CN104262991A - Method for semi-continuous production of fluorescent whitening agent - Google Patents
Method for semi-continuous production of fluorescent whitening agent Download PDFInfo
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Abstract
The invention relates to a method for semi-continuous production of a fluorescent whitening agent and belongs to the field of production methods of fluorescent whitening agents. The method comprises the following steps: adding an acid binding agent at a uniform speed according to the molar ratio of cyanuric chloride to 4, 4-diaminostilbene-2, 2-disulfonic acid till the disappearance of an amino group to obtain 4, 4'-bis (4, 6-dichlorotriazine-2-amino) stilbene-2, 2'-disulfonate sodium; adding according to the molar ratio of 4, 4'-bis (4, 6-dichlorotriazine-2-amino) stilbene-2, 2'-disulfonate sodium to aniline, and reacting under the control of the acid binding agent and heating till the disappearance of the amino group to obtain a second-step condensation product for later use; and adding according to the molar ratio of diethanolamine to the second-step condensation product, further reacting an obtained third-step condensation product with the acid binding agent, then feeding into a pipeline reactor to obtain a reaction solution, and performing cooling, suction filtration, impurity removal, desalting and concentration to obtain a finished product. According to the method provided by the invention, the conversion rate of the reaction can be ensured, the product quality can be stabilized, the production efficiency can be improved, the productivity per unit time can be increased, the integrated production cost can be reduced, and the market competitiveness of an enterprise can be improved.
Description
Technical field
The present invention relates to the method for white dyes, be specifically related to the method for the semi-continuous production white dyes of the two triazines liquid of a kind of toluylene.
Background technology
The two triazines white dyes of toluylene, because its whitening performance is superior, the more high advantage of cost performance, is widely used in papermaking, washing composition and printing and dyeing industry.Single with regard to paper industry, large-scale paper plant is increasing, and the requirement of market to paper product is more and more higher, following trend is required to white dyes: uniform quality and whitening performance is superior, suitable serialization self-feeding, stable storing, pollution-free, high resolution etc.Therefore, the disulfonic acid class I liquid I white dyes that whitening performance is excellent is the main product of existing market demand.
At present, the production of domestic disulfonic acid class I liquid I white dyes generally all takes the step mode of production, this is determined by the feature of such reaction itself, the general production technique taked in the organic synthesis stage divides three, for BA (83#) product, comprise: a reaction, cyanuric chloride and DSD acid are reacted; Two reactions, a product and aniline reaction; Three-step reaction, two products and diethanolamine react.Carrying out in this reaction process of three, general meeting is carried out in two stills: undertaken complete by one and two reactions in reactor, material is proceeded in autoclave again and carry out three reactions, the raw material of each portion reaction adds by certain proportioning in batches, release, without the turnover of material in process after reaction terminates in batches.
Patent CN1287200A discloses a kind of liquid fluorescent whitening agent and production technique thereof, being produced by Four processes such as feed purification process, organic synthesis, work in-process purification process and the concentrated finished products of refinement, is the production method of typical intermittent liquid white dyes.
Patent CN103571220A and EP02405998.2 discloses a kind of amphoteric flourescent whitening agents and preparation method thereof, be all with cyanuric chloride, DSD acid etc. are raw material, obtain corresponding product through three intermittent reactions, there is production capacity equally lower, the problems such as production cost is high.
Patent CN102926279A discloses a kind of preparation method of composition of liquid fluorescent bleaching agent, contains step three reactions equally, then adopts nanofiltration membrane mode to carry out nanofiltration desalination process to obtain the finished product.
The mode of production of the disulfonic acid class I liquid I white dyes cited by above-mentioned patent, be batch production, this is the mode that most domestic white dyes producer generally adopts, and it is little that batch production exists facility investment, and reaction conversion ratio is high, the advantages such as range of product easy switching, but compared with producing with continous way, labor strength is large, and quality product is stability contorting not easily, small scale, production capacity are lower, are unwell to the inferior positions such as scale operation and but cannot avoid.Therefore, above-mentioned two kinds of modes of production, in limited cost investment, are combined by how association reaction feature, play the advantage of two kinds of modes of production to greatest extent, the transformation efficiency reacted can be ensured, labor strength can be reduced to a certain extent again, stabilized product quality, enhance productivity, reduce comprehensive production cost, improve the market competitiveness of enterprise, there is very major and immediate significance.
Summary of the invention
The object of the invention is to solve prior art exists can not the problem of continuous prodution, and the method for the semi-continuous production white dyes providing a kind of rhythmic reaction mode to combine with successive reaction mode.
The method of a kind of semi-continuous production white dyes of the present invention, comprises the following steps:
1) trash ice 100 ~ 300g, water 200 ~ 300g, cyanuric chloride 30 ~ 50g is added in a kettle., stir and pull an oar 0.5 ~ 2.0 hour, again according to cyanuric chloride: 4,4-diaminobenzil-2, the mol ratio of 2-disulfonic acid=1.0:0.45 ~ 0.5 at the uniform velocity added in 2.0 ~ 3.0 hours, reacting system PH value is controlled for 3.0 ~ 5.0 with acid binding agent, and keep pH value 0.5 ~ 1.5 hour, regulate PH=4.5 ~ 5.0 again, reaction, until amino disappearance, obtains 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate;
2) again to step 1) obtain 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) in toluylene-2,2 ＇-sodium disulfonate according to 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate: the mol ratio of aniline=1.0:1.8 ~ 2.0 adds aniline, controls reacting system PH value for 5.0 ~ 7.0 with acid binding agent, reacts at being warming up to 25 ~ 45 DEG C, after amino disappearance, obtain two step condensation products for subsequent use;
3) again by pipeline reactor heat up be: one section is warming up to 50 ~ 95 DEG C, two sections be warming up to 100 ~ 150 DEG C for subsequent use;
4) to step 2) in the two step condensation products that obtain according to diethanolamine: the mol ratio of two step condensation product=3.0 ~ 2.4:1 adds diethanolamine and obtains three step condensation products, and then the three step condensation products obtained and acid binding agent were overlapped flow controlled volume pump with two according to the reacting weight of 1.0:1.0 ~ 1.2 in 4.0 ~ 6.0 hours sends into step 3) heat up one section with two segment pipe reactors in obtain reaction solution;
5) by step 4) obtained reaction solution is when being cooled to 30 ~ 55 DEG C, use Büchner funnel suction filtration, removing impurity, by the filtrate that obtains through nanofiltration membrane at 30 ~ 60 DEG C, carry out desalination and concentration under the pressure of 0.6 ~ 1.8MPa and obtain reaction solution, when specific conductivity is 150 ~ 400 μ S/cm, stop nanofiltration, obtain finished product.
Described step 4) in the reacting weight of the three step condensation products that obtain and acid binding agent be 1.5 ~ 2.5 hours by the time of a segment pipe reactor, be 2.5 ~ 3.5 hours by the time of second stage reactor.
Described acid binding agent to be mass percent be 10 ~ 15% the NaHCO3 aqueous solution, the Na2CO3 aqueous solution of 10 ~ 15%, 30 ~ 33%NaOH aqueous solution.
Compared with prior art, the mode of production of the present invention to the two triazines liquid fluorescent whitening agent of traditional toluylene is improved, and batch production is become the combination of intermittent type and continous way, compared with traditional technology, has the following advantages:
(1) first and second step reaction adopts traditional batch production, ensures that transformation efficiency at inhomogeneous reaction stage each material is in higher level, the convenient product switched without type simultaneously;
(2) in three-step reaction, by the reacting weight needed for diethanolamine and acid binding agent, the volume pump controlled with two cover flows adds in pipeline reactor simultaneously, adds, and undertaken heating up and insulation reaction by pipeline reactor within the identical time, replace traditional autoclave reaction process, reaction process is more safe and reliable, achieves continuous prodution, reduces energy consumption, while increasing production capacity, stabilize quality product.
Embodiment
Embodiment 1
The method of a kind of semi-continuous production white dyes of the present invention, comprises the following steps:
1) in uncovered beaker, trash ice 100g, water 200g, cyanuric chloride 30g is added, stir and pull an oar 0.5 hour, again according to cyanuric chloride: 4,4-diaminobenzil-2, the mol ratio of 2-disulfonic acid=1.0:0.45 at the uniform velocity added in 2.0 hours, reacting system PH value is controlled for 3.0 with acid binding agent, and keep pH value 0.5 hour, regulate PH=4.5 again, reaction, until amino disappearance, obtains 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate;
2) again to step 1) obtain 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2, according to 4 in 2 ＇-sodium disulfonate, 4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate: the mol ratio of aniline=1.0:1.8 adds aniline, be that the NaHCO3 aqueous solution of 10 ~ 15% is for acid binding agent control reacting system PH value is for 5.0 with mass percent, react at being warming up to 25 DEG C, after amino disappearance, obtain two step condensation products for subsequent use;
3) again by pipeline reactor heat up be: one section is warming up to 50 DEG C, two sections be warming up to 100 DEG C for subsequent use;
4) to step 2) in the two step condensation products that obtain according to diethanolamine: the mol ratio of two step condensation product=3.0:1 adds diethanolamine and obtains three step condensation products, and then by the three step condensation products obtained and mass percent be 10 ~ 15% the NaHCO3 aqueous solution in 4.0 hours, overlap flow controlled volume pump with two according to the reacting weight of 1.0:1.0 and send into step 3) heat up one section with two segment pipe reactors in obtain reaction solution; Described step 4) in the reacting weight of the three step condensation products that obtain and acid binding agent be 1.5 hours by the time of a segment pipe reactor, be 2.5 hours by the time of second stage reactor;
5) by step 4) obtained reaction solution is when being cooled to 30 DEG C, use Büchner funnel suction filtration, removing impurity, by the filtrate that obtains through WTM-1812D type nanofiltration membrane at 30 DEG C, carry out desalination and concentration under the pressure of 0.6MPa and obtain reaction solution, when specific conductivity is 150 μ S/cm, stop nanofiltration, obtain finished product.
Embodiment 2
The method of a kind of semi-continuous production white dyes of the present invention, comprises the following steps:
1) in uncovered beaker, trash ice 300g, water 300g, cyanuric chloride 50g is added, stir and pull an oar 2.0 hours, again according to cyanuric chloride: 4,4-diaminobenzil-2, the mol ratio of 2-disulfonic acid=1.0:0.5 at the uniform velocity added in 3.0 hours, be that the Na2CO3 aqueous solution of 10 ~ 15% is for acid binding agent control reacting system PH value is for 5.0 with mass percent, and keep pH value 1.5 hours, regulate PH=5.0 again, reaction, until amino disappearance, obtains 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate;
2) again to step 1) obtain 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) in toluylene-2,2 ＇-sodium disulfonate according to 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate: the mol ratio of aniline=1.0:2.0 adds aniline, controls reacting system PH value for 7.0 with acid binding agent, reacts at being warming up to 45 DEG C, after amino disappearance, obtain two step condensation products for subsequent use;
3) again by pipeline reactor heat up be: one section is warming up to 95 DEG C, two sections be warming up to 150 DEG C for subsequent use;
4) to step 2) in the two step condensation products that obtain according to diethanolamine: the mol ratio of two step condensation product=2.4:1 adds diethanolamine and obtains three step condensation products, and then by the three step condensation products obtained and mass percent be 10 ~ 15% the Na2CO3 aqueous solution in 6.0 hours, overlap flow controlled volume pump with two according to the reacting weight of 1.0:1.2 and send into step 3) heat up one section with two segment pipe reactors in obtain reaction solution; Described step 4) in the reacting weight of the three step condensation products that obtain and acid binding agent be 2.5 hours by the time of a segment pipe reactor, be 3.5 hours by the time of second stage reactor.
5) by step 4) obtained reaction solution is when being cooled to 55 DEG C, use Büchner funnel suction filtration, removing impurity, by the filtrate that obtains through WTM-1812D type nanofiltration membrane at 60 DEG C, carry out desalination and concentration under the pressure of 1.8MPa and obtain reaction solution, when specific conductivity is 400 μ S/cm, stop nanofiltration, obtain finished product.
Embodiment 3
The method of a kind of semi-continuous production white dyes of the present invention, comprises the following steps:
1) in uncovered beaker, trash ice 200g, water 250g, cyanuric chloride 40g is added, stir and pull an oar 1.5 hours, again according to cyanuric chloride: 4,4-diaminobenzil-2, the mol ratio of 2-disulfonic acid=1.0:0.47 at the uniform velocity added in 2.5 hours, with mass percent be 30 ~ 33%NaOH aqueous solution control reacting system PH value for 4.0, and keep pH value 1.0 hours, regulate PH=4.8 again, reaction, until amino disappearance, obtains 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate;
2) again to step 1) obtain 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) in toluylene-2,2 ＇-sodium disulfonate according to 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate: the mol ratio of aniline=1.0:1.9 adds aniline, is that 30 ~ 33%NaOH aqueous solution controls reacting system PH value for 6.0 with mass percent, reacts at being warming up to 35 DEG C, after amino disappearance, obtain two step condensation products for subsequent use;
3) again by pipeline reactor heat up be: one section is warming up to 70 DEG C, two sections be warming up to 130 DEG C for subsequent use;
4) to step 2) in the two step condensation products that obtain according to diethanolamine: the mol ratio of two step condensation product=2.8:1 adds diethanolamine and obtains three step condensation products, and then is that the reacting weight of 30 ~ 33%NaOH solution according to 1.0:1.1 overlapped the controlled volume pump of flow with two and send into step 3 in 5.0 hours by the three step condensation products obtained and mass percent) heat up one section with two segment pipe reactors in obtain reaction solution; Described step 4) in the reacting weight of the three step condensation products that obtain and acid binding agent be 2.0 hours by the time of a segment pipe reactor, be 3.0 hours by the time of second stage reactor.
5) by step 4) obtained reaction solution is when being cooled to 45 DEG C, use Büchner funnel suction filtration, removing impurity, by the filtrate that obtains through WTM-1812D type nanofiltration membrane at 45 DEG C, carry out desalination and concentration under the pressure of 1.5MPa and obtain reaction solution, when specific conductivity is 300 μ S/cm, stop nanofiltration, obtain finished product.
Claims (3)
1. a method for semi-continuous production white dyes, is characterized in that comprising the following steps:
1) trash ice 100 ~ 300g, water 200 ~ 300g, cyanuric chloride 30 ~ 50g is added in a kettle., stir and pull an oar 0.5 ~ 2.0 hour, again according to cyanuric chloride: 4,4-diaminobenzil-2, the mol ratio of 2-disulfonic acid=1.0:0.45 ~ 0.5 at the uniform velocity added in 2.0 ~ 3.0 hours, reacting system PH value is controlled for 3.0 ~ 5.0 with acid binding agent, and keep pH value 0.5 ~ 1.5 hour, regulate PH=4.5 ~ 5.0 again, reaction, until amino disappearance, obtains 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate;
2) again to step 1) obtain 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) in toluylene-2,2 ＇-sodium disulfonate according to 4,4 ＇-two (4,6-dichlorotriazine-2-is amino) toluylene-2,2 ＇-sodium disulfonate: the mol ratio of aniline=1.0:1.8 ~ 2.0 adds aniline, controls reacting system PH value for 5.0 ~ 7.0 with acid binding agent, reacts at being warming up to 25 ~ 45 DEG C, after amino disappearance, obtain two step condensation products for subsequent use;
3) again by pipeline reactor heat up be: one section is warming up to 50 ~ 95 DEG C, two sections be warming up to 100 ~ 150 DEG C for subsequent use;
4) to step 2) in the two step condensation products that obtain according to diethanolamine: the mol ratio of two step condensation product=3.0 ~ 2.4:1 adds diethanolamine and obtains three step condensation products, and then the three step condensation products obtained and acid binding agent were overlapped flow controlled volume pump with two according to the reacting weight of 1.0:1.0 ~ 1.2 in 4.0 ~ 6.0 hours sends into step 3) heat up one section with two segment pipe reactors in obtain reaction solution;
5) by step 4) obtained reaction solution is when being cooled to 30 ~ 55 DEG C, use Büchner funnel suction filtration, removing impurity, by the filtrate that obtains through WTM-1812D type nanofiltration membrane at 30 ~ 60 DEG C, carry out desalination and concentration under the pressure of 0.6 ~ 1.8MPa and obtain reaction solution, when specific conductivity is 150 ~ 400 μ S/cm, stop nanofiltration, obtain finished product.
2. the method for a kind of semi-continuous production white dyes according to claim 1, it is characterized in that: step 4) in the reacting weight of the three step condensation products that obtain and acid binding agent be 1.5 ~ 2.5 hours by the time of a segment pipe reactor, be 2.5 ~ 3.5 hours by the time of second stage reactor.
3. the method for a kind of semi-continuous production white dyes according to claim 1, is characterized in that: described acid binding agent is mass percent is the NaHCO3 aqueous solution of 10 ~ 15%, the Na2CO3 aqueous solution of 10 ~ 15% or 30 ~ 33%NaOH aqueous solution.
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Cited By (3)
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| CN105806820A (en) * | 2016-05-11 | 2016-07-27 | 江南大学 | Continuous flow synthetic method for glycoprotein fluorescence probe molecule |
| CN106634013A (en) * | 2016-12-16 | 2017-05-10 | 山西青山化工有限公司 | Device for preparing toluylene bis(triazinyl) particular fluorescent whitening agent and preparation method thereof |
| CN112778229A (en) * | 2019-11-05 | 2021-05-11 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105806820A (en) * | 2016-05-11 | 2016-07-27 | 江南大学 | Continuous flow synthetic method for glycoprotein fluorescence probe molecule |
| CN105806820B (en) * | 2016-05-11 | 2018-09-28 | 江南大学 | A kind of continuous flow synthetic method of glycoprotein fluorescent probe molecule |
| CN106634013A (en) * | 2016-12-16 | 2017-05-10 | 山西青山化工有限公司 | Device for preparing toluylene bis(triazinyl) particular fluorescent whitening agent and preparation method thereof |
| CN106634013B (en) * | 2016-12-16 | 2018-12-14 | 山西青山化工有限公司 | A kind of device and preparation method thereof preparing the double triazines granular pattern fluorescent whitening agents of talan |
| CN112778229A (en) * | 2019-11-05 | 2021-05-11 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
| CN112778229B (en) * | 2019-11-05 | 2022-07-29 | 上海合丽亚化工科技有限公司 | Method for continuously preparing fluorescent whitening agent |
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