CN114672828A - A kind of method that utilizes galvanic cell technology to produce benzranthrone - Google Patents

Abstract

The invention discloses a method for producing benzanthrone by using a primary battery technology, belonging to the field of fine chemical engineering. The reaction is carried out in a galvanic cell apparatus consisting of a cathode cell, an anode cell and a permeable membrane. Concentrated sulfuric acid with the same concentration is added into a cathode tank and an anode tank to serve as reaction media, an aluminum plate serves as an anode, stainless steel 316L serves as a cathode, anthraquinone and glycerol are added into the cathode tank, reduction and cyclization reactions are carried out in the cathode tank, the anode and the cathode are directly connected through leads, the reaction process is accompanied by current, and electrons flow from the anode to the cathode through connecting leads. The anode tank simultaneously produces aluminum sulfate. Compared with the prior art, the method for producing the benzanthrone does not add a metal reducing agent in the main reactor, avoids the pollution of metal ions, can conveniently and completely recycle the aluminum sulfate generated by the anode, has secondary utilization value, simultaneously has high utilization rate of raw materials, does not contain metal salt in the mother liquor sulfuric acid, and can be concentrated and recycled.

Description

A kind of method that utilizes galvanic cell technology to produce benzranthrone

technical field

The invention belongs to the field of fine chemicals, and in particular relates to a method for producing benzranthrone by galvanic cell technology.

Background technique

Anthraquinone dyes are the most used type of dyes except azo dyes. Dyes with anthraquinone-like structure are mainly divided into four categories according to application: acid, reactive, disperse and vat dyes. They have three main advantages: one is excellent light fastness, and the other is that they can produce bright colors. Among dark dyes such as orange-red, violet, blue, green, especially blue, anthraquinone dyes occupy irreplaceable positions. Important position, the third is the low toxicity of anthraquinone dyes to the human body. At present, dark dyes are still dominated by dyes with anthraquinone structure, especially bright high-grade lightfast dyes. Anthraquinone series is still the first choice.

Benzoanthrone is obtained by direct synthesis of anthraquinone, and the characteristics of dyes synthesized with benzathrone are similar to those synthesized by anthraquinone, and are also classified as anthraquinone dyes. Because the solubility of most anthraquinone compounds in various solvents is very low, most of the reactions involving most anthraquinones are carried out in sulfuric acid medium, and the treatment of waste acid and wastewater is the production of anthraquinone dyes issues that must be addressed first.

Benzoranthrone is an important intermediate of anthraquinone dyes, mainly used in the production of vat olive T, vat violet RR, vat brilliant green FFB, vat olive green B, vat gray M, vat black BBN and other vat dyes, these vat dyes For dyeing and printing of high-grade cotton fabrics, it has excellent sun resistance. Benzoanthrone itself is also used as a sensitizer in degradable thermoplastic products, and is also an important organic light-emitting material.

The structural formula of benzranthrone is as follows:

Chemical name: Benzoanthrone

English name: Benzanthrone

Molecular formula: C ₁₇ H ₁₀ O

Relative molecular mass: 230.27g/mol

CAS number: 82-05-3

There are many synthetic methods of benzrathone. Anthraquinone is used as raw material, concentrated sulfuric acid is used as solvent and dehydrating agent under certain conditions to generate intermediate product and glycerol to undergo ring-closure reaction is the most important one. All of the methods use anthraquinone and glycerol or acrolein as reaction raw materials, but the selection of reducing agent varies greatly between methods, which directly affects the yield and cost benefit of the reaction, as well as the effect of environmental protection and energy saving.

The traditional process uses metals such as Zn, Fe, and Al as reducing agents. The equipment is simple, the operation is convenient, and the reaction is simple and easy. However, a large amount of metal reducing agents is required, the cost is high, the treatment process is complicated, the metal ions are difficult to recover, and the pollution is serious. To solve this problem, everyone is looking for a reducing agent that can replace the metal. For example, NaH ₂ PO ₂ , Pd/C catalyst, electrolytic reduction in electrolytic cell, and anthrone as reducing agent, etc., but due to problems such as cost, efficiency, reaction equipment, and raw material utilization, it is difficult to realize industrialization.

SUMMARY OF THE INVENTION

In order to solve the key problems of difficult recovery of metal ions and low utilization rate of raw materials in the prior art, the present invention proposes a method for producing benzoraanthone without waste acid, which does not require a metal reducing agent, has high utilization rate of raw materials, and can be concentrated and recycled in mother liquor sulfuric acid. .

In order to solve the above-mentioned problems, the technical scheme proposed by the present invention is as follows:

A method for producing benzranthrone by utilizing galvanic cell technology, the reaction is carried out in a galvanic cell device composed of a cathode cell, an anode cell and a permeable membrane; the permeable membrane separates the cathode cell and the anode cell; the cathode cell and the anode cell are combined with Concentrated sulfuric acid of the same concentration is used as the reaction medium, aluminum plate is used as the anode, stainless steel 316L is used as the cathode, anthraquinone and glycerol are added to the cathode tank, the reduction and cyclization reactions are carried out in the cathode tank, the anode and the cathode are directly connected with wires, and the reaction process is accompanied by An electric current is generated and electrons flow from the anode to the cathode through the connecting wires. The anode cell also produces aluminum sulfate. Specifically include the following steps:

(1) Anthraquinone, sulfuric acid and glycerol are placed in the cathode tank of the reactor, the anode tank is sulfuric acid of the same concentration, and the inserted electrodes are directly connected to form a primary cell for reaction;

(2) the reaction generates electric current, and the reaction degree of anthraquinone and the generation situation of benzranthrone are tracked by liquid chromatography;

(3) after the reaction is complete, washing the reaction solution with water to neutrality obtains a solid crude product, and obtains a fine product of benzrathrone after the alkali cooking and drying;

Anodic reaction: Al-3e ^- →Al ³⁺

Cathodic reaction:

Preferably, in the step (1), the anode material is aluminum, the cathode material is 316L stainless steel electrode, the 316L stainless steel electrode contains 2% Mo, and the cathode tank and the anode tank are separated by a permeable membrane.

Preferably, the concentration of sulfuric acid used in the step (1) is 70-95%; preferably, the concentration of sulfuric acid used in the step (1) is 85-92%.

Preferably, in the step (1), the mass ratio of anthraquinone to sulfuric acid is 1:3-60. The amount of sulfuric acid varies with the capacity of the reactor and the size of the filter cloth window; further, in the step (1), the mass ratio of anthraquinone to sulfuric acid is 1:2-10.

Preferably, the reactor in the step (1) is placed in an oil bath, and the temperature is 50°C to 180°C; further, the temperature of the oil bath in the step (1) is 70°C to 150°C.

Preferably, in the step (1), the molar ratio of anthraquinone and glycerol is 1:1-3; in the further step (1), the molar ratio of anthraquinone and glycerol is 1:1.02-1.5.

Preferably, the current in the steps (1) and (2) is above 100 mA.

Compared with the prior art, the advantages of the present invention are: 316L stainless steel electrode is used as the cathode, and aluminum electrode is used as the anode, no metal reducing agent is needed, the pollution of metal ions is avoided, and the Al ₂ (SO ₄ ) ₃ produced by the anode can be It is convenient and completely recycled as a flocculant, and has secondary utilization value. At the same time, the utilization rate of raw materials is high, and the mother liquor sulfuric acid does not contain metal salts, which can be concentrated and recycled, which not only reduces the cost, but also has no waste acid.

Description of drawings

Figure 1 is a diagram of primary battery equipment;

Fig. 2 is the ¹ H NMR chart of benzranthrone prepared in Example 1;

Fig. 3 is the gas chromatogram in the benzranthrone GC-MS chromatography prepared by embodiment 1;

Fig. 4 is the mass spectrogram in the benzranthrone GC-MS chromatography prepared by embodiment 1;

Detailed ways

In order to further describe the present invention in detail, the following specific examples are given, but only for explanations and explanations for better understanding of the technology, and are not limited thereto.

Example 1:

The reaction is carried out in a galvanic cell device consisting of a cathode cell, an anode cell and a permeable membrane (see Figure 1). Add 150 mL of 87% sulfuric acid, 20 g of anthraquinone, and 14 mL of glycerol into the cathode tank, and surround the tank wall with a 316L stainless steel mesh as the positive electrode of the primary battery, in which the anthraquinone undergoes a reduction reaction, and the anode tank is added to the cathode tank and other liquid levels. 87% sulfuric acid, add aluminum plate as anode, connect the anode and cathode directly with wires, and connect the ammeter in series to measure the current generated by the electrochemical reaction, heat up to 80 ° C, the initial current is greater than 190 mA, the reaction solution is bright yellow, and the reaction liquid is bright yellow. As the reaction progressed, the color of the reaction solution deepened, and after stirring for 10 hours, 34% of the anthraquinone remained, and the current was 120 mA to 140 mA.

The reaction solution was transferred to a 250 mL three-necked flask, and the temperature was continued to rise to 140° C. for 2 h until the reaction was complete. Then washed with distilled water to neutrality to obtain the crude product, then placed in the reaction kettle, added 200 mL of deionized water, 2 g of sodium hydroxide, controlled the temperature at 150°C, and the pressure at 1200KPa～1800KPa, kept the temperature for 2h after reaching the temperature, washed with water and dried after the reaction was completed. 21.1 g of fine benzrathone was obtained, the yield was 95.5%, and the content was 96.3% (HPLC internal method). The anolyte was filtered to obtain 35.0 g of aluminum sulfate containing a small amount of sulfuric acid.

Example 2

The reaction is carried out in a galvanic cell device consisting of a cathode cell, an anode cell and a permeable membrane (see Figure 1). Add 150 mL of 90% sulfuric acid and 20 g of anthraquinone into the cathode tank, and make a 316L mesh around the tank wall as the positive electrode of the primary battery, in which the anthraquinone undergoes a reduction reaction, and the anode tank is added with 87% sulfuric acid at the level of the cathode tank, etc. Add an aluminum plate as the anode, connect the anode and the cathode with a wire directly, and connect the ammeter in series to measure the current generated by the electrochemical reaction. The temperature is raised to 80 ° C, the initial current is 170 mA to 190 mA, and the reaction solution is bright yellow. With the progress of the reaction The color of the reaction solution deepened, stirred for 7h, the remaining anthraquinone was 38%, and the current was 130mA-150mA.

7.7mL of glycerol was added to the above reaction solution, heated and stirred for 4h, the remaining anthraquinone was 20%, and the current was 100mA-110mA.

The reaction solution was transferred to a 250 mL three-necked flask, and the temperature was continued to be heated to 140° C. for 2 h to complete the reaction. Then washed with distilled water to neutrality to obtain the crude product, then placed in the reaction kettle, added 200 mL of deionized water, 2 g of sodium hydroxide, controlled the temperature at 150°C, and the pressure at 1200KPa～1800KPa, kept the temperature for 2h after reaching the temperature, washed with water and dried after the reaction was completed. 21.6 g of benzranthrone fine products were obtained, the yield was 97.9%, and the content was 98.5% (HPLC internal method). The anolyte was filtered to obtain 34.1 g of aluminum sulfate containing a small amount of sulfuric acid.

Example 3

The reaction is carried out in a galvanic cell device consisting of a cathode cell, an anode cell and a permeable membrane (see Figure 1). Add 150 mL of 90% sulfuric acid and 20 g of anthraquinone into the cathode tank, and make the positive electrode of the primary battery with a 316L stainless steel mesh around the tank wall, in which the anthraquinone undergoes a reduction reaction, and add 87% sulfuric acid in the anode tank and the cathode tank. , add an aluminum plate as the anode, connect the anode and the cathode with a wire directly, and connect the ammeter in series to measure the current generated by the electrochemical reaction, heat up to 80 ° C, the initial current is 170mA ~ 190mA, the reaction solution is bright yellow, and as the reaction progresses The color of the reaction solution was deepened, stirred for 11 h, the remaining anthraquinone was 9%, and the current was 60 mA to 80 mA.

Transfer the reaction solution to a 250mL three-necked flask, continue to heat up to 140°C, add glycerol dropwise while heating, add 7.7mL dropwise in 15min, continue stirring and heating for 4h to stop the reaction. Then washed with distilled water to neutrality to obtain the crude product, then placed in the reactor, added 200 mL of deionized water, 2 g of sodium hydroxide, controlled the temperature at 150 ° C, the pressure at 1200 KPa ~ 1800 KPa, kept the temperature for 2 hours after reaching the temperature, washed and dried after the reaction was completed. 20.99 g of fine benzrathone was obtained, the yield was 95.0%, and the content was 95.8% (HPLC internal method). The anolyte was filtered to obtain 36 g of aluminum sulfate containing a small amount of sulfuric acid.

The above is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. Any person familiar with the technical field can easily think of changes or substitutions within the scope of the technical solutions disclosed in the present invention. , all should be covered within the protection scope of the present invention.

Claims (10)

1. A method for producing benzanthrone by using a galvanic cell technology is characterized in that: the reaction is carried out in a galvanic cell device consisting of a cathode cell, an anode cell and a permeable membrane; the permeable membrane separates the cathode tank from the anode tank; concentrated sulfuric acid is used as a reaction medium in the cathode tank and concentrated sulfuric acid is used as an anode in the anode tank, stainless steel 316L is used as a cathode, anthraquinone and glycerol are added in the cathode tank, reduction and cyclization reactions are carried out in the cathode tank, the anode and the cathode are directly connected by a lead, current is generated in the reaction process, and electrons flow from the anode to the cathode through a connecting lead; the anode tank simultaneously produces aluminum sulfate.

2. The method for producing benzanthrone by using galvanic technology according to claim 1, characterized in that a galvanic cell consisting of a cathode cell, an anode cell, a permeable membrane is used as a reactor.

3. The method for producing benzanthrone by using galvanic technology, according to claim 1, characterized in that the anode material is aluminum and the cathode material is 316L stainless steel electrode; concentrated sulfuric acid with the same concentration is added into the cathode tank and the anode tank as reaction media.

4. The method for producing benzanthrone by using galvanic technology according to claim 1, characterized in that the concentration of sulfuric acid used is 70-95%.

5. The method for producing benzanthrone by using the galvanic cell technology as claimed in claim 1, wherein the mass ratio of anthraquinone to sulfuric acid is 1: 3-60.

6. The method for producing benzanthrone by using galvanic technology as claimed in claim 1, wherein the molar ratio of anthraquinone to glycerol is 1: 1-3.

7. The method for producing benzanthrone according to the galvanic technology, as claimed in claim 1, characterized in that the reaction temperature is 50 ℃ to 180 ℃.

8. The method for producing benzanthrone by using galvanic technology according to claim 1, characterized in that the concentration of sulfuric acid used is 85-92%.

9. The method for producing benzanthrone by using the galvanic cell technology as claimed in claim 1, wherein the mass ratio of anthraquinone to sulfuric acid is 1: 2-10.

10. The method for producing benzanthrone by using the galvanic cell technology as claimed in claim 1, wherein the molar ratio of anthraquinone to glycerol is 1: 1.02-1.5; the reaction temperature is 70-150 ℃.

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