CN112898212B - Method for preparing cyanuric acid by using ionic liquid - Google Patents
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- CN112898212B CN112898212B CN202110115841.7A CN202110115841A CN112898212B CN 112898212 B CN112898212 B CN 112898212B CN 202110115841 A CN202110115841 A CN 202110115841A CN 112898212 B CN112898212 B CN 112898212B
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004202 carbamide Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012265 solid product Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 10
- -1 1-butyl-3-methylimidazole dicyandiamide salt Chemical class 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 32
- 238000000197 pyrolysis Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 239000012043 crude product Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- ISAOUZVKYLHALD-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)NC1=O ISAOUZVKYLHALD-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- USVZHTBPMMSRHY-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-chlorophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Cl USVZHTBPMMSRHY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing cyanuric acid by using ionic liquid, which comprises the steps of carrying out condensation reaction on the ionic liquid as a solvent and urea under the conditions of vacuum, stirring and heating, centrifuging a reaction product, and washing an obtained solid product with water to obtain a crude product cyanuric acid. The ionic liquid is used as a novel solvent for preparing cyanuric acid by a solvent method, urea is effectively dissolved, the heat transfer efficiency is high, the energy consumption is reduced, the condensation temperature is reduced to 190-210 ℃ from 220-280 ℃ of the traditional direct pyrolysis method, the energy consumption is saved by 16-24%, the yield of the prepared crude cyanuric acid is 86.6-90.7%, the purity is 90.7-96.4%, and the urea conversion rate is more than 80%. The operation process is reduced, the generation of wastes and the use of sulfuric acid in the subsequent refining process are reduced, the solvent volatilization problem is solved, the recovery is simple, and the method is green and environment-friendly.
Description
Technical Field
The invention relates to a production method for preparing cyanuric acid, in particular to a production method for preparing cyanuric acid by using an ionic liquid method, and belongs to the field of fine chemical engineering.
Background
Cyanuric acid, also called cyanuric acid, can be directly used as a stabilizer of a swimming pool chlorine treatment agent, a flame retardant of nylon and polyester, and is also an important intermediate product of a series of fine chemical products, and relates to various fields of medicines, pesticides, fuel coatings, light industry and the like. The chloro derivative chloroisocyanuric acid is an excellent water treatment agent and a bactericide, and plays an important role in sterilization and disinfection during the prevention and control of the new crown pneumonia epidemic situation.
In theory, the synthetic route of cyanuric acid comprises five routes of phosgene method, cyanuric acid trimerization, hydrocyanic acid oxidation, cyanuric chloride hydrolysis, urea pyrolysis and the like, but the four former synthetic routes have toxic raw materials, complex process and high cost, and industrialization cannot be realized at present. At present, the process route for producing cyanuric acid which is generally adopted at home and abroad is a urea melting pyrolysis method.
The urea melting pyrolysis method is the main method of the current industrial production, and the pyrolysis method is divided into three methods, namely a direct pyrolysis method (melting method), a molten salt pyrolysis method and a solvent method according to reaction media. The direct thermal decomposition method is a process for directly melting and synthesizing cyanuric acid by urea, and becomes a mainstream process of the current industrial production due to high yield and simple equipment. The product produced by the process is blocky, the wall sticking phenomenon exists in the reaction, the energy consumption is large, the crude product can form a fine product only by refining and post-treatment, and the subsequent treatment is easy to cause pollution.
The solvent method is characterized in that a high-boiling point inert solvent is used as a heating medium, and then the high-purity product is prepared through the procedures of solvent removal, water washing, drying and the like, the urea is dispersed more uniformly due to the existence of the solvent, the concentration of reactants is relatively reduced, the reaction tends to be mild, and the contact between ammonia and cyanuric acid is reduced, so that the content of the phthalein amine impurities is reduced, the product purity is improved, and continuous operation can be realized. Wu Shi Guang, Qiu Yu E, Yan Yu Gui, etc. all use dimethyl formamide (DMF) as solvent to synthesize cyanuric acid, the yield is 80%, 10.2017, 27 days, the carcinogen list published by the international cancer research institution of world health organization is primarily finished and referred, and dimethyl formamide is in the 2A carcinogen list, so the solvent is not suitable for the industrial production of cyanuric acid. In the existing research, the solvent method still has more problems, such as high solvent price, complex recovery process and difficult industrialization; in the actual operation, the solvent still volatilizes, which is not in accordance with the concept of green chemistry, and the like. Therefore, the selection of a proper, economical and environment-friendly solvent has become the key point for improving the synthesis process of cyanuric acid.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a production method for preparing cyanuric acid by using an ionic liquid method.
The technical scheme is as follows: the invention relates to a method for preparing cyanuric acid by using ionic liquid, which comprises the following steps:
(1) adding the ionic liquid into a reaction kettle, stirring in vacuum, and heating;
(2) adding urea into the reaction kettle at a constant speed, continuously stirring, and heating for condensation reaction;
(3) after the condensation reaction is carried out for a period of time, stopping heating to obtain slurry;
(4) and centrifuging the slurry in the reaction kettle, and washing the obtained solid product with water to obtain the cyanuric acid.
Further, in the step (1), the ionic liquid is one or a mixture of more than one of 1-butyl-3-methylimidazole dicyandiamide salt, 1-butyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole methanesulfonate.
Further, in the step (1), the heating temperature is 140-.
Further, in the step (2), the liquid-solid ratio of the ionic liquid to the urea in the reaction kettle is 2.0-4: 1L/Kg.
Further, in the step (2), the uniform speed is 20-40 Kg/min.
Further, in the step (2), the condensation reaction temperature is 190-210 ℃.
Further, in the step (3), the condensation reaction time is 3-5 h.
Further, in the step (4), the centrifugation temperature is room temperature, the centrifugation rotation speed is 500-.
Further, in the step (4), the water is distilled water or purified water.
The reaction mechanism of the invention using urea as raw material and acidic ionic liquid as solvent is as follows:
description of the reaction mechanism: under the action of acidic ionic liquid, urea produces carbonyl protonation and electron transfer, and then eliminates ammonia to obtain 1-aminocarbonyl carbocation, and loses hydrogen ion to produce cyanic acid and isocyanic acid structure capable of interconverting. At high temperature, carbon-nitrogen triple bonds in the cyanic acid structure are broken to generate cyanuric acid.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the ionic liquid adopted by the invention is imidazole ionic liquid, and the ionic liquid is used as an adjustable green solvent, and has low melting point and very low vapor pressure, so that the ionic liquid is a high-quality green substitute of a volatile organic solvent. The ionic liquid is used as a novel solvent for preparing cyanuric acid by a solvent method, urea can be effectively dissolved, the heat transfer efficiency is high, the energy consumption is reduced, the condensation temperature for preparing the cyanuric acid is reduced to 190-210 ℃ from 220-280 ℃ by the traditional direct pyrolysis method, the energy consumption is saved by 16-24.0%, the reaction yield is 86.6-90.7%, the purity of the cyanuric acid is 90.7-96.4%, the urea conversion rate is more than 80%, the subsequent operation process is reduced, and the generation of waste is greatly reduced. The used ionic liquid can be recovered only by centrifugation and water distillation after reaction, the problem of solvent evaporation is solved, the problems of difficult recovery and pollution in the production process of the traditional solvent method are effectively solved, and the method is green and environment-friendly.
Detailed Description
The technical solution of the present invention is further explained below.
Example 1
Taking a proper amount of 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid, adding the ionic liquid into a reaction kettle, starting a stirring device, and starting a vacuum circulating pump. When the temperature is heated to 150 ℃, feeding is carried out at the speed of 20Kg/min, and urea is fed according to the ratio of the volume (mL) of the solvent to the mass (g) of the urea of 2: 1. And (3) rapidly heating to 210 ℃ for condensation reaction, after reacting for 3h, cooling the obtained slurry to room temperature, centrifuging for 3h at the rotating speed of 500r/min, and washing the centrifugal product with distilled water to obtain a crude product cyanuric acid. Compared with the traditional direct pyrolysis method, the method saves the energy consumption by 16 percent, the reaction yield is 89.4 percent, the purity of cyanuric acid is 90.7 percent, and the urea conversion rate is 81.1 percent.
Example 2
Taking a proper amount of 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid, adding the ionic liquid into a reaction kettle, starting a stirring device, and starting a vacuum circulating pump. When the temperature is heated to 140 ℃, feeding is carried out at the speed of 30Kg/min, and the ratio of the volume (mL) of the solvent to the mass (g) of the urea is 2.5: 1. Heating to 200 ℃ rapidly for condensation reaction, cooling the obtained slurry to room temperature after 4h of reaction, centrifuging for 2.5h at the rotating speed of 700r/min, washing the centrifuged product with purified water, and obtaining the centrifuged product, namely the crude cyanuric acid. Compared with the traditional direct thermal decomposition method, the method saves the energy consumption by 20 percent, has the reaction yield of 87.3 percent, the purity of the cyanuric acid of 93.5 percent and the urea conversion rate of 81.6 percent.
Example 3
Taking a proper amount of 1-butyl-3-methylimidazole dicyandiamide ionic liquid, adding the ionic liquid into a reaction kettle, starting a stirring device, starting a vacuum circulating pump, feeding at a speed of 20Kg/min when heating to 145 ℃, and keeping the uniform speed, wherein the ratio of the volume (mL) of a solvent to the mass (g) of urea is 4: 1. Rapidly heating to 190 ℃ for condensation reaction, after 5 hours of reaction, cooling the obtained slurry to room temperature, then centrifuging for 2 hours at the rotating speed of 1000r/min, washing the centrifugal product with distilled water, and obtaining the centrifugal product which is crude cyanuric acid. Compared with the traditional direct pyrolysis method, the method saves the energy consumption by 24 percent, the reaction yield is 90.7 percent, the purity of cyanuric acid is 96.4 percent, and the urea conversion rate is 87.4 percent.
Example 4
Taking a proper amount of 1-butyl-3-methylimidazole mesylate ionic liquid, adding the ionic liquid into a reaction kettle, starting a stirring device, and starting a vacuum circulating pump. When heated to 150 ℃, the mixture is fed at a rate of 40Kg/min, according to a ratio of solvent volume (mL) to urea mass (g) of 2.5: 1. Heating to 200 ℃ rapidly for condensation reaction, after reacting for 4h, cooling the obtained slurry to room temperature, centrifuging for 0.5h at the rotating speed of 1500r/min, washing the centrifugal product with distilled water, and obtaining the centrifugal product, namely the crude cyanuric acid. Compared with the traditional direct pyrolysis method, the method saves the energy consumption by 20 percent, the reaction yield is 86.6 percent, the purity of cyanuric acid is 92.5 percent, and the urea conversion rate is 80.1 percent.
Comparative example 1
Preparing crude cyanuric acid by a traditional solvent method, adding a proper amount of sulfolane into a reaction kettle, starting a stirring device, and starting a vacuum circulating pump. While heating to 150 ℃, urea was dosed at 30Kg/min with the ratio of solvent volume (ml) to urea mass (g) being 3: 1. Heating to 200 ℃ for condensation reaction, and stopping heating after 4 hours of reaction. After the reaction is finished, the obtained slurry is cooled to room temperature and then is centrifuged for 2 hours at the rotating speed of 1000r/min, the centrifuged product is washed by distilled water, and the centrifuged product is crude cyanuric acid. The yield of the reaction for preparing the cyanuric acid is 53.6 percent, the purity of the cyanuric acid is 96.6 percent, and the conversion rate of the urea is 51.8 percent.
Comparative example 2
The crude cyanuric acid is prepared by a traditional solvent method, a proper amount of n-octanol is taken and added into a reaction kettle, a stirring device is started, and a vacuum circulating pump is started. When the temperature is heated to 140 ℃, 20Kg/min of urea is added according to the ratio of the volume (ml) of the solvent to the mass (g) of the urea of 3: 1. Heating to 198 deg.c for condensation reaction, and stopping heating after 4 hr reaction. After the reaction is finished, the obtained slurry is cooled to room temperature and then is centrifuged for 2 hours at the rotating speed of 1000r/min, the centrifugal product is washed by distilled water, the using amount of the distilled water is 1.5 times of that of the solvent, and the centrifugal product is the crude cyanuric acid. The reaction yield of preparing cyanuric acid is 42.1%, the purity of cyanuric acid is 91.6%, and the urea conversion rate is 38.6%.
Comparative example 3
The method comprises the steps of preparing crude cyanuric acid by a traditional direct pyrolysis method, placing solid urea in porcelain basins, filling 3.5Kg of urea in each porcelain basin, feeding the porcelain basins into a brick kiln built by refractory bricks, heating to 220 ℃ for condensation reaction, moving the porcelain basins to a cooling area after 5 hours of reaction, cooling to room temperature, transferring the materials in the porcelain basins to a crusher, and obtaining a crushed product, namely the crude cyanuric acid. The reaction yield of preparing cyanuric acid is 70.4%, the purity of cyanuric acid is 82.9%, and the urea conversion rate is 58.4%.
Comparative example 4
The method comprises the steps of preparing crude cyanuric acid by a traditional direct pyrolysis method, placing solid urea in porcelain basins, filling 3.5Kg of urea in each porcelain basin, feeding the porcelain basins into a brick kiln built by refractory bricks, heating to 280 ℃ for condensation reaction, moving the porcelain basins to a cooling area after 5 hours of reaction, cooling to room temperature, transferring the materials in the porcelain basins to a crusher, and obtaining a crushed product, namely the crude cyanuric acid. The reaction yield of preparing cyanuric acid is 74.5%, the purity of cyanuric acid is 90.3%, and the conversion rate of urea is 67.3%.
The content of cyanuric acid in the above examples and comparative examples was determined according to the method for determining the content in cyanuric acid (HG/T4818-2015) 5.3, and the specific technical results of the examples and comparative examples are shown in the following table.
As can be seen from the table: the ionic liquid is used as a novel solvent for preparing the cyanuric acid by a solvent method, can effectively dissolve the urea, has high heat transfer efficiency, can be reacted at the temperature of 190 plus one of 210 ℃, has energy consumption and the purity of the recovered crude cyanuric acid on the same level compared with a solvent method production process, but has greatly improved yield, the conversion rate of the urea is more than 80 percent, and greatly reduces the material consumption in the subsequent refining process and the energy use in the operation process. The problems that sulfolane, n-octanol and the like as solvents have obvious defects of flammability, corrosivity, irritation and the like, the industrialization difficulty is high, the green chemical concept is not met are solved, and the effect is obvious. Compared with the traditional direct pyrolysis production process, the condensation reaction temperature is obviously reduced, the energy consumption is reduced, and the yield and the purity of the cyanuric acid and the urea conversion rate are obviously improved.
Claims (8)
1. A method for preparing cyanuric acid by using ionic liquid is characterized by comprising the following steps:
(1) adding an ionic liquid into a reaction kettle, stirring in vacuum, and heating, wherein the ionic liquid is one or a mixture of more than one of 1-butyl-3-methylimidazole dicyandiamide salt, 1-butyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole methanesulfonate;
(2) adding urea into the reaction kettle at a constant speed, continuously stirring, and heating for condensation reaction;
(3) after the condensation reaction is carried out for a period of time, stopping heating to obtain slurry;
(4) and centrifuging the slurry in the reaction kettle, and washing the obtained solid product with water to obtain the cyanuric acid.
2. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (1), the heating temperature is 140-150 ℃.
3. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (2), the liquid-solid ratio of the ionic liquid to the urea in the reaction kettle is 2-4: 1L/Kg.
4. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (2), the uniform speed is 20-40 Kg/min.
5. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (2), the condensation reaction temperature is 190-210 ℃.
6. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (3), the condensation reaction time is 3-5 h.
7. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (4), the centrifugation temperature is room temperature, the centrifugation speed is 500-.
8. The method for preparing cyanuric acid by using ionic liquid as claimed in claim 1, wherein: in the step (4), the water is distilled water or purified water.
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| CN202110115841.7A CN112898212B (en) | 2021-01-28 | 2021-01-28 | Method for preparing cyanuric acid by using ionic liquid |
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| CN202110115841.7A CN112898212B (en) | 2021-01-28 | 2021-01-28 | Method for preparing cyanuric acid by using ionic liquid |
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| CN101624380A (en) * | 2009-08-01 | 2010-01-13 | 山东天一化学有限公司 | Technical method for liquid phase synthesizing cyanuric acid |
| CN101830859A (en) * | 2010-05-14 | 2010-09-15 | 菏泽沃蓝化工有限公司 | Production method of isocyanuric acid |
| CN102285928A (en) * | 2011-08-29 | 2011-12-21 | 王铁招 | CA (Cyanuric Acid) liquid phase catalytic synthesis method |
| CN102516188A (en) * | 2011-12-12 | 2012-06-27 | 河北克尔化工有限公司 | Preparation method of high-yield cyanuric acid and its derivatives sodium dichloroisocyanurate and trichloroisocyanuric acid |
| CN105906577A (en) * | 2016-04-26 | 2016-08-31 | 王建伍 | Production process of pyrolysis cyanuric acid |
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| CN101624380A (en) * | 2009-08-01 | 2010-01-13 | 山东天一化学有限公司 | Technical method for liquid phase synthesizing cyanuric acid |
| CN101830859A (en) * | 2010-05-14 | 2010-09-15 | 菏泽沃蓝化工有限公司 | Production method of isocyanuric acid |
| CN102285928A (en) * | 2011-08-29 | 2011-12-21 | 王铁招 | CA (Cyanuric Acid) liquid phase catalytic synthesis method |
| CN102516188A (en) * | 2011-12-12 | 2012-06-27 | 河北克尔化工有限公司 | Preparation method of high-yield cyanuric acid and its derivatives sodium dichloroisocyanurate and trichloroisocyanuric acid |
| CN105906577A (en) * | 2016-04-26 | 2016-08-31 | 王建伍 | Production process of pyrolysis cyanuric acid |
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