CN115772075A - Preparation method of chloranil - Google Patents
Preparation method of chloranil Download PDFInfo
- Publication number
- CN115772075A CN115772075A CN202211578100.3A CN202211578100A CN115772075A CN 115772075 A CN115772075 A CN 115772075A CN 202211578100 A CN202211578100 A CN 202211578100A CN 115772075 A CN115772075 A CN 115772075A
- Authority
- CN
- China
- Prior art keywords
- chloranil
- reaction
- chlorine
- temperature
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 8
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- RXPRRQLKFXBCSJ-GIVPXCGWSA-N vincamine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C[C@](O)(C(=O)OC)N5C2=C1 RXPRRQLKFXBCSJ-GIVPXCGWSA-N 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000009518 sodium iodide Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 229940090668 parachlorophenol Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of chloranil, which comprises the following steps: adding p-chlorophenol into a solvent to be fully dissolved, heating the material to 65 ℃, and then adding iron powder to carry out reduction reaction; after the reduction reaction is finished, adding a catalyst into the material, starting to introduce chlorine, and reacting the material at 60-82 ℃; and when the reaction product turns golden yellow, stopping introducing the chlorine gas, cooling, performing solid-liquid separation, washing the solid, and drying to obtain the chloranil. The tail gas generated by the method for preparing the chloranil is only hydrogen chloride gas, is diluted into hydrochloric acid by water, and can be sold as commercial hydrochloric acid when the concentration reaches more than 30 percent. The tail gas is convenient to treat, does not pollute the environment and has low cost.
Description
Technical Field
The invention belongs to the technical field of fine chemical production, and particularly relates to a preparation method of chloranil.
Background
Chloranil is a pigment and a medical intermediate, and is a main raw material for preparing permanent violet. The permanent violet has outstanding tinting strength and brightness, excellent heat resistance, seepage resistance, oxidation resistance and good light fastness, has wide application range, is popular in the fields of anticorrosive paint, plastics, organic glass, rubber, textile printing and dyeing, solvent amount, water-based ink, packaging printing, building materials, daily chemicals and the like, and is also used in the offset printing, gravure printing and flexographic printing industries.
It is important to obtain high purity chloranil. Chinese patent application No.: 2022109409051 discloses a process for preparing chloranil, which comprises dissolving p-nitrophenol in solvent, adding catalyst, heating to 60 deg.C, and introducing chlorine; materials are mixed at 60-The reaction is carried out at 82 ℃ to obtain tetrachlorobenzoquinone. The tetrachlorobenzoquinone prepared by the process has high purity, the reduced product is golden yellow in natural color, and the melting range is short. However, the tail gas generated by the reaction contains NO gas, the NO gas is directly discharged to pollute the atmosphere, and the NO gas is easily oxidized to generate NO 2 Further polluting the air. Therefore, the exhaust gas NO needs to be treated, but the flow of treating NO gas is complicated, the equipment is expensive, and the treatment cost is high.
Disclosure of Invention
The invention aims to provide a preparation method of chloranil, which solves the technical problem that tail gas generated during the preparation of chloranil pollutes the environment in the prior art.
In order to solve the problems, the invention is realized by the following technical scheme:
the preparation method of chloranil comprises the following steps:
adding p-chlorophenol into a solvent for full dissolution, heating the material to 65 ℃, and then adding a reducing agent for reaction;
after the reduction reaction is finished, adding a catalyst into the material, starting to introduce chlorine, and reacting the material at 60-82 ℃; and when the reaction product turns golden yellow, stopping introducing the chlorine, cooling, performing solid-liquid separation, washing the solid, and drying to obtain the chloranil.
The tail gas generated by adopting the method to prepare the chloranil is only hydrogen chloride gas, is diluted into hydrochloric acid by water, and can be sold as commodity hydrochloric acid when the concentration reaches more than 30 percent. The tail gas is convenient to treat, does not pollute the environment and has low cost.
Further improved, the reducing agent is iron powder, and the solvent is a mixed solution of distilled water, hydrochloric acid and glacial acetic acid;
according to the volume ratio, the distilled water: hydrochloric acid: glacial acetic acid =349.6:2.4:448;
wherein, the concentration of the hydrochloric acid is 32 percent, and the concentration of the glacial acetic acid is 99 percent.
Further improvement, the dosage ratio of the solvent, the parachlorophenol and the iron powder is 800ml:45g:6g.
In a further improvement, the catalyst is a mixed catalyst formed by sodium bromide with the purity of 99%, sodium iodide with the purity of 99% and sodium fluoride with the purity of 99%;
the mass ratio of the parachlorophenol to the mixed catalyst is 100: (4-6).
By adding the catalyst, the reaction time is greatly shortened, the efficiency is improved, and the cost is reduced.
Further improvement, the materials in the reaction container are heated by adopting water bath, and the initial temperature of the water bath is set to be 60-75 ℃; after the reduction reaction is finished, after the temperature in the reaction vessel is restored to 65 ℃, adding a catalyst, and introducing chlorine gas into the reaction vessel for 180-300 min.
The further improvement is that after the reduction reaction is finished, the material is filtered, and the catalyst is added into the filtrate for subsequent reaction.
The further improvement is that the water bath continuously heats the reaction vessel, and after chlorine gas is introduced, the materials start to react, and the process is divided into three stages:
early stage: setting the water bath temperature at 65-73 deg.c, heating for 10-30 min and chlorine flow rate of 0.03L/min;
in the middle stage: setting the water bath temperature at 73-75 ℃, heating for 110-200 min, and introducing chlorine flow at 0.05L/min;
and (3) later stage: setting the water bath temperature at 81-82 deg.c, heating for 60-70 min and chlorine flow rate of 0.025L/min.
Further improvement, after the reaction is finished, cooling the materials to 30-35 ℃, and then filtering to separate solid from liquid, wherein the liquid can be recycled; the solid is washed to be neutral by purified water with the temperature of 50-60 ℃, and then is dried to obtain the chloranil. In the cooling process, solid is precipitated, and the lower the temperature is, the more favorable the solid precipitation is, but the too low temperature is, the refrigeration energy consumption is large, and the cost is greatly increased. The solid separated out by cooling is chloranil, and when the washing temperature is not higher than 60 ℃, the temperature is too high to facilitate the operation of workers.
Further improvement, the drying conditions are as follows: the temperature is 80 ℃, the drying time is 50-70min, and the vacuum degree of the drying oven is more than or equal to 0.09MPa.
Further improved, after the reaction is finished, the free chlorine in the reactor is removed through negative pressure vacuum pumping, and then cooling is carried out.
Compared with the prior art, the invention has the beneficial effects that:
the tetrachlorobenzoquinone prepared by the process has high purity, the reduced product is golden yellow in natural color, and the melting range is short. The generated tail gas is only hydrogen chloride gas, and is diluted into hydrochloric acid by water, and the hydrochloric acid can be sold as commodity hydrochloric acid when the concentration reaches more than 30%. The tail gas treatment is convenient, the environment is not polluted, and the cost is greatly reduced.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
The first embodiment is as follows:
in this example, chloranil was prepared in the laboratory, the reaction vessel was a flask, and the heating device was a water tank. The preparation method comprises the following steps:
the method comprises the following steps: the flask, stirrer and condenser were assembled to ensure that the flask did not vibrate when the stirrer was turned, and then the ground chloride pipe was assembled.
Step two: 800ml of the prepared solvent was measured and added to the flask via a funnel while the stirrer was started to stir.
In this embodiment, the solvent is a mixture of distilled water, hydrochloric acid and glacial acetic acid; calculated according to the volume ratio, the ratio of distilled water: hydrochloric acid: glacial acetic acid =349.6:2.4:448; wherein, the concentration of the hydrochloric acid is 32 percent, and the concentration of the glacial acetic acid is 99 percent.
The hydrochloric acid contains hydrogen chloride, i.e. chloride ions are present. The chloride ions react with the iron powder to produce gaseous hydrogen chloride gas and ferric chloride (which is a chlorinated catalyst dissolved in the solution), which consumes the reducing agent iron powder. Therefore, the hydrochloric acid content is strictly controlled, and if the iron powder is consumed in a large amount due to an excessive hydrochloric acid content, the total amount of the reducing agent is increased, which results in an increase in cost and an increase in by-products.
Step three: 45g of solid p-chlorophenol and 6g of iron powder were weighed separately and added to the solvent in the flask via a funnel. Then stirring is started, and simultaneously a water tank is started to heat the materials, and the temperature of the water tank is maintained at 60-75 ℃. The purity of p-chlorophenol was 99%. A mercury thermometer was inserted into the flask after being inserted into the ground-neck, and the mercury head of the thermometer was inserted below 10mm of the liquid surface.
Adding iron powder and p-chlorophenol to perform reduction reaction, and removing chloride ions in the p-chlorophenol. The reduction reaction is a heat release process, the temperature in the flask is slightly higher than the temperature in the water tank in the reaction process, the reaction time is about 150min, and after the reaction is finished, the temperature in the flask is recovered to be the same as that in the water tank.
The reducing agent is of a wide variety. For example, the hydrogen has strong reducing capability and no pollution, but the hydrogen is easy to explode, has high risk and large investment; naOH is also a good reducing agent, but is not suitable for this solution. The applicant verifies through a large number of experiments that iron powder is finally selected as a reducing agent.
Step four: after the reduction reaction is finished, filtering the materials to remove mechanical impurities and solid substances generated by the reaction, wherein the filtrate is transparent, quickly filling the filtrate into a flask, and continuously heating the materials by using a water tank; then 4.5g of mixed catalyst was added, and the mixture was stirred continuously, and then chlorine gas was introduced to carry out the subsequent reaction.
The catalyst is a mixed catalyst formed by sodium bromide with the purity of 99%, sodium iodide with the purity of 99% and sodium fluoride with the purity of 99%. Wherein, the content of the sodium bromide is 0.5 to 5g, the content of the sodium iodide is 0.5 to 5g, and the content of the sodium fluoride is 0.5 to 3g. Determining the content of each component according to specific requirements as long as the mass ratio of the parachlorophenol to the mixed catalyst is 100: (4-6).
In this example, it is necessary to dissolve the weighed solid mixed catalyst in pure water, and then add the catalyst solution to the flask for reaction. The mass ratio of the mixed catalyst to water is as follows: water =1: (1-2), the water content cannot be excessive, otherwise, the volume of the mother liquor in the flask is influenced, and the subsequent reaction is further influenced.
Step five: after chlorine gas is introduced, the materials start to react, and the process is divided into three stages:
early stage: setting the water bath temperature at 65-73 deg.c, heating for 10-30 min and chlorine flow rate of 0.03L/min;
in the middle stage: setting the water bath temperature at 73-75 ℃, heating for 110-200 min, and introducing chlorine flow at 0.05L/min;
and (3) later stage: setting the water bath temperature at 81-82 deg.c, heating for 60-70 min and chlorine flow rate of 0.025L/min.
The chlorine is bottled chlorine with the purity of 99.9 percent, and the chlorine introducing time is 180-300 min.
The tail gas generated in the reaction process is only hydrogen chloride, and the hydrogen chloride gas is diluted by water to become hydrochloric acid, wherein the content of the hydrochloric acid is 30-32%. The tail gas is convenient to treat, the environment is not polluted, and the cost is greatly reduced.
In the reaction process, the color of the materials changes: tan → red → crimson → orange → dark yellow → gold.
When the reaction of the materials turns to golden yellow, the reaction is finished, the chlorine valve is closed, and the chlorine is stopped from being introduced. The total amount of chlorine gas introduced amounted to 115g. The ineffective chlorine flux and the loss amount are not considered.
Step five: after the reaction is finished, removing free chlorine in the reactor by negative pressure vacuumizing; then discharging the hot water in the water tank, adding cold water for cooling, and cooling the material to 30 ℃; and then carrying out solid-liquid separation on the tetrachlorobenzoquinone by adopting a vacuum pump and a Buchner funnel, washing the filtered solid by adopting purified water at 50 ℃ to be neutral, and finally drying to obtain tetrachlorobenzoquinone.
The filtered liquid was analyzed and the reaction consumption was 10-20ml. Calculated by glacial acetic acid, the content is only reduced by 2-4%, and the method can be recycled and reduce the cost.
The drying conditions are as follows: the temperature is 80 deg.C, the drying time is 50-70min, and the vacuum degree of the drying oven is not less than 0.09Mpa. The water content of chloranil is less than 0.5%.
78g of the tetrachlorobenzoquinone prepared at this time is weighed, the theoretical yield value is 86g, the molar yield is 90.7 percent, and the yield is good.
The appearance of the prepared chloranil is golden yellow and powdery, and the original color of the product is reduced.
And (3) carrying out melting point, melting range and chromatographic detection on trace tetrachlorobenzoquinone prepared at this time, wherein an automatic melting point instrument is adopted to detect that the melting point is 292.3-292.6 ℃, and the melting range is 0.3 ℃. The purity of chloranil detected by a high performance liquid chromatograph is 99.3%.
Chinese patent application No.: 2022109409051, name: a method for preparing chloranil. For the earlier stage of research and development, the raw material adopted is p-nitrophenol. However, when the method is used for producing chloranil, the tail gas generated by the reaction contains NO gas, the NO gas is directly discharged to pollute the atmosphere, and the NO gas is easily oxidized to generate NO 2 Further polluting the air. Therefore, the exhaust gas NO needs to be treated, but the flow of treating the NO gas is complicated and the equipment is expensive. Therefore, through a great deal of research, the applicant improves the original scheme, adopts p-chlorophenol as a raw material, develops a mixed catalyst formed by sodium bromide, sodium iodide and sodium fluoride, and has the advantages of high reaction efficiency, high purity of finished products, easy treatment of tail gas, no pollution and low cost.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of chloranil is characterized by comprising the following steps:
adding p-chlorophenol into a solvent for full dissolution, heating the materials to 65 ℃, and then adding a reducing agent for reaction;
after the reduction reaction is finished, adding a catalyst into the materials, starting to introduce chlorine, and reacting the materials at 60-82 ℃; and when the reaction product turns golden yellow, stopping introducing the chlorine, cooling, performing solid-liquid separation, washing the solid, and drying to obtain the chloranil.
2. The method of producing chloranil according to claim 1, wherein the solvent is a mixture of distilled water, hydrochloric acid and glacial acetic acid;
according to the volume ratio, the distilled water: hydrochloric acid: glacial acetic acid =349.6:2.4:448;
wherein, the concentration of the hydrochloric acid is 32 percent, and the concentration of the glacial acetic acid is 99 percent.
3. The method for preparing chloranil according to claim 2, wherein the reducing agent is iron powder, and the solvent, the parachlorophenol and the iron powder are used in a ratio of 800ml:45g:6g.
4. The method for producing chloranil according to claim 3, wherein said catalyst is a mixed catalyst of sodium bromide, sodium iodide and sodium fluoride;
the mass ratio of the p-chlorophenol to the mixed catalyst is 100: (4-6).
5. The method for preparing chloranil according to claim 4, wherein the materials in the reaction vessel are heated by a water bath, and the initial temperature of the water bath is set to be 60-75 ℃; after the reduction reaction is finished, after the temperature in the reaction vessel is restored to 65 ℃, adding the mixed catalyst, and introducing chlorine into the reaction vessel for 180-300 min.
6. The method of producing chloranil according to claim 5, wherein after the reduction reaction is completed, the material is filtered, and a catalyst is added to the filtrate to carry out a subsequent reaction.
7. The method for preparing chloranil according to claim 5 or 6, wherein the reaction vessel is continuously heated by a water bath, and after chlorine gas is introduced, the reaction of the materials is started, and the process is divided into three stages:
in the early stage: setting the water bath temperature at 65-73 deg.c, heating for 10-30 min and chlorine flow rate of 0.03L/min;
in the middle stage: setting the water bath temperature at 73-75 ℃, heating for 110-200 min, and introducing chlorine flow at 0.05L/min;
and (3) later stage: setting the water bath temperature at 81-82 deg.c, heating for 60-70 min and chlorine flow rate of 0.025L/min.
8. The method for preparing chloranil according to claim 7, wherein after the reaction is finished, the material is cooled to 30-35 ℃, and then is filtered to separate solid from liquid, and the liquid can be recycled; the solid is washed to be neutral by purified water at 50-60 ℃, and then dried to obtain chloranil.
9. The method of claim 8, wherein after the reaction, the free chlorine gas in the reactor is removed by vacuum pumping under negative pressure, and then the temperature is lowered by cooling.
10. The method for preparing chloranil according to claim 9, wherein the drying conditions are: the temperature is 80 ℃, the drying time is 50-70min, and the vacuum degree of the drying oven is more than or equal to 0.09MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211578100.3A CN115772075B (en) | 2022-12-09 | Preparation method of tetrachlorobenzoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211578100.3A CN115772075B (en) | 2022-12-09 | Preparation method of tetrachlorobenzoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115772075A true CN115772075A (en) | 2023-03-10 |
| CN115772075B CN115772075B (en) | 2024-06-07 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN108101762A (en) * | 2017-12-20 | 2018-06-01 | 夏月宏 | 2,3,5,6- tetrachloroquinones and preparation method thereof |
| CN115340450A (en) * | 2022-08-07 | 2022-11-15 | 丁平 | Preparation method of chloranil |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866399A (en) * | 2017-03-03 | 2017-06-20 | 南通书创药业科技有限公司 | Tetrachloroquinone and preparation method thereof |
| CN108101762A (en) * | 2017-12-20 | 2018-06-01 | 夏月宏 | 2,3,5,6- tetrachloroquinones and preparation method thereof |
| CN115340450A (en) * | 2022-08-07 | 2022-11-15 | 丁平 | Preparation method of chloranil |
Non-Patent Citations (4)
| Title |
|---|
| GHASSAN AL-SAYYED，等: "Semiconductor-sensitized photodegradation of 4-chlorophenol in water", J. PHOTOCHEM. PHOTOBIOL. A: CHEM., vol. 58, pages 111 * |
| HANS LIIBBECKE AND PETER BOLDT: "Nonpollutative Chlorination and Chlorinating Oxidation of Phenols", ANGRW. CHEM. 1111. ED. ENGL., vol. 15, no. 10, pages 159 * |
| SOHAIL AHMAD，等: "Role of Hydroxyl Functionalized Ionic Liquids in Oxygenation and Oxidation of Phenols with H2O2 Catalysed by Iron(III) Porphyrins", CURRENT ORGANIC CHEMISTRY, vol. 16, pages 2991 * |
| 陈小明: "氯气氧化法合成四氯苯醌的研究", 广东化工, vol. 39, no. 14 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106745246B (en) | A kind of method for preparing vanadic sulfate | |
| CN106517177A (en) | Method for purifying graphite by using high-pressure alkaline leaching | |
| CN101139338A (en) | Preparation of 2,2-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt | |
| CN1843938A (en) | Method for preparing vanadium pentoxide | |
| CN112724700B (en) | Process for synthesizing permanent violet RL by one-pot method | |
| CN107446381A (en) | The method that nitrating wasting acid of Disperse Blue-56 recycles | |
| CN103979705B (en) | Method for recovering potassium nitrate from anthraquinone dye alkali wastewater | |
| CN104310447A (en) | Green recovery treatment method of 1,4-dihydroxy anthraquinone waste sulfuric acid | |
| CN108622938A (en) | A method of preparing ammonium dimolybdate from containing molybdenum solution | |
| CN115340450A (en) | Preparation method of chloranil | |
| CN102732727B (en) | Method for extracting vanadium from high vanadium-sodium-aluminum-silicon slag | |
| CN115772075B (en) | Preparation method of tetrachlorobenzoquinone | |
| CN115772075A (en) | Preparation method of chloranil | |
| CN101845235A (en) | Method for preparing aniline black in dye industry | |
| CN105540926B (en) | A kind of method using acid waste water co-producing white carbon black and inorganic salts | |
| CN106349733B (en) | A kind of technique and its equipment for synthesizing disperse red FB | |
| CN112062148A (en) | Method for preparing cuprous chloride by using copper-containing sludge in electroplating circuit board wastewater | |
| CN108623442B (en) | Method for reducing dioxin in tetrachlorobenzoquinone preparation | |
| CN104371347B (en) | A kind of Vat Blue RSN preparation method | |
| CN110591407A (en) | Synthetic method of low-toxicity low-harm environment-friendly solvent purple 13 | |
| CN107473943A (en) | A kind of preparation method of 2,6 orcin | |
| CN106810412A (en) | A kind of production method of the method and Dispersant MF for improving sulfonating reaction efficiency | |
| CN104744365A (en) | Method for directly preparing light-emitting material 8-hydroxyquinoline copper | |
| CN102944642B (en) | A kind of preparation method of iodine value reagent of improvement | |
| CN104371346B (en) | A kind of vat brown RP dyestuff preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |