CN114438528B - Electrochemical preparation method of benzanthrone - Google Patents
Electrochemical preparation method of benzanthrone Download PDFInfo
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- CN114438528B CN114438528B CN202210181372.3A CN202210181372A CN114438528B CN 114438528 B CN114438528 B CN 114438528B CN 202210181372 A CN202210181372 A CN 202210181372A CN 114438528 B CN114438528 B CN 114438528B
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- benzanthrone
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- sulfuric acid
- electrolyte
- anthraquinone
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- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012965 benzophenone Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 1
- JACFBUVEFBYGAX-UHFFFAOYSA-N 4395-53-3 Chemical compound N1C(C2=C(C(C3=CC=CC=C3C2=O)=O)C=C2)=C2C2=CC=C3C(=O)C4=CC(NC5=C6C(=O)C7=CC=CC=C7C(C6=CC=C5)=O)=CC=C4C4=CC=C1C2=C43 JACFBUVEFBYGAX-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- HHKPGQSPFVLKMV-UHFFFAOYSA-N vat olive green b Chemical compound N1C(C2=C(C(C3=CC=CC=C3C2=O)=O)C=C2)=C2C2=CC=C3C(=O)C4=CC=CC=C4C4=CC=C1C2=C43 HHKPGQSPFVLKMV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an electrochemical preparation method of benzanthrone, which comprises the following steps: (1) Electrolyte and anthraquinone are sequentially added into an electrolytic cell without a diaphragm, a cathode and an anode are inserted, and nitrogen is introduced; (2) Stirring and heating to the reaction temperature, powering on, simultaneously dropwise adding glycerol into an electrolytic cell, and reacting at constant temperature and constant current; (3) After the reaction is completed, the electrolyte is diluted to 60% of the mass fraction of the acid, the product is separated out, filtered and washed, and then the benzanthrone is obtained after drying. The advantages are that: 1. the invention adopts the electrochemical method to prepare the benzanthrone, has simple process and mild reaction condition; 2. no organic solvent is added in the reaction process, no heavy metal salt is generated, and the method is an environment-friendly organic synthesis reaction; 3. the reaction product is easy to separate, the content of the benzanthrone is high, and an additional treatment process is not needed; 4. the main pollutants in the electrolyte are some sulphonates of anthraquinone or benzophenone, which are easy to remove, and the electrolyte after purification can be recycled.
Description
Technical field:
the invention relates to the technical field of electrochemical organic synthesis, in particular to an electrochemical preparation method of benzanthrone.
The background technology is as follows:
the benzanthrone is also called benzanthrone, is an important anthraquinone dye intermediate, and can be used for producing various vat dyes, such as vat dark blue BO, vat brilliant green FFB, vat ash M, vat olive green B, vat olive green T, vat black BBN and the like; its molecular formula is C 17 H 10 O, its molecular structure is as follows:
the traditional synthesis process of the benzanthrone comprises the following steps: anthraquinone and glycerin are synthesized into benzanthrone by taking iron powder or zinc powder as a reducing agent and copper sulfate as a catalyst under the condition of concentrated sulfuric acid. During the reaction, a large amount of heavy metal salts such as ferrous sulfate, ferric sulfate, copper sulfate and the like are generated, and the concentrated sulfuric acid cannot be further purified and reused due to the fact that the concentrated sulfuric acid contains a large amount of metal ions, so that the concentrated sulfuric acid is wasted; if the treatment is improper, the environment is polluted; meanwhile, the iron powder or zinc powder is also wrapped on the benzanthrone, so that the content of the obtained benzanthrone product is low, generally only 85%, and in order to obtain the benzanthrone with high content, an additional treatment process is required, and the production cost and the equipment investment are increased.
Patent CN110668930A discloses a novel production method of benzanthrone, which is greatly improved compared with the traditional process, provides a new feasible research direction for us, but the catalytic hydrogenation reaction involved in the reaction process is carried out under the conditions of high temperature and high pressure and simultaneously introducing hydrogen, the process is dangerous, and the requirements on equipment are severe; the product of catalytic hydrogenation, namely the anthracenol, has active property and poor control and is easy to oxidize; organic solvents are used in the reaction, an independent solvent recovery system needs to be established, an auxiliary system is huge, and equipment investment is large.
The invention comprises the following steps:
in order to overcome the defects of complex synthesis process and serious environmental pollution of the existing benzanthrone, the invention aims to provide an electrochemical preparation method of benzanthrone, which has the advantages of simple process, mild condition and environmental friendliness.
The synthetic route of the invention is as follows:
the invention is implemented by the following technical scheme: an electrochemical preparation method of benzanthrone comprises the following steps:
(1) Electrolyte and anthraquinone are sequentially added into an electrolytic cell without a diaphragm, a cathode and an anode are inserted, and nitrogen is introduced;
(2) Stirring and heating to the reaction temperature at a heating rate of 1-2 ℃/min, powering on, simultaneously dropwise adding glycerol into an electrolytic cell, and reacting under the conditions of constant temperature and constant current;
(3) After the reaction is finished, water is added into the electrolyte, the electrolyte is diluted until the mass fraction of acid is 60%, a product is precipitated, the product is filtered, and a filter cake is washed until the pH value is 6-7, and then the product is placed in a constant temperature oven for drying, so that the benzanthrone is obtained.
Further, in the step (1), the electrolyte is a concentrated sulfuric acid solution.
Further, the concentration of the concentrated sulfuric acid solution is 85%.
Further, in the step (1), the cathode is one of a carbon electrode, a platinum electrode or a copper electrode; the anode is one of a carbon electrode, a glass electrode, a platinum electrode or a copper electrode.
Further, in the step (1), the mass of the electrolyte is 3 to 6 times that of anthraquinone.
Further, in the step (2), the glycerol is added in an amount of: the molar ratio of anthraquinone to glycerin is ensured to be 0.1-1.
Further, the glycerin in the step (2) is added dropwise for 1-4 hours.
Further, the reaction temperature of the step (2) is 80-120 ℃.
Further, the current in the energizing step in the step (2) is 3-10A.
Further, the drying temperature in the step (3) is 105-120 ℃ and the drying time is 6-12 h.
The invention has the advantages that: 1. the invention adopts the electrochemical method to prepare the benzanthrone, has simple process and mild reaction condition; 2. no organic solvent is added in the reaction process, no heavy metal salt is generated, and the method is an environment-friendly organic synthesis reaction; 3. the reaction product is easy to separate, the content of the benzanthrone is high, and no additional treatment process is needed; 4. the main pollutants in the electrolyte are some sulphonates of anthraquinone or benzophenone, which are very easy to remove under the dual actions of acid precipitation and activated carbon adsorption, and the purified electrolyte can be recycled.
The specific embodiment is as follows:
the principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1:
adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into an electrolytic cell which takes a carbon electrode as a cathode and an anode respectively, stirring under the protection of nitrogen, heating the solution to 100 ℃ at a heating rate of 1 ℃/min, electrifying, adjusting the current to 3A, and simultaneously dropwise adding 0.1mol of glycerol for 2 hours; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing the filter cake to pH 6-7, and then placing the filter cake in a constant temperature oven at 105 ℃ for drying for 12 hours to obtain the benzanthrone.
Example 2:
adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into an electrolytic cell with a platinum electrode as a cathode and a glass electrode as an anode, stirring under the protection of nitrogen, and heating the solution to 80 ℃ at a heating rate of 2 ℃/min; electrifying, regulating the current to 10A, and simultaneously dropwise adding 0.048mol of glycerol for 1h; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing the filter cake to pH 6-7, and then placing the filter cake in a constant temperature oven at 105 ℃ for drying for 6 hours to obtain the benzanthrone.
Example 3:
adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into an electrolytic cell which takes a platinum electrode as a cathode and an anode respectively, stirring under the protection of nitrogen, and heating the solution to 120 ℃ at a heating rate of 2 ℃/min; electrifying, regulating the current to 3A, and simultaneously dropwise adding 0.48mol of glycerol for 4 hours; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing the filter cake to pH 6-7, and then placing the filter cake in a constant temperature oven at 105 ℃ for drying for 12 hours to obtain the benzanthrone.
Example 4:
the three methods for preparing benzanthrone of examples 1 to 3 and the benzanthrone products obtained were respectively subjected to tests of yield and benzanthrone content and purity, and the test results are shown in Table 1.
Table 1 results of measurement of yield, purity and content of benzanthrone in examples
| Example 1 | Example 2 | Example 3 | |
| Yield rate | 95％ | 96％ | 94％ |
| Purity of | 99.5％ | 99.6％ | 98.9％ |
| Content of | 97.6％ | 98.2％ | 96.8％ |
As can be seen from Table 1, compared with the yield of about 87%, the purity of about 99% and the content of about 85% in the traditional process, the purity of the method provided by the invention can reach the purity of the traditional process, the yield and the content of the method are obviously improved compared with the traditional process, the utilization ratio of raw materials can be greatly improved, and the subsequent reduction of benzanthrone serving as an intermediate and the application performance of the product of the disperse dye are improved.
The foregoing description of the preferred embodiments of the present invention is not intended to be limiting, but rather, any modifications, equivalents, improvements, etc. that fall within the spirit and scope of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. An electrochemical preparation method of benzanthrone is characterized by comprising the following steps: adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into a diaphragm-free electrolytic cell with a carbon electrode as a cathode and an anode respectively, stirring under the protection of nitrogen, heating the solution to 100 ℃ at a heating rate of 1 ℃ per minute, electrifying, adjusting the current to 3A, and simultaneously dropwise adding 0.1mol of glycerol for 2 hours; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing a filter cake to pH 6-7, and then placing the filter cake in a 105 ℃ constant temperature oven for drying for 12 hours to obtain the benzanthrone.
2. An electrochemical preparation method of benzanthrone is characterized by comprising the following steps: adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into a diaphragm-free electrolytic cell with a platinum electrode as a cathode and a glass electrode as an anode, stirring under the protection of nitrogen, and heating the solution to 80 ℃ at a heating rate of 2 ℃ per minute; electrifying, regulating the current to 10A, and simultaneously dropwise adding 0.048mol of glycerol for 1h; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing a filter cake to pH 6-7, and then placing the filter cake in a 105 ℃ constant temperature oven for drying for 6 hours to obtain the benzanthrone.
3. An electrochemical preparation method of benzanthrone is characterized by comprising the following steps: adding 0.048mol of anthraquinone and 50g of 85% sulfuric acid solution into a diaphragm-free electrolytic cell with a platinum electrode as a cathode and an anode respectively, stirring under the protection of nitrogen, and heating the solution to 120 ℃ at a heating rate of 2 ℃ per minute; electrifying, regulating the current to 3A, and simultaneously dropwise adding 0.48mol of glycerol for 4 hours; when the electric quantity reaches 10560 coulomb, stopping electrifying; and diluting the concentration of the sulfuric acid solution to 60%, filtering, washing a filter cake to pH 6-7, and then placing the filter cake in a 105 ℃ constant temperature oven for drying for 12 hours to obtain the benzanthrone.
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| CN202210181372.3A CN114438528B (en) | 2022-02-25 | 2022-02-25 | Electrochemical preparation method of benzanthrone |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4311565A (en) * | 1979-05-30 | 1982-01-19 | Ciba-Geigy Ag | Electrochemical process for the production of benzanthrone |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4311565A (en) * | 1979-05-30 | 1982-01-19 | Ciba-Geigy Ag | Electrochemical process for the production of benzanthrone |
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