CN103146221B - Method and device for continuously producing dyes - Google Patents
Method and device for continuously producing dyes Download PDFInfo
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- CN103146221B CN103146221B CN201310078687.6A CN201310078687A CN103146221B CN 103146221 B CN103146221 B CN 103146221B CN 201310078687 A CN201310078687 A CN 201310078687A CN 103146221 B CN103146221 B CN 103146221B
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Abstract
The invention discloses a method and a device for continuously producing dyes. The method comprises the following steps: adding diazotization reaction raw materials into an ingredient kettle, controlling temperature in the kettle, allowing the materials to flow in a tubular reactor through an overflow orifice, detecting the reaction state through an online detection device, continuously discharging the diazotization compound solution obtained through the reaction, continuously feeding the diazotization compound solution and a coupling component solution according to a specified ratio, allowing the materials to flow into the tubular reactor through the overflow orifice, detecting the reaction state through the online detection device, transferring the coupling reaction materials into a crystal transformation kettle, performing crystal transformation, and performing filter pressing to obtain a dye filter cake, wherein the filter cake mother solution and the wash water are circulated for preparing the coupling component solution. The reaction temperature, material flow and reaction state detection device are automatically subjected to interconnected control. According to the method, automatic and continuous dye production is realized, the production capacity, the product quality and yield are improved, the labor intensity and working conditions of workers are improved, the waste water, water gas and waste residue amounts in the dye production process are greatly reduced, and circular economy and cleaner production process are realized.
Description
Technical field
The present invention relates to a kind of method of continuous production dyestuff and realize the device of the method.
Background technology
Dyestuffs industries is one of historical the longest industry in Fine Chemical Industry.Along with the development of China light and textile industries, dyestuffs industries is also developed rapidly in recent years; Especially since entering the new millennium, China's dyestuffs industries development is more rapid, and output, export volume and consumption all leap to the first in the world.
The preparation of general dyestuff is comprised of step diazotization reaction and coupled reaction.In diazotization reaction, diazonium salt at high temperature easily decomposes, and the preparation of diazonium salt is a thermopositive reaction, and therefore, production process is quite high to the requirement of conducting heat.In coupled reaction, diazonium salt also easily decomposes, if diazonium salt molecule can not collide and react with coupling component molecule in the short period of time at the utmost point, will soon decompose.
In conventional batch reactor, be difficult to guarantee that each field of reactor all stirs, local stoicheiometry departs from reaction conditions, the phenomenon such as non-uniform temperature in reactor, capital causes diazonium salt to decompose, and various side reactions occur and causes that diazonium salt quality is not good and dyestuffs purity is on the low side, yield is on the low side.
The mode of production of China's dyestuff is still relatively backward at present, and automatic control technology is not yet on the actual application in DYE PRODUCTION process, and the automation level of enterprise is generally lower.Why like this, be because DYE PRODUCTION technical process complexity, trivial operations, processing medium have certain toxicity and corrodibility and inflammable and explosive property, high to the security requirement of producing, be difficult to automatically in control, realizing the reasons such as automatic detection reaction terminal and Quality Feedback.
In addition, dye industry is as traditional Fine Chemical Industry, and " three wastes " (waste water,waste gas and industrial residue) quantity discharged is large, and especially contaminated wastewater is the most serious, is restricting the development of whole industry.Can reduces " three wastes " that in production process, produce and has become the key issue that can dye industry continue development.
Summary of the invention
Key of the present invention is continuous and automaticization production dyestuff, has realized online detection and the automatic interlock flow control of reaction end.
The invention provides a kind of method of continuous production dyestuff, comprise reaction raw materials ratio continuous feeding to batching kettle is according to the rules prepared burden, the material continuous feeding of joining in batching kettle reacts and continuous discharge to tubular reactor, it is characterized in that, by the response behaviour proofing unit detection reaction state arranging on tubular reactor end, if reaction mass continuous discharge while having reacted after testing, if reacted after testing, reaction mass is back to batching kettle or proceeds to adjusting still, again batching (when proportion scale occurs when abnormal) as required, then continued reaction.
The response behaviour proofing unit that the present invention produces in the method for dyestuff is continuously preferably polar voltages Controlling System and potential measurement Controlling System.
The present invention produces polar voltages Controlling System in the method for dyestuff continuously and the electrode materials of potential measurement Controlling System is preferably a kind of or its alloy that is selected from Au, Pt, Ag, Sb, Mo, Cr, graphite.
The present invention produces the method for dyestuff continuously, is preferably the method for continuous production azoic dyestuff, comprises coupled reaction step, and coupled reaction is monitored by the potential measurement Controlling System that is arranged on tubular type coupling reactor end.
The method that the present invention produces dyestuff continuously preferably includes: diazo solution and coupling component solution are supplied to prepare burden to batching kettle by measuring and testing device ratio according to the rules continuously;
Streams in batching kettle is carried out coupled reaction to tubular type coupling reactor, controls coupled reaction temperature at-10 ℃～20 ℃;
The potential measurement Controlling System that coupled reaction material arranges on tubular type coupling reactor end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle or proceed to adjusting still, again prepare burden as required, then continued coupled reaction;
In transfer still and, if yes, regulate reaction mass in still to proceed in brilliant still and turn brilliant; By turning the brilliant material that turns obtaining after crystalline substance, adopt pressure filter to carry out press filtration, washing, obtain dyestuff filter cake.
The present invention produces in the method for dyestuff continuously, preferably in coupled reaction step, the flow of the flow of feed product diazo solution and coupling component solution and the heat-eliminating medium in refrigerating unit and temperature of reaction are carried out to interlocked control, comprise set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
The present invention produces in the method for dyestuff continuously, as the raw material diazonium compound of coupled reaction and the mol ratio of coupling component, is preferably 1:0.95～1.05.
The present invention produces in the method for dyestuff continuously, the washing water that the mother liquid coming preferably press filtration being produced, washing produce carry out categorised collection, be mixed with making beating liquid, the mass percent of controlling acid in making beating liquid is 2～15%, for the preparation of coupling component solution.
The present invention produces in the method for dyestuff continuously, and preferred described method also comprises diazotization reaction step, and diazotization reaction is monitored by the polar voltages Controlling System that is arranged on tubular type diazotization reaction device end.
The present invention produces in the method for dyestuff continuously, and preferably diazotization reaction step comprises:
Diazo component, nitrosyl sulfuric acid and optional acid are prepared burden to batching kettle by measuring apparatus ratio continuously feeding according to the rules;
Streams in batching kettle is to tubular type diazotization reaction device, and controlling diazotization reaction temperature is-10 ℃～30 ℃;
The polar voltages Controlling System that diazotization reaction material arranges on tubular type diazotization reaction device end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle or proceed to adjusting still, again prepare burden as required, then continued diazotization reaction;
In transfer still and, if yes, regulate diazo solution in still as the raw material of coupled reaction, for follow-up coupled reaction.
The present invention produces in the method for dyestuff continuously, preferably in diazotization reaction step, feed product diazo component, optional acid and the flow of nitrosyl sulfuric acid and the flow of the heat-eliminating medium in refrigerating unit and temperature of reaction are carried out to interlocked control, comprise set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
The present invention produces in the method for dyestuff continuously, and preferably diazo component, nitrosyl sulfuric acid and optional sour mol ratio are 1:1.0～1.1:0～8.
The present invention produces in the method for dyestuff continuously, and preferred described batching kettle material is titanium or stainless steel, and it has high temperature resistant, corrosion resistant characteristic.The temperature of batching kettle is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe.
The present invention produces in the method for dyestuff continuously, preferred described batching kettle is provided with overflow port, material flows out from described overflow port, described overflow port place is provided with vibration filters, the filtering net aperture of described vibration filters is 10～60 orders, the material of described filtering net is to be selected from any one of titanium, stainless steel, glass fibre, charcoal fiber, fluoroplastics, and it has high temperature resistant, corrosion resistant characteristic.
The present invention produces in the method for dyestuff continuously, and preferred described tubular reactor material is titanium or stainless steel, and the temperature in tubular reactor is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe.
The present invention produces in the method for dyestuff continuously, and preferred described tubular reactor adopts baffling, shunting and homogenizing pump technology to make material reaction homogenizing and stabilization.
The present invention produces in the method for dyestuff continuously, and preferably described tubular reactor is 1 stage reactor or 2 grades of above reactors, and turning brilliant still is 1～3.
The present invention produces in the method for dyestuff continuously, preferably by DCS Controlling System, automatically controls.
The present invention also provides a kind of device of continuous production dyestuff, it is characterized in that comprising, the response behaviour proofing unit arranging on raw material feed device, measuring apparatus, batching kettle, tubular reactor, tubular reactor end and optional adjusting still, when the device operation of described continuous production dyestuff, operational process comprises:
Reaction raw materials ratio continuous feeding to batching kettle is according to the rules prepared burden, the material continuous feeding of joining in batching kettle reacts and continuous discharge to tubular reactor, whether the response behaviour proofing unit detection reaction arranging on tubular reactor end completes, the material continuous discharge having reacted, reacting uncompleted material returns to batching kettle or proceeds to adjusting still, again prepare burden as required, then continued reaction.
In the device of continuous production dyestuff of the present invention, preferably described response behaviour proofing unit is polar voltages Controlling System or potential measurement Controlling System.
In the device of continuous production dyestuff of the present invention, the electrode materials of preferred described polar voltages Controlling System or potential measurement Controlling System is a kind of or its alloy that is selected from Au, Pt, Ag, Sb, Mo, Cr, graphite.
The device of continuous production dyestuff of the present invention is preferably the device of continuous production azoic dyestuff, comprise coupled reaction part, described coupled reaction partly comprises tubular type coupling reactor and is arranged on the potential measurement Controlling System as response behaviour proofing unit on described tubular type coupling reactor end.
In the device of continuous production dyestuff of the present invention, preferred described coupled reaction partly comprises: the potential measurement Controlling System arranging on raw material feed device, measuring apparatus, batching kettle, tubular type coupling reactor, described tubular type coupling reactor end, refrigerating unit, device for monitoring temperature, transfer still, optional adjusting still, turn brilliant still and pressure filter, when the device operation of described continuous production dyestuff, coupled reaction part operational process comprises:
Diazo solution and coupling component solution supply to prepare burden to batching kettle by measuring apparatus ratio according to the rules continuously;
Streams in batching kettle is carried out coupled reaction to tubular type coupling reactor;
The potential measurement Controlling System that coupled reaction material arranges on tubular type coupling reactor end detects, the material continuous discharge having reacted is to transfer still, react uncompleted material and be back to batching kettle or proceed to adjusting still, again prepare burden as required, then continued coupled reaction;
In transfer still and, if any, regulate reaction mass in still to proceed in brilliant still and turn brilliant;
Turn the crystalline substance that turns obtaining after crystalline substance and expect to proceed in pressure filter to carry out press filtration, washing, obtain dyestuff filter cake.
In the device of continuous production dyestuff of the present invention, the preferred measuring apparatus to coupling reactive moieties, refrigerating unit, the device for monitoring temperature control that links, thereby when operation, flow and the temperature of reaction of heat-eliminating medium in the flow of raw material feed device Raw material diazo solution and coupling component solution and refrigerating unit are carried out to interlocked control, control process comprises set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
In the device of continuous production dyestuff of the present invention, preferably also comprise diazotization reaction part, described diazotization reaction partly comprises tubular type diazotization reaction device and is arranged on the polar voltages Controlling System as response behaviour proofing unit on described tubular type diazotization reaction device end.
In the device of continuous production dyestuff of the present invention, preferred described diazotization reaction partly comprises: raw material feed device, measuring apparatus, batching kettle, tubular type diazotization reaction device, be arranged on polar voltages Controlling System, refrigerating unit, device for monitoring temperature, transfer still and optional adjusting still on tubular type diazotization reaction device, when the device operation of described continuous production dyestuff, the operational process of diazotization reaction part comprises:
Diazo component, nitrosyl sulfuric acid and optional acid are prepared burden to batching kettle by measuring apparatus ratio continuously feeding according to the rules;
Streams in batching kettle is carried out diazotization reaction to tubular type diazotization reaction device;
The polar voltages Controlling System that diazotization reaction material arranges on tubular type diazotization reaction device end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle or proceed to adjusting still, again prepare burden as required, then continued diazotization reaction;
Transfer still and, if any, regulate still as the raw material feed device of coupled reaction, diazo solution is wherein supplied with to follow-up coupled reaction.
In the device of continuous production dyestuff of the present invention, preferably to diazotization reaction measuring apparatus partly, refrigerating unit, the device for monitoring temperature control that links, thereby in when operation by raw material feed device Raw material diazo component, in nitrosyl sulfuric acid and optional sour flow and refrigerating unit, flow and the temperature of reaction of heat-eliminating medium are carried out interlocked control, control process comprises set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
In the device of continuous production dyestuff of the present invention, preferred described batching kettle material is titanium or stainless steel, and it has high temperature resistant, corrosion resistant characteristic.Batching kettle temperature is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe by device for monitoring temperature.
In the device of continuous production dyestuff of the present invention, preferred described batching kettle is provided with overflow port, material flows out from described overflow port, described overflow port place is provided with vibration filters, the filtering net aperture of described vibration filters is 10～60 orders, the material of described filtering net is to be selected from any one of titanium, stainless steel, glass fibre, charcoal fiber, fluoroplastics, and it has high temperature resistant, corrosion resistant characteristic.
In the device of continuous production dyestuff of the present invention, preferred described tubular reactor material is titanium or stainless steel, and the temperature in tubular reactor is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe by device for monitoring temperature.
In the device of continuous production dyestuff of the present invention, preferred described tubular reactor adopts baffling, shunting and homogenizing pump technology to make material reaction homogenizing and stabilization.
In the device of continuous production dyestuff of the present invention, preferably described tubular reactor is 1 stage reactor or 2 grades of above reactors, and turning brilliant still is 1～3.
The device of continuous production dyestuff of the present invention is preferably controlled automatically by DCS Controlling System.
Beneficial effect of the present invention is mainly reflected in: realized dyestuff automatic continuous production, throughput, quality product and yield have been improved, workman's labour intensity and working condition are improved simultaneously, the three wastes in DYE PRODUCTION process produce also and significantly reduce, reduce environmental pollution, realized recycling industries and clean production technique.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the present invention produces dye method one example continuously.
Fig. 2 is the schematic diagram that the present invention produces device one example of dyestuff continuously.
Description of reference numerals: A is cage device; B1, B2, B3 are scale tank; P1, P2 are batching kettle; F1, F2 are vibration filters; E1 is polar voltages Controlling System, and E2 is potential measurement Controlling System; K1, K2, K3, K4 are device for monitoring temperature; G1 is tubular type diazotization reaction device, and G2 is tubular type coupling reactor; D1～D10 is pump or volume pump; J is coupling component solution; X1, X2 are work in-process still; Z1, Z2 are transfer still; M is for turning brilliant still; N is for regulating still.
Embodiment
The method and apparatus of serialization of the present invention being produced to dyestuff referring to accompanying drawing describes.
Fig. 2 shown device carries out automatization control by DCS Controlling System.
In Fig. 2, to diazotization reaction raw material measuring apparatus D1, D2, D3, refrigerating unit (shell-and tube condenser in the cooling jacket in batching kettle P1 and tubular reactor G1 and pipe, not shown), the device for monitoring temperature control that links, by diazo component, nitrosyl sulfuric acid, in optional sour flow and refrigerating unit, flow and the diazotization reaction temperature of heat-eliminating medium are carried out interlocked control, when temperature of reaction is during higher than set higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction lower than set lower value time, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
And, to coupling reaction raw materials measuring apparatus D5 and D6, refrigerating unit (shell-and tube condenser in the cooling jacket in batching kettle P2 and tubular reactor G2 and pipe, not shown), the device for monitoring temperature control that links, flow and the coupled reaction temperature of heat-eliminating medium in the flow of diazo solution and coupling component solution and refrigerating unit are carried out to interlocked control, when temperature of reaction is during higher than set higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction lower than set lower value time, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
In Fig. 2, diazo component is continuously fed in batching kettle P1 by solid measuring apparatus D1 with cage A, and simultaneously nitrosyl sulfuric acid and optional acid is continuously fed in batching kettle P1 by volume pump D2, D3, and this batching kettle P1 is provided with overflow port.
Material overflow in batching kettle P1, to tubular type diazotization reaction device G1, is controlled diazotization reaction temperature, and through polar voltages Controlling System E1 detection reaction state, the material having reacted (diazo solution) continuously flow in transfer still Z1; If reacted, material is gone to work in-process still X1, then blowback batching kettle P1, again prepare burden as required, then continued reaction.
Coupling component is used by the making beating liquid with regulation acid concentration of filter cake mother liquid coming, washing water preparation and is pulled an oar, preparation coupling component solution J, and pump is to coupling component solution measures groove B3.
Diazo solution in transfer still Z1 mixes by certain mass ratio with the coupling component solution J in scale tank B3, and continuous pump is prepared burden to batching kettle P2 simultaneously, and batching kettle P2 has overflow port.
Material in batching kettle P2 reacts to tubular type coupling reactor G2 by overflow port overflow, controls coupled reaction temperature, and through potential measurement Controlling System E2 detection reaction state, the material Continuous Flow of having reacted is to transfer still Z2; If reacted, uncompleted reaction mass is gone to work in-process still X2, then pump, to regulating still N, is prepared burden as required again, has then continued coupled reaction.
Coupled reaction material in transfer still Z2 and adjusting still N pumps into turn in brilliant still M and turns brilliant, controls and turns brilliant temperature, obtains turning brilliant material.
To turn brilliant and expect that proceeding to pressure filter carries out press filtration, and wash, obtain dyestuff filter cake.Filter cake mother liquid coming, washing water carry out categorised collection, and the making beating liquid with mother liquid coming, washing water preparation with regulation acid concentration carries out recycle.
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1:
The N that drops into 1980kg in coupling component making beating pot, N-diethyl-3-acetylaminoaniline, pulls an oar with the making beating liquid that 20000kg sulfuric acid mass percent is 3%, obtains coupling component solution J, stand-by.
The nitrosyl sulfuric acid (content is 28%) that adds 420kg in batching kettle P1, open chilled brine, control temperature in the kettle at 20 ℃～30 ℃, slowly twist into 2, 4-dinitrobenzene-6-chloroaniline (diazo component) 200kg mixes and is made into initiator, then by 2, 4-dinitrobenzene-6-chloroaniline (diazo component), nitrosyl sulfuric acid respectively measure control is 571kg/h, 1200kg/h carries out Automatic continuous charging, mixture flow to tubular type diazotization reaction device G1 and reacts from overflow port, after polar voltages Controlling System E1 detection reaction completes, flow to transfer still Z1, by volume pump D5 continuous pump to batching kettle P2.
Obtain 2, diazo solution and N after 4-dinitrobenzene-6-chloroaniline diazotization, N-diethyl-3-acetylaminoaniline coupling component solution J is continuously pumped into batching kettle P2 with the flow of 1771kg/h and 5770kg/h respectively, and the mol ratio of controlling diazonium compound and coupling component is 1:1.04.
The material of above-mentioned mixing flow in tubular type coupling reactor G2 and reacts through overflow port, and temperature is controlled at 0 ± 2 ℃.After potential measurement Controlling System E2 detection reaction completes, flow to transfer still Z2, then pump into and turn brilliant still M, control and turn 50 ± 2 ℃ of brilliant temperature.Turn brilliant rear material entrance pressure filter, through press filtration, washing, obtain 63 DISPERSE Violet 63 93:1 dyestuff filter cake.Simultaneously by filter cake mother liquid coming, washing water respectively pump to mother liquid coming, washing water storage tank, carry out recycled after being mixed with making beating liquid.
Adopt the method and apparatus of above-mentioned continuous production dyestuff to prepare 63 DISPERSE Violet 63 93:1 dyestuff filter cake, realized automatic continuous production, product yield and quality product have been improved, compare with intermittent reaction, dyestuff yield has improved approximately 3%, filter cake purity has improved approximately 2.5%, and filter cake intensity has improved approximately 5%.
Embodiment 2:
In coupling component making beating pot, drop into the N of 700kg, N-diethyl-3-acetylaminoaniline, pulls an oar with the making beating liquid that the sulfuric acid mass percent of 15000kg is 4.5%, obtains coupling component solution J, stand-by.
The nitrosyl sulfuric acid (content is 28%) that adds 380kg in batching kettle P1, the sulfuric acid of 660kg, open chilled brine, control temperature in the kettle at 0 ℃～5 ℃, slowly twist into 2 cyano 4 nitro 6 bromo aniline 200kg and mix and be made into initiator, join complete, by 2 cyano 4 nitro 6 bromo aniline (diazo component), sulfuric acid and nitrosyl sulfuric acid respectively measure control are 300kg/h, 990kg/h, 570kg/h carries out Automatic continuous charging, mixture flow to tubular type diazotization reaction device G1 and reacts from overflow port, after polar voltages Controlling System E1 has reacted, flow to transfer still Z1, pass through again volume pump D5 continuous pump to batching kettle P2.
Diazo solution and N after the 2 cyano 4 nitro 6 bromo aniline diazotization obtaining, N-diethyl-3-acetylaminoaniline coupling component solution J is continuously pumped into batching kettle P2 with the flow of 1860kg/h and 6262kg/h respectively, and the mol ratio of controlling diazonium compound and coupling component is 1:1.02.
The material of above-mentioned mixing is flow in tubular type coupling reactor G2 and reacted through overflow port, and temperature is controlled at 8 ± 2 ℃.After potential measurement Controlling System E2 detection reaction completes, from flowing to transfer still Z2, then pump into and turn brilliant still M; When coupled reaction does not complete after testing, coupled reaction streams is to work in-process still X2, then by pump D9 pump to regulating still N, batching again, has continued after reaction as required, pumps into and turns brilliant still M.Control turns 60 ± 2 ℃ of brilliant temperature.Turn brilliant rear material entrance pressure filter, through press filtration, washing, obtain EX-SF DISPERSE BLUE EX-SF 300 183:1 dyestuff filter cake.Filter cake mother liquid coming, washing water are distinguished to pump to mother liquid coming, washing water storage tank simultaneously, carry out recycled.
Adopt the method and apparatus of above-mentioned continuous production dyestuff to prepare EX-SF DISPERSE BLUE EX-SF 300 183:1 dyestuff filter cake, realized automatic continuous production, product yield and quality product have been improved, compare with intermittent reaction, dyestuff yield has improved approximately 3.5%, filter cake purity has improved approximately 1.5%, and filter cake intensity has improved approximately 5%.
Embodiment 3:
In coupling component making beating pot, put into the 3-(N of 2050kg, N-diallyl) amino-4-methoxyacetanilide, with the making beating liquid that 20000kg sulfuric acid mass percent is 6%, pull an oar, obtain coupling component solution J, stand-by.
The nitrosyl sulfuric acid (content is 28%) that adds 690kg in batching kettle P1, open chilled brine, control temperature in the kettle at 20 ℃～30 ℃, slowly twist into 2, 4-dinitrobenzene-6-bromaniline 330kg is hybridly prepared into initiator, join complete, by 2, 4-dinitrobenzene-6-bromaniline (diazo component), nitrosyl sulfuric acid respectively measure control is 495kg/h, 1035kg/h carries out continuously feeding, mixture flow to tubular type diazotization reaction device G1 and reacts from overflow port, after polar voltages Controlling System E1 detection reaction completes, flow to transfer still Z1, use again volume pump D5 continuous pump to batching kettle P2.When reaction being detected and do not complete, diazotization reaction product pump is back to batching kettle P1, and batching again, has continued diazotization reaction as required.
Obtain 2, diazo solution and 3-(N after 4-dinitrobenzene-6-bromaniline diazotization, N-diallyl) amino-4-methoxyacetanilide coupling component solution J is continuously pumped into batching kettle P2 with the flow of 1530kg/h and 6615kg/h respectively, and the mol ratio of controlling diazonium compound and coupling component is 1:1.04.
Material flow in tubular type coupling reactor G2 and reacts through batching kettle P2 overflow port, and temperature is controlled at 0 ± 2 ℃.After potential measurement Controlling System E2 detection reaction completes, flow to transfer still Z2, then pump into and turn brilliant still M, control and turn 50 ± 2 ℃ of brilliant temperature.Turn brilliant rear material entrance pressure filter, through press filtration, washing, obtain EX-SF DISPERSE BLUE EX-SF 300 291:1 dyestuff filter cake.Filter cake mother liquid coming, washing water are distinguished to pump to mother liquid coming, washing water storage tank simultaneously, carry out recycled.
Adopt the method and apparatus of above-mentioned continuous production dyestuff to prepare EX-SF DISPERSE BLUE EX-SF 300 291:1 dyestuff filter cake, realized automatic continuous production, product yield and quality product have been improved, compare with intermittent reaction, dyestuff yield has improved approximately 2.8%, filter cake purity has improved approximately 2.0%, and filter cake intensity has improved approximately 7%.
The present invention has realized the merging of diazotization and coupled reaction two large independent process and online detection and the automatic interlock flow control of producing, and realized continuously reaction end.Improve production efficiency, reduced cost of labor, realized the mode of production green, environmental protection, there is excellent technique effect.
Claims (33)
1. a method of producing continuously dyestuff, comprise reaction raw materials ratio continuous feeding to batching kettle is according to the rules prepared burden, the material continuous feeding of joining in batching kettle reacts and continuous discharge to tubular reactor, it is characterized in that, by the response behaviour proofing unit detection reaction state arranging on tubular reactor end, if reaction mass continuous discharge while having reacted after testing, if reacted after testing, reaction mass is back to batching kettle, again prepare burden as required, then continued reaction.
2. the method for continuous production dyestuff as claimed in claim 1, is characterized in that described response behaviour proofing unit is polar voltages Controlling System or potential measurement Controlling System.
3. the method for continuous production dyestuff as claimed in claim 2, the electrode materials that it is characterized in that described polar voltages Controlling System or potential measurement Controlling System is a kind of or its alloy that is selected from Au, Pt, Ag, Sb, Mo, Cr, graphite.
4. the method for continuous production dyestuff as claimed in claim 1, it is the method for azoic dyestuff of producing continuously, comprises coupled reaction step, coupled reaction is monitored by the potential measurement Controlling System that is arranged on tubular type coupling reactor end.
5. the method for continuous production dyestuff as claimed in claim 4, is characterized in that, comprising: diazo solution and coupling component solution are supplied to prepare burden to batching kettle by measuring and testing device ratio according to the rules continuously;
Streams in batching kettle is carried out coupled reaction to tubular type coupling reactor, controls coupled reaction temperature at-10 ℃～20 ℃;
The potential measurement Controlling System that coupled reaction material arranges on tubular type coupling reactor end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle, again prepare burden as required, then continued coupled reaction;
Reaction mass in transfer still proceeds in brilliant still and turns brilliant; By turning the brilliant material that turns obtaining after crystalline substance, adopt pressure filter to carry out press filtration, washing, obtain dyestuff filter cake.
6. the method for continuous production dyestuff as claimed in claim 5, it is characterized in that, in coupled reaction step, feed product diazo solution and the flow of coupling component solution and the flow of heat-eliminating medium and temperature of reaction are carried out to interlocked control, comprise set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
7. the method for the continuous production dyestuff as described in claim 5 or 6, is characterized in that, the mol ratio of described diazonium compound and coupling component is 1:0.95～1.05.
8. the method for the continuous production dyestuff as described in claim 5 or 6, it is characterized in that, the washing water that the mother liquid coming that press filtration is produced, washing produce carry out categorised collection, be mixed with making beating liquid, the mass percent of controlling acid in making beating liquid is 2～15%, for the preparation of coupling component solution.
9. the method for the continuous production dyestuff as described in claim 4～6 any one, is characterized in that, described method also comprises diazotization reaction step, and diazotization reaction is monitored by the polar voltages Controlling System that is arranged on tubular type diazotization reaction device end.
10. the method for continuous production dyestuff as claimed in claim 9, is characterized in that, diazotization reaction step comprises:
Diazo component, nitrosyl sulfuric acid and optional acid are prepared burden to batching kettle by measuring apparatus ratio continuously feeding according to the rules;
Streams in batching kettle is to tubular type diazotization reaction device, and controlling diazotization reaction temperature is-10 ℃～30 ℃;
The polar voltages Controlling System that diazotization reaction material arranges on tubular type diazotization reaction device end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle, again prepare burden as required, then continued diazotization reaction;
Diazo solution in transfer still is as the raw material of coupled reaction, for follow-up coupled reaction.
The method of 11. continuous production dyestuffs as claimed in claim 10, it is characterized in that, in diazotization reaction step, feed product diazo component, optional acid and the flow of nitrosyl sulfuric acid and the flow of heat-eliminating medium and temperature of reaction are carried out to interlocked control, comprise set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
The method of 12. continuous production dyestuffs as claimed in claim 11, is characterized in that, diazo component, nitrosyl sulfuric acid and optional sour mol ratio are 1:1.0～1.1:0～8.
The method of 13. continuous production dyestuffs as described in claim 4～6 any one, is characterized in that described batching kettle material is titanium or stainless steel, and the temperature of batching kettle is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe.
The method of 14. continuous production dyestuffs as described in claim 4～6 any one, it is characterized in that, described batching kettle is provided with overflow port, material flows out from described overflow port, described overflow port place is provided with vibration filters, the filtering net aperture of described vibration filters is 10～60 orders, and the material of described filtering net is to be selected from any one of titanium, stainless steel, glass fibre, charcoal fiber, fluoroplastics.
15. as described in claim 4～6 any one the method for continuous production dyestuff, it is characterized in that described tubular reactor material is titanium or stainless steel, the temperature in tubular reactor is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe.
16. as described in claim 4～6 any one the method for continuous production dyestuff, it is characterized in that described tubular reactor adopts baffling, shunting and homogenizing pump technology to make material reaction homogenizing and stabilization.
The method of 17. continuous production dyestuffs as described in claim 4～6 any one, is characterized in that described tubular reactor is 1 stage reactor or 2 grades of above reactors, and turning brilliant still is 1～3.
The method of the continuous production dyestuff described in 18. claim 1～6 any one, it is controlled automatically by DCS Controlling System.
19. 1 kinds of devices of producing continuously dyestuff, it is characterized in that comprising, the response behaviour proofing unit arranging on raw material feed device, measuring apparatus, batching kettle, tubular reactor, tubular reactor end, when the device operation of described continuous production dyestuff, operational process comprises:
Reaction raw materials ratio continuous feeding to batching kettle is according to the rules prepared burden, the material continuous feeding of joining in batching kettle reacts and continuous discharge to tubular reactor, whether the response behaviour proofing unit detection reaction arranging on tubular reactor end completes, the material continuous discharge having reacted, react uncompleted material and return to batching kettle, again prepare burden as required, then continued reaction.
The device of 20. continuous production dyestuffs as claimed in claim 19, is characterized in that described response behaviour proofing unit is polar voltages Controlling System or potential measurement Controlling System.
The device of 21. continuous production dyestuffs as claimed in claim 20, is characterized in that, the electrode materials of described polar voltages Controlling System or potential measurement Controlling System is a kind of or its alloy that is selected from Au, Pt, Ag, Sb, Mo, Cr, graphite.
The device of 22. continuous production dyestuffs as claimed in claim 19, it is to produce continuously the device of azoic dyestuff, comprise coupled reaction part, described coupled reaction partly comprises tubular type coupling reactor and is arranged on the potential measurement Controlling System as response behaviour proofing unit on described tubular type coupling reactor end.
The device of 23. continuous production dyestuffs as claimed in claim 22, it is characterized in that, described coupled reaction partly comprises: the potential measurement Controlling System arranging on raw material feed device, measuring apparatus, batching kettle, tubular type coupling reactor, described tubular type coupling reactor end, refrigerating unit, device for monitoring temperature, transfer still, turn brilliant still and pressure filter, when the device operation of described continuous production dyestuff, coupled reaction part operational process comprises:
Diazo solution and coupling component solution supply to prepare burden to batching kettle by measuring apparatus ratio according to the rules continuously;
Streams in batching kettle is carried out coupled reaction to tubular type coupling reactor;
The potential measurement Controlling System that coupled reaction material arranges on tubular type coupling reactor end detects, and the material continuous discharge having reacted, to transfer still, reacts uncompleted material and is back to batching kettle, according to again preparing burden, has then continued coupled reaction;
Reaction mass in transfer still proceeds in brilliant still and turns brilliant;
Turn the crystalline substance that turns obtaining after crystalline substance and expect to proceed in pressure filter to carry out press filtration, washing, obtain dyestuff filter cake.
The device of 24. continuous production dyestuffs as claimed in claim 23, it is characterized in that, measuring apparatus to coupling reactive moieties, refrigerating unit, the device for monitoring temperature control that links, thereby when operation, flow and the temperature of reaction of heat-eliminating medium in the flow of raw material feed device Raw material diazo solution and coupling component solution and refrigerating unit are carried out to interlocked control, control process comprises set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
The device of 25. continuous production dyestuffs as described in claim 22～24 any one, it is characterized in that, also comprise diazotization reaction part, described diazotization reaction partly comprises tubular type diazotization reaction device and is arranged on the polar voltages Controlling System as response behaviour proofing unit on described tubular type diazotization reaction device end.
The device of 26. continuous production dyestuffs as claimed in claim 25, it is characterized in that, described diazotization reaction partly comprises: raw material feed device, measuring apparatus, batching kettle, tubular type diazotization reaction device, be arranged on polar voltages Controlling System, refrigerating unit, device for monitoring temperature, transfer still on tubular type diazotization reaction device, when the device operation of described continuous production dyestuff, the operational process of diazotization reaction part comprises:
Diazo component, nitrosyl sulfuric acid and optional acid are prepared burden to batching kettle by measuring apparatus ratio continuously feeding according to the rules;
Streams in batching kettle is carried out diazotization reaction to tubular type diazotization reaction device;
The polar voltages Controlling System that diazotization reaction material arranges on tubular type diazotization reaction device end detects, the material continuous discharge having reacted is to transfer still, react uncompleted product pump and be back to batching kettle, again prepare burden as required, then continued diazotization reaction;
Transfer still, as the raw material feed device of coupled reaction, is supplied with follow-up coupled reaction by diazo solution wherein.
The device of 27. continuous production dyestuffs as claimed in claim 26, it is characterized in that, measuring apparatus to diazotization reaction part, refrigerating unit, the device for monitoring temperature control that links, thereby in when operation by raw material feed device Raw material diazo component, in nitrosyl sulfuric acid and optional sour flow and refrigerating unit, flow and the temperature of reaction of heat-eliminating medium are carried out interlocked control, control process comprises set temperature upper lower limit value, when temperature of reaction is during higher than higher limit, turn in proportion or close each feed product flow down, tune up the flow of heat-eliminating medium simultaneously, when temperature of reaction is during lower than lower value, turn the flow of heat-eliminating medium down, until temperature of reaction is within the scope of bound.
The device of 28. continuous production dyestuffs as described in claim 22～24 any one, it is characterized in that described batching kettle material is titanium or stainless steel, batching kettle temperature is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe by device for monitoring temperature.
The device of 29. continuous production dyestuffs as described in claim 22～24 any one, described batching kettle is provided with overflow port, material flows out from described overflow port, described overflow port place is provided with vibration filters, the filtering net aperture of described vibration filters is 10～60 orders, and the material of described filtering net is to be selected from any one of titanium, stainless steel, glass fibre, charcoal fiber, fluoroplastics.
The device of 30. continuous production dyestuffs as described in claim 22～24 any one, it is characterized in that described tubular reactor material is titanium or stainless steel, the temperature in tubular reactor is controlled by this dual-cooled device of shell-and tube condenser in cooling jacket and pipe by device for monitoring temperature.
The device of 31. continuous production dyestuffs as described in claim 22～24 any one, is characterized in that described tubular reactor adopts baffling, shunting and homogenizing pump technology to make material reaction homogenizing and stabilization.
The device of 32. continuous production dyestuffs as described in claim 22～24 any one, is characterized in that described tubular reactor is 1 stage reactor or 2 grades of above reactors, and turning brilliant still is 1～3.
The device of 33. continuous production dyestuffs as described in claim 19～24 any one, it is controlled automatically by DCS Controlling System.
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| CN201310078687.6A CN103146221B (en) | 2013-03-12 | 2013-03-12 | Method and device for continuously producing dyes |
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| CN103709791B (en) * | 2013-12-23 | 2015-09-02 | 浙江花蝶染料化工有限公司 | The dispersed dye prepared the method for dispersed dye and institute's using appts and obtain |
| CN105367444B (en) * | 2015-11-13 | 2018-03-20 | 浙江闰土研究院有限公司 | A kind of continuous diazotization process of dyestuff |
| CN105348847B (en) * | 2015-11-13 | 2017-10-10 | 浙江闰土研究院有限公司 | A kind of continuous coupling process of dyestuff |
| CN107012617A (en) * | 2017-06-16 | 2017-08-04 | 江苏华艺服饰有限公司 | A kind of clothing hangs dye dyeing apparatus |
| CN108047751B (en) * | 2017-12-29 | 2019-11-22 | 沈阳化工研究院有限公司 | A kind of band ester group azo dispersion dyes serialization coupling process |
| CN111378296B (en) * | 2018-12-31 | 2021-05-11 | 沈阳化工研究院有限公司 | Production system and process method for preparing high-transparency and high-strength monoazo pigment |
| CN111378297B (en) * | 2018-12-31 | 2021-05-11 | 沈阳化工研究院有限公司 | Production system and process method for continuously synthesizing bisazo pigment |
| CN110845860A (en) * | 2019-11-20 | 2020-02-28 | 浙江工业大学 | Production process and synthesis system for automatic continuous liquid azo dye |
| CN111704806B (en) * | 2020-06-22 | 2021-05-11 | 清华大学 | Continuous preparation method of disperse dye |
| CN112538030A (en) * | 2020-11-05 | 2021-03-23 | 乐威医药（江苏）股份有限公司 | Low-temperature continuous reactor and working method for producing diazo compound |
| CN113372734B (en) * | 2021-05-21 | 2023-02-17 | 浙江亿得新材料股份有限公司 | Cycle-based orange dye synthesis method |
| CN113861719B (en) * | 2021-09-30 | 2023-10-17 | 浙江闰土染料有限公司 | Clean preparation method of cationic yellow |
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| CN103146221A (en) | 2013-06-12 |
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