CN102285928B - CA (Cyanuric Acid) liquid phase catalytic synthesis method - Google Patents
CA (Cyanuric Acid) liquid phase catalytic synthesis method Download PDFInfo
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Abstract
The invention discloses a CA (Cyanuric Acid) liquid phase catalytic synthesis method which comprises the following steps of: (1) heating and dehydrating urea; (2) adding an organic solvent, a catalyst and the CA, heating to make the urea have a condensation reaction at backflow temperature, obtaining heat slurry consisting of the CA and the organic solvent, wherein the organic solvent is N,N-dimethylformamide or N,N-dimethylacetylamide, the catalyst is sodium dihydrogen phosphate or disodium hydrogen phosphate, and the CA finished product is a common industrial product; and (3) cooling down the heat slurry obtained from the step (2), carrying out solid-liquid separation to obtain a CA filter cake containing the organic solvent, washing the filter cake in clear water till no organic solvent is residual, and drying to obtain white CA crystals. According to the CA liquid phase catalytic synthesis method disclosed by the invention, the CA finished product can be directly obtained without refining, and the solvent can be recycled after recovery treatment, thus the production cost is low, the production yield is high, the quality is good, no three wastes pollute the environment, and the production is safe; and the CA liquid phase catalytic synthesis method is suitable for industrial production.
Description
Technical field
The method that the present invention relates to the synthetic tricyanic acid of a kind of liquid-phase catalysis, belongs to technical field of organic synthesis in chemical industry.
Background technology
Tricyanic acid or cyanuric acid (be called for short CA) are a kind of important chemical intermediates, take it as raw material can synthesize hundreds of important derivatives, new compound, also in continuous increase, relates to the every field such as medicine, agricultural chemicals, dyestuff, coating and auxiliary agent.The series chemical product that its downstream obtains exploitation mainly comprises: sterilizing agent series, comprises chlorated fulminuric acid compounds trichloroisocyanuric acid and Surchlor GR 60; Halogen is containing nitrogen combustion inhibitor tricyanic acid-trimeric cyanamide (MCA); Polyester powder coating solidifying agent dai serge gram (TGIC), other organic compound such as tricarbimide ester compound trihydroxyethyl isocyanuric fat, three propenyl tricarbimide fat, triglycidyl group chlorinated isocyanurates.
The production method of tricyanic acid mainly contains urea fused-salt pyrolysis method, urea direct pyrolysis method, liquid phase method.The fused salt pyrolysis method technical process of bibliographical information is complicated, equipment corrosion is serious, and product yield is low, does not have industrial value (USP4109089, SU254517).Urea direct pyrolysis method comprises scorification, it is the solid phase method of general indication, comprising some, improve one's methods as metal melting method (EP249498, ES540265), microwave irradiation (CN1121513), instead expect method (US4474957, US2943088), partial recycle process, reaction extrusion molding, solid phase method (ZL 200620004029.8) is the main method of the current suitability for industrialized production of China, and additive method only limits to laboratory study achievement.Solid phase method carries out condensation reaction by urea direct heating and obtains cyanuric acid crude product, 260～280 ℃ of temperature of reaction, and tricyanic acid content 70～75% in crude product then boils thick product for a long time the refining tricyanic acid finished product that obtains in mineral acid.In direct polycondensation process, there is melting and solidification process in urea and intermediate product thereof, a large amount of ammonia gas as byproduct can not be discharged smoothly, make crude product kind contain a large amount of amidess and with a large amount of intermediate product biurets and contracting triuret, treating process produces a large amount of acid waste water, contains a large amount of air and carbonic acid gas and make it to be fully recycled in ammonia gas as byproduct.But because this method technique is simple, with low content of technology, the twentieth century production capacity nineties increases sharply, be still at present the major industry method that China produces tricyanic acid.Liquid phase method technique makes urea in a certain proportion of organic solvent, carry out condensation reaction, and speed of response is moderate, and ammonia gas as byproduct is got rid of smoothly, without refining, reaches finished product requirement.The difficult point of this method is that solvent recovering system is complicated, and solvent price is more expensive, and product is often with color.The organic solvent that liquid phase method is used mainly contains high boiling tetramethylene sulfone, dodecylbenzene, ethylene glycol, trichloro-benzene, N-cyclohexyl pyrrolidone, N-Methyl pyrrolidone etc., above-mentioned solvent boiling point is high, expensive, equipment requirements condition is harsh, product colour can not remove, and investment is large, compares not have an advantage with solid phase method.(USP2872447, USP2729637, US 3,297,697 (1967), ZL 01139819,1, day JP 57-116054).Adopt the liquid phase method (USP3297697, CN 101624380A) of relatively low boiling point solvent) can obtain the product suitable with the refining rear product whiteness of solid phase method, temperature of reaction is low, long reaction time, amides by product is higher, and under boiling point, reaction has increased the energy consumption of reaction.It is how to improve temperature of reaction, raising speed of reaction and improve the quality of products that lower boiling liquid phase method wants to obtain breakthrough key.
Summary of the invention
The object of the present invention is to provide a kind of method that technique is simple, cost is lower, the liquid-phase catalysis of production safety synthesizes tricyanic acid.
For realizing object of the present invention, the inventor has conscientiously studied the different preparation methods' of tricyanic acid advantage and disadvantage, defect while having proposed to avoid adopting low boiling point solvent through concentrating on studies for many years retains again the method for the synthetic tricyanic acid of liquid-phase catalysis of liquid phase method advantage, makes liquid phase method really have industrial prospect.
The present invention uses lower, the cheap N of boiling point, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE is solvent, reduced solvent cost, employing preheats urea method, reduce the contained physics moisture of urea surface as far as possible, avoided the loss that under high temperature, hydrolysis of urea causes raw material urea, improved product yield; Adopt the method that adds in advance a small amount of finished product, improved temperature of reaction, shortened the reaction times; Add catalyzer to improve speed of response; To distillation urea, adopt the method reclaiming afterwards that first distils to avoid the reaction times increasing because dripping urea or urea soln; Under the prerequisite that guarantees quality product, dwindle the amount of organic solvent used, thereby reduced solvent loss.
Particularly, method of the present invention comprises the following steps:
(1), by Urea, remove its surperficial physics moisture;
(2) under agitation condition, in urea, add organic solvent, catalyzer and tricyanic acid finished product, stir and 160 ℃～176 ℃ of reflux temperatures at urea condensation is reacted 4～6 hours, obtain the hot slurry being formed by tricyanic acid and organic solvent;
Wherein, described organic solvent is DMF or N,N-dimethylacetamide, and catalyzer is SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, and tricyanic acid finished product is general industry product;
(3) hot slurry step (2) being obtained is cooling, carries out solid-liquid separation and obtains the tricyanic acid filter cake that contains organic solvent, residual to organic solvent-free with clear water washing leaching cake, after being dried, obtains white tricyanic acid xln finished product.
In step of the present invention (1), Urea to 80～90 ℃, 10～20 minutes heat-up times; Its excess-three kind material adds order not make significant difference, without the joining day of controlling above-mentioned organic solvent.
Step (2), in feed liquid, the mass ratio of urea and organic solvent is (1: 1)～(1: 2.5);
In feed liquid, the mass ratio of urea and catalyzer is (1: 0.002)～(1: 0.004);
In feed liquid, the mass ratio of urea and tricyanic acid finished product is (1: 0.05)～(1: 0.1);
The beneficial effect that the present invention obtains is: the processing method that adopts the synthetic tricyanic acid of liquid-phase catalysis, directly obtained meeting the tricyanic acid finished product of industrial goods specification of quality, product yield is high, good product quality, without safety and environmental issue, be a kind of environmental protection synthetic method.
Embodiment
The following examples are used for illustrating the present invention, but do not limit the present invention.
Embodiment 1
100 grams of urea are heated to 80 ℃ in reactor, under agitation condition, constant temperature dehydration is 15 minutes, add N, 100 grams of dinethylformamides, 0.4 gram of catalyzer SODIUM PHOSPHATE, MONOBASIC, 5 grams of tricyanic acids, under agitation condition, be warming up to backflow, at 165 ℃ of reflux temperatures, urea carries out condensation reaction 5 hours, obtains the hot slurry being comprised of tricyanic acid and DMF.Under agitation condition, be cooled to room temperature, make tricyanic acid sufficient crystallising, use vacuumfilter suction filtration, it is residual to organic solvent-free with clear water washing tricyanic acid filter cake after suction filtration completes, obtain tricyanic acid filter cake, in loft drier, under 110 ℃ of conditions, dry 3 hours, obtain 58.3 grams of white tricyanic acids.In this example, by weighing before and after reflux exchanger reaction, determine that urea distillation number is 3 grams, after reaction, in solvent, containing tricyanic acid, it is 7.2 grams, calculating productive rate is 87% (calculation of yield method: productive rate=(180 (A-C+D)/129 (100-B)) * 100%, wherein: A: the real grams that obtains tricyanic acid, B: urea distillation grams, C: add tricyanic acid grams before reaction, the contained tricyanic acid grams of solvent in the time of D:25 ℃, reaction process is not considered solvent loss, the tricyanic acid adding before reaction and the tricyanic acid of generation are not considered purity difference, in the time of 25 ℃, tricyanic acid is at N, solubleness in dinethylformamide is 7.2%, at N, solubleness in N-N,N-DIMETHYLACETAMIDE is 3%.Example is identical therewith with comparative example calculation of yield method below).
Embodiment 2
100 grams of urea are heated to 80 ℃ in reactor, under agitation condition, heat 15 minutes, add 200 grams of DMFs, 0.2 gram of catalyzer SODIUM PHOSPHATE, MONOBASIC, 10 grams of tricyanic acids, under agitation condition, be warming up to backflow, at 160 ℃ of reflux temperatures, urea carries out condensation reaction 6 hours, below operate same example 1, obtain 51.2 grams of white tricyanic acids, urea distils several 3 grams, after reaction, solvent is containing 14.4 grams of tricyanic acids, productive rate 80%.
Embodiment 3
100 grams of urea are heated to 80 ℃ in reactor, under agitation condition, heat 15 minutes, add 200 grams of N,N-dimethylacetamide, 0.2 gram of catalyzer SODIUM PHOSPHATE, MONOBASIC, 6 grams of tricyanic acids, under agitation condition, be warming up to backflow, at 176 ℃ of reflux temperatures, urea carries out condensation reaction 4 hours, below operate same example 1, obtain 63.3 grams of white tricyanic acids, urea distils several 4 grams, after reaction, solvent is containing 6 grams of tricyanic acids, productive rate 92%
Embodiment 4
100 grams of urea are heated to 90 ℃ in reactor, under agitation condition, heat 20 minutes, add 250 grams of N,N-dimethylacetamide, 0.2 gram of catalyzer SODIUM PHOSPHATE, MONOBASIC, 7.5 grams of tricyanic acids, under agitation condition, be warming up to backflow, at 174 ℃ of reflux temperatures, urea carries out condensation reaction 5 hours, below operate same example 1, obtain 62.6 grams of white tricyanic acids, urea distils several 4 grams, after reaction, solvent is containing 7.5 grams of tricyanic acids, productive rate 91%.
Comparative example 1
By the enforcement 3 in CN101624380A, operate: 125 grams of DMFs are heated to 152 ℃ in reactor, keep refluxing.Under agitation condition, 50 grams of solid ureas are added in reactor, 50 grams of urea were at the uniform velocity added through 6 hours, in reinforced process, keep refluxing, make urea condensation reaction 2 hours after feeding in raw material under stirring and 160 ℃ of conditions, below operation is with example 1, obtain 19.3 grams of white tricyanic acids, 0 gram of urea distillation amount, after reaction, solvent is containing 9 grams of tricyanic acids, productive rate 79%.
Comparative example 2
100 grams of urea are heated to 80 ℃ in reactor, under agitation condition, heat 10 minutes, add 200 grams of N,N-dimethylacetamide, 6 grams of tricyanic acids, under agitation condition, be warming up to backflow, at 176 ℃ of reflux temperatures, urea carries out condensation reaction 4 hours, below operate same example 1, obtain 59.2 grams of white tricyanic acids, urea distils several 4 grams, after reaction, solvent is containing 6 grams of tricyanic acids, productive rate 86%.
Comparative example 3
100 grams of urea are heated to 80 ℃ in reactor, under agitation condition, heat 15 minutes, add 200 grams of N,N-dimethylacetamide, 0.2 gram of catalyzer Sodium phosphate dibasic, under agitation condition, be warming up to backflow, at 172 ℃ of reflux temperatures, urea carries out condensation reaction 5 hours, below operate same example 1, obtain 58.5 grams of white tricyanic acids, urea distils several 4 grams, after reaction, solvent is containing 6 grams of tricyanic acids, productive rate 85%.
Comparative example 4
By the enforcement 5 in CN101624380A, operate: 250 grams of N,N-dimethylacetamide are heated to 165 ℃ in reactor, keep refluxing.Under agitation condition, 50 grams of solid ureas are added in reactor, 50 grams of urea were at the uniform velocity added through 2 hours, in reinforced process, keep refluxing, make urea condensation reaction 3 hours after feeding in raw material under stirring and 168 ℃ of conditions, below operation is with example 1, white tricyanic acid grams 21.17,0 gram of urea distillation amount, after reaction, solvent is containing 7.5 grams of tricyanic acids, productive rate 80%.
Embodiment and comparative example quality index detect contrast table
What below provide is the main content of tricyanic acid and amides foreign matter content analytical procedure:
(1) tricyanic acid content analysis adopts potentiometric titration (about the comparison of potentiometric titration and other analytical procedure is referring to < < Purity determination of cyanuric acid by using gravimetric analysis > >, China's chlor-alkali 2004, No8, p25-27; Amide content adopts DMF insolubles method, and other index adopts traditional analysis method.
(2) amides foreign matter content analytical procedure
Correctly take sample 5g, while stir, slowly add in 100mLDMF, stir one hour.Use the glass fiber filter paper (Bg) (keeping particle dia 0.5um) of known weight to carry out suction strainer.Then, with the DMF of about 50mL, divide cleaning for several times, after finally cleaning with acetone, in the thermostatic drier of 105-110 ℃, be dried 1 hour, and in mid-cold its weight of rear title of moisture eliminator (Ag).Press column count formula and calculate DMF insoluble substance (%).
DMF insoluble substance (%)=(A-B/ sample g) * 100-ash content (%)
At this, the weight of filter paper after A=filters
The weight of filter paper before B=filters.
Claims (2)
1. liquid-phase catalysis synthesizes a method for tricyanic acid, it is characterized in that: comprise the following steps:
(1), by Urea, remove the physics moisture of urea surface;
(2) under agitation condition, in urea, add organic solvent, catalyzer and tricyanic acid finished product, stir and 160 ℃～176 ℃ of reflux temperatures at urea condensation is reacted 4～6 hours, obtain the hot slurry being formed by tricyanic acid and organic solvent;
Wherein, described organic solvent is N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE, described catalyzer is SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, and described tricyanic acid finished product is general industry product, and in feed liquid, the mass ratio of urea and organic solvent is 1: 1～1: 2.5, in feed liquid, the mass ratio of urea and catalyzer is 1: 0.002～1: 0.004, and in feed liquid, the mass ratio of urea and tricyanic acid finished product is 1: 0.05～1: 0.1;
(3) hot slurry step (2) being obtained is cooling, carries out solid-liquid separation and obtains the tricyanic acid filter cake that contains organic solvent, residual to organic solvent-free with clear water washing leaching cake, after being dried, obtains white tricyanic acid xln product.
2. the method for the synthetic tricyanic acid of liquid-phase catalysis according to claim 1, is characterized in that: in step (1), the Urea time is 10～20 minutes, and dehydration temperaturre is 80～90 ℃.
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| CN111925337B (en) * | 2020-07-29 | 2023-03-31 | 郑州大学 | Preparation method of cyanuric acid |
| CN112898212B (en) * | 2021-01-28 | 2022-09-09 | 山东大明消毒科技有限公司 | Method for preparing cyanuric acid by using ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1421433A (en) * | 2001-11-30 | 2003-06-04 | 中国石油天然气股份有限公司 | Diethylene glycol solvent process of producing tricyanic acid |
| CN1600781A (en) * | 2003-09-27 | 2005-03-30 | 中国石油天然气股份有限公司 | Method for producing cyanuric acid through vibrated fluidized bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1421433A (en) * | 2001-11-30 | 2003-06-04 | 中国石油天然气股份有限公司 | Diethylene glycol solvent process of producing tricyanic acid |
| CN1600781A (en) * | 2003-09-27 | 2005-03-30 | 中国石油天然气股份有限公司 | Method for producing cyanuric acid through vibrated fluidized bed |
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