, by
Accurate in temperature control, diazonium salt decomposes seldom, will not influence the progress of subsequent coupling reaction, therefore can guarantee continuous life
The concentration of diazonium salt maintains higher range when production, so as to guarantee with a batch of azo active dyestuff performance it is close or
It is identical, adapt to the actual demand of industry.
Further, the present invention is based on the inventive concepts of above-mentioned continuous process system, also provide a kind of hypergravity
The continuous production method of azo active dyestuff.Incorporated by reference to shown in Fig. 3, this method comprises:
S1: diazo component and diazo reagent are passed through premix component and premixed；
S2: the reaction solution formed after premix is passed through spiral coil reactor and carries out diazo reaction generation diazonium salt；
S3: the diazonium salt and coupling component are passed through to the hypergravity coupling reaction list being connected with the diazo-reaction
Member carries out coupling reaction and generates the azo active dyestuff.
The continuous production method of the azo active dyestuff of hypergravity provided by the invention, first by using spiral
Coil reactor is applied to diazo-reaction, since the reaction cavity of spiral coil reactor is helical disk tubulose, when needing temperature
When degree control, heat exchange jacket etc. can be directly set in coil pipe outer wall, since the pipe diameter of spiral coil is small, tube wall
It is relatively thin, therefore the heat exchange jacket being arranged on outer side wall can be direct by metal pipe-wall by thermal energy or cold energy in a very short period of time
It is transmitted in reaction system, and since caliber is small, it is uniform to manage intracorporal reaction solution heat transfer, to reach accurate temperature controlling
Purpose can accurately control the lifting of system temperature, largely reduce the decomposition of diazonium salt.In addition, the present invention is further
By spiral coil reactor in conjunction with high-gravity technology, diazo-reaction and coupling reaction differentiation are treated, diazo-reaction
It is carried out in spiral coil reactor, supergravity reactor can largely improve conversion ratio and production for coupling reaction
The quality of product.And spiral coil reactor can accurate temperature controlling, the decomposition of diazonium salt is avoided, under cooperating in this way, due to temperature control
System is accurate, and diazonium salt decomposes seldom, will not influence the progress of subsequent coupling reaction, therefore can guarantee diazonium when continuous production
The concentration of salt maintains higher range, close or identical with a batch of azo active dyestuff performance so as to guarantee, fits
Answer the actual demand of industry.
Method provided by the invention is described in detail below with reference to two specific examples.
1, the continuous production of Reactive dye red M-3BE dyestuff
In the embodiment, the diazo component includes para-ester and nitrite, and the diazo reagent includes hydrochloric acid, institute
Stating coupling component includes H acid and sodium carbonate.
Diazo-reaction process are as follows: carry out para-ester and nitrite mixed liquor and hydrochloric acid solution in advance by premix component
It is mixed, as shown in Fig. 2, being then continuously input into spiral coil reactor respectively by pipeline, diazonium salt solution or suspension are obtained,
Diazo-reaction carries out at preferably 0 DEG C to 15 DEG C at -10 DEG C to+40 DEG C, when charging the hydrogen ion of diazo-reaction hydrochloric acid with it is right
The molar ratio of position ester is 2~8:1, preferably 3:1, and the molar ratio of sodium nitrite and para-ester is 1~2:1, preferably 1.01~1.1:
1, feed flow rate is in 0.08~0.8m/s, preferably 0.25~0.7m/s.
Acid coupling reaction process are as follows: diazonium salt and coupling component are continuously input into rotating packed bed reactor respectively
In, acid coupling product is generated through hybrid reaction, reaction temperature is 0 DEG C to 45 DEG C, preferably 10 DEG C~15 DEG C；PH is 1~6, excellent
Select pH=1~1.5；Supergravity reactor revolving speed is 1200~3200rpm, preferably 1800~2000rpm.
Alkaline coupling reaction process are as follows: acid coupling product is input into high-gravity rotating bed react with sodium carbonate liquor respectively
In device, azo-compound is generated through hybrid reaction, reaction temperature is 0 DEG C to 45 DEG C, preferably 10 DEG C~15 DEG C；PH is 8~12, excellent
Select pH=7.5-8.5；Supergravity reactor revolving speed is 1200~3200rpm, preferably 1800~2000rpm.
Those skilled in the art are illustrated, and the above method is summarized as following expressions, by as shown in connection with fig. 4, preparing
Method includes:
S11: the mixed liquor of para-ester and nitrite is passed through in premix component with hydrochloric acid and is premixed.
S12: the mixed solution that para-ester, nitrite and hydrochloric acid are formed is passed through spiral coil reactor and carries out diazonium
Reaction generates para-ester diazonium salt suspension.
S13: the para-ester diazonium salt suspension, H acid and sodium carbonate are passed through hypergravity coupling reaction unit and carried out
Acid coupling reaction and alkaline coupling reaction generate the Reactive dye red M-3BE dyestuff.
In the embodiment, as shown in connection with fig. 5, step S11 is specifically included:
S111: para-ester and nitrite are carried out being mixed to form mixed liquor according to the ratio that molar ratio is 1:1-1:2.
S112: it is described pre- that the mixed liquor and hydrochloric acid according to para-ester and hydrionic molar ratio are that 1:2-1:8 is passed through
Mixed component.
In the embodiment, as shown in connection with fig. 6, step S12 is specifically included:
S121: being -10 to 40 DEG C by the intracorporal temperature of reaction chamber that heating unit controls the spiral coil reactor.
S122: being 1-8 by the range that sodium carbonate adjusts pH.
S123: under the reaction environment that temperature is -10 to 40 DEG C, the range of pH is 1-8, by para-ester, nitrite with
And the mixed solution that hydrochloric acid is formed is passed through spiral coil reactor progress diazo reaction generation para-ester diazonium salt suspension.
Further, in some embodiments, as shown in fig. 7, above-mentioned steps S13 is specifically included:
S131: the H acid solution and the sodium carbonate liquor are mixed to form the H acid double sodium salt solution that pH is 6.5-7.5.
S132: the H acid double sodium salt solution and diazonium salt circulation are pumped into the hypergravity coupling reaction unit
In reaction chamber, it is anti-that acid coupling is carried out by the reaction temperature that heat exchange unit adjusts the arrival acid coupling of the temperature in the reaction chamber
It should obtain acid coupling product.
S133: the reaction that the acid coupling product and sodium carbonate liquor are pumped into the hypergravity coupling reaction unit is held
In chamber, the reaction temperature progress alkaline coupling reaction that the temperature in the reaction cavity reaches alkaline coupling is adjusted by heating unit
Obtain alkaline coupling product.
The Reactive dye red M-3BE dyestuff is obtained finally, saltouing, drying and refining the alkaline coupling product.
Further, it in some embodiments, it is desirable to adjust the reaction environment of coupling reaction, specifically includes:
S141: being 0-45 DEG C by the intracorporal temperature of reaction chamber that heating unit adults couple closes reaction member
S142: being 1-8 by the range that sodium carbonate adjusts pH.
It can guarantee above-mentioned reaction in reasonable reaction environment in this way.It is below to show with certain specific experiment parameters
Example is illustrated the performance of the Reactive dye red M-3BE dyestuff of continuous production method production through the invention.
(a) preparation (spiral coil reactor) of para-ester diazonium salt
Weigh 7.4g para-ester and add water 30ml, then plus the stirring of 10%Na2CO3 solution, room-temperature dissolution to pH=7.5~8.5,
1.8gNaNO2 stirring and dissolving is added, referred to as alkaline para-ester and sodium nitrite mixed liquor.
The hydrochloric acid that alkaline para-ester and sodium nitrite mixed liquor and 75ml concentration are 1mol/L is squeezed into spiral shell by peristaltic pump
The premix component of capstan pipe reactor, the feed rate of alkaline para-ester and sodium nitrite mixed liquor are 25ml/min, hydrochloric acid into
Doses is 50ml/min, and the flow of hydrochloric acid and the molar ratio of alkalinity para-ester are 3:1.Temperature is controlled by thermostat collet at 5 DEG C.
Obtain faint yellow para-ester diazonium salt suspension.
(b) acid coupling reaction (supergravity reactor)
The H acid powder for weighing 4.7g, adds water 30ml, adds the stirring of 10%Na2CO3 solution, room-temperature dissolution to pH=6.5
~7.5, referred to as H acid double sodium salt solution.Spiral coil reactor outlet is connect with high-gravity rotating bed one of entrance,
H acid double sodium salt solution is adjusted flow by constant-flux pump to connect for 24ml/min with another high-gravity rotating bed entrance, point
Two stock materials are squeezed into high-gravity rotating bed, and temperature is controlled by thermostat collet at 15 DEG C or so, and revolving bed revolving speed is 2000rpm.H
Sour double sodium salt solution feed amount and the molar ratio of para-ester diazonium salt are 1:2, obtain aubergine acid coupling product.
(c) alkaline coupling reaction (supergravity reactor)
The acid coupling reaction product of above-mentioned acid coupling reaction revolving bed outlet, which is adjusted flow by constant-flux pump, is
99ml/min is connect with one of entrance of alkaline coupling reaction revolving bed, and 10%Na2CO3 solution is adjusted by constant-flux pump
Flow is that 10ml/min is connect with alkaline coupling reaction another entrance of revolving bed, and two stock materials is divided to be greater than in high-gravity rotating bed,
Temperature is controlled by thermostat collet at 15 DEG C or so, and revolving bed revolving speed is 1800rpm, obtains black-and-blue alkaline coupling product.
Feed liquid is saltoutd, is dried, purification, then after drying, Reactive dye red M-3BE dyestuff is obtained, yield is up to 98.5%,
Sample purity is up to 94%.
2, the continuous production of active yellow M-5G
In the embodiment, the diazo component includes para-ester and nitrite, and the diazo reagent includes hydrochloric acid, institute
Stating coupling component includes 1- (the chloro- 4- sulfonic acid of 2,5- bis-) -3- methyl -5- pyrazolone and sodium carbonate.
Diazo-reaction process are as follows: carry out para-ester and nitrite mixed liquor and hydrochloric acid solution in advance by premix component
It is mixed, as shown in Fig. 2, being then continuously input into spiral coil reactor respectively by pipeline, diazonium salt solution or suspension are obtained,
Diazo-reaction carries out at preferably 0 DEG C to 20 DEG C at -10 DEG C to+40 DEG C, when charging the hydrogen ion of diazo-reaction hydrochloric acid with it is right
The molar ratio of position ester is 2~8:1, preferably 3:1, and the molar ratio of sodium nitrite and para-ester is 1~2:1, preferably 1.01~1.1:
1, feed flow rate is in 0.08~0.8m/s, preferably 0.4~0.8m/s.
Coupling reaction process are as follows: diazonium salt and coupling component are continuously input into rotating packed bed reactor respectively, passed through
Coupling reaction generates coupling product, and reaction temperature is 0 DEG C to 45 DEG C, preferably 5 DEG C~15 DEG C；PH is 1~8, preferably pH=6~8；
Rotating packed bed reactor revolving speed is 500~2500rpm, preferably 1000~2000rpm.
Those skilled in the art are illustrated, and the above method can be summarized as following expressions, by as shown in connection with fig. 8,
Preparation method includes:
S21: the mixed liquor of para-ester and nitrite is passed through in premix component with hydrochloric acid and is premixed.
S22: the mixed solution that para-ester, nitrite and hydrochloric acid are formed is passed through spiral coil reactor and carries out diazonium
Reaction generates para-ester diazonium salt suspension.
S23: by the para-ester diazonium salt suspension, 1- (the chloro- 4- sulfonic acid of 2,5- bis-) -3- methyl -5- pyrazolone with
And sodium carbonate is passed through hypergravity coupling reaction unit and carries out the coupling reaction generation active yellow M-5G dyestuff.
In the embodiment, step S21 is specifically included:
S211: by para-ester and nitrite according to molar ratio be 1:1-1:2 carry out be mixed to form mixed liquor.
S212: it is described pre- that the mixed liquor and hydrochloric acid according to para-ester and hydrionic molar ratio are that 1:2-1:8 is passed through
Mixed component.
In the embodiment, step S22 is specifically included:
S221: being -10 to 40 DEG C by the intracorporal temperature of reaction chamber that heating unit controls the spiral coil reactor.
S222: being 1-8 by the range that sodium carbonate adjusts pH.
S223: under the reaction environment that temperature is -10 to 40 DEG C, the range of pH is 1-8, by para-ester, nitrite with
And the mixed solution that hydrochloric acid is formed is passed through spiral coil reactor progress diazo reaction generation para-ester diazonium salt suspension.
Further, in some embodiments, above-mentioned steps S23 is specifically included:
S231: by the 1- (the chloro- 4- sulfonic acid of 2,5- bis-) -3- methyl -5- pyrazolone solution and the sodium carbonate liquor
The range for being mixed to form pH is the coupling component solution of 6.5-7.5.
S232: the coupling component solution and diazonium salt circulation are pumped into the anti-of the hypergravity coupling reaction unit
It answers in cavity, the reaction temperature progress coupling reaction that the temperature in the reaction cavity reaches coupling reaction is adjusted by heating unit
Obtain coupling product.
The active yellow M-5G dyestuff is obtained finally, the coupling product is saltoutd, dry and is refined.
Further, it in some embodiments, it is desirable to adjust the reaction environment of coupling reaction, specifically includes:
S241: being 0-45 DEG C by the intracorporal temperature of reaction chamber that heating unit adults couple closes reaction member
S242: being 1-8 by the range that sodium carbonate adjusts pH.
It can guarantee above-mentioned reaction in reasonable reaction environment in this way.It is below to show with certain specific experiment parameters
Example is illustrated the performance of the active yellow M-5G dyestuff of continuous production method production through the invention.
(a) preparation (spiral coil reactor) of para-ester diazonium salt
Weigh 11.1g para-ester and add water 90ml, then plus the stirring of 10%Na2CO3 solution, room-temperature dissolution to pH=6.5~
7.5, add 2.9gNaNO2 stirring and dissolving, referred to as para-ester and sodium nitrite mixed liquor.
The hydrochloric acid that para-ester and sodium nitrite mixed liquor and 119ml concentration are 1mol/L is squeezed into helical disk by constant-flux pump
The feed rate of the premix component of pipe reactor, para-ester and sodium nitrite mixed liquor is 30ml/min, and hydrochloric acid inlet amount is
40ml/min, the flow of hydrochloric acid and the molar ratio of para-ester are 3:1.Temperature is controlled by thermostat collet at 5 DEG C.It obtains faint yellow
Para-ester diazonium salt suspension.
(b) coupling reaction (supergravity reactor)
1- (2,5- bis- chloro- 4- the sulfonic acid) -3- methyl -5- pyrazolone powder for weighing 12.8g, adds water 45ml, adds
The stirring of 10%Na2CO3 solution, room-temperature dissolution to pH=6.5~7.5, referred to as coupling component solution.Spiral coil reactor is gone out
Mouth is connect with one of entrance of rotating packed bed reactor, and coupling component solution is adjusted flow by constant-flux pump and is
15ml/min is connect with another entrance of rotating packed bed reactor, and two stock materials is divided to squeeze into rotating packed bed reactor
In, temperature is controlled by thermostat collet at 10 DEG C or so, and revolving bed revolving speed is 1400rpm.Coupling component solution feed amount with it is right
The molar ratio of position ester diazonium salt is 1:1, obtains yellow coupling product.
Feed liquid is saltoutd, is dried, purification, then after drying, active yellow M-5G dyestuff is obtained, yield is up to 97.5%,
Sample purity is up to 95%.
Obviously, either Reactive dye red M-3BE dyestuff or active yellow M-5G can reach in high yield and the sample of high-purity
Product, and it is almost the same with a batch of properties of product, certainly, although the present invention is with Reactive dye red M-3BE dyestuff and active yellow M-5G
As the example of continuous production, but not indicate that the present invention can be only used to two above-mentioned examples, from hair of the invention
From the point of view of bright design, the type of azo active dyestuff and main body of the invention design have no direct correlation.It is to be understood that ability
Domain those of ordinary skill combines inventive concept proposed by the present invention, can be applied in any azo active dyestuff, the present invention exists
This does not do exhaustion.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of continuous production system of the azo active dyestuff of hypergravity, which is characterized in that the system comprises:
Diazo-reaction unit, the diazo-reaction unit include:
Component is premixed, diazo component and diazo reagent are premixed, and
Spiral coil reactor is connected to the premix component, so that the reaction solution after premix is reacted in the spiral coil
Diazo-reaction is carried out in device generates diazonium salt；
The system further comprises the hypergravity coupling reaction unit being connected with the diazo-reaction, the overweight couple
Reaction member is closed to contaminate for making diazonium salt and coupling component carry out the coupling reaction generation azo activity under Elevated Gravity
Material.
2. system according to claim 1, which is characterized in that the premix component includes the first perfusion tube and the second infusion
Pipe；
First perfusion tube is sheathed on the outside of second perfusion tube, and first perfusion tube and second infusion
With gap for one of circulation of diazo component and diazo reagent between pipe, the cavity in second perfusion tube is for weight
Nitrogen component and the circulation of the another one of diazo reagent；
First perfusion tube is mixed close to the formation of one end of the spiral coil reactor for diazo component and diazo reagent
Pre-mix zone, second perfusion tube extends to the inlet of the pre-mix zone, and sprays the diazo component to the pre-mix zone
With the another one of diazo reagent.
3. system according to claim 2, which is characterized in that the pre-mix zone include close on its inlet reducing diameter part and
The flat part being integrally connected to the reducing diameter part.
4. system according to claim 1, which is characterized in that the hypergravity coupling reaction unit includes:
Supergravity reactor is connected to the spiral coil reactor, and
For the diazonium salt after diazo reaction to be pumped into the pump of the high gravity rotating packed bed reactor.
5. system according to claim 4, which is characterized in that the pump is polytetrafluoro constant-flux pump.
6. system according to claim 1, which is characterized in that the spiral coil in the spiral coil reactor is using poly-
Urethane is made.
7. system according to claim 1, which is characterized in that the interior table of the spiral coil in the spiral coil reactor
Face is combined with urethane material.
8. system according to claim 1, which is characterized in that the azo active dyestuff be Reactive dye red M-3BE dyestuff or
Active yellow M-5G dyestuff.
9. system according to claim 1, which is characterized in that the system further comprises heat exchange unit, the heat exchange
Unit is for controlling the intracorporal temperature of the spiral coil reactor reaction chamber and the hypergravity coupling reaction unit process chamber
Intracorporal temperature.
10. system according to claim 9, which is characterized in that the heat exchange unit includes:
It is set in the pipeline collet of the pipeline external of the spiral coil reactor, the pipeline collet has and can be passed through liquid
Cavity；
It is set in the shell collet that the supergravity reactor forms the outer side of shell of reaction cavity, the shell collet has can
It is passed through the cavity of liquid；And
For the heat-exchanger rig for being passed through liquid in the pipeline collet and the shell collet to be heated or cooled.
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| CN109894069A (en) * | 2019-04-23 | 2019-06-18 | 大连鼎燕医药化工有限公司 | It is used to prepare the thermal decomposition reactor and its system, continuous preparation process of fluorinated aromatic hydrocarbon |
| CN112371072A (en) * | 2020-11-05 | 2021-02-19 | 浙江迪邦化工有限公司 | System and process for continuously producing diazonium salt solution |
| CN112457683A (en) * | 2020-11-26 | 2021-03-09 | 北京化工大学 | Continuous production system of nanometer azo-dye |
| CN112592602A (en) * | 2020-11-04 | 2021-04-02 | 北京化工大学 | Continuous production system of nano disperse dye |
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| US20110257424A1 (en) * | 2010-04-15 | 2011-10-20 | Shanghai Research Institute Of Petrochemical Technology Sinopec | Process for Producing C1-C4 Alkyl Nitrite |
| CN105668615A (en) * | 2016-01-27 | 2016-06-15 | 柳州豪祥特科技有限公司 | Technology for preparing SnO2 nano-powder with continuous hydrothermal method |
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| CN101870824A (en) * | 2010-06-08 | 2010-10-27 | 北京化工大学 | Method for preparing azo colouring agent by utilizing supergravity reactor |
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| CN109894069A (en) * | 2019-04-23 | 2019-06-18 | 大连鼎燕医药化工有限公司 | It is used to prepare the thermal decomposition reactor and its system, continuous preparation process of fluorinated aromatic hydrocarbon |
| CN112592602A (en) * | 2020-11-04 | 2021-04-02 | 北京化工大学 | Continuous production system of nano disperse dye |
| CN112592602B (en) * | 2020-11-04 | 2022-06-28 | 北京化工大学 | Continuous production system of nano disperse dye |
| CN112371072A (en) * | 2020-11-05 | 2021-02-19 | 浙江迪邦化工有限公司 | System and process for continuously producing diazonium salt solution |
| CN112457683A (en) * | 2020-11-26 | 2021-03-09 | 北京化工大学 | Continuous production system of nanometer azo-dye |
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