CN109232206B - Method for preparing cyclohexanone by using cyclohexanol distillation residual liquid - Google Patents
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- CN109232206B CN109232206B CN201811219094.6A CN201811219094A CN109232206B CN 109232206 B CN109232206 B CN 109232206B CN 201811219094 A CN201811219094 A CN 201811219094A CN 109232206 B CN109232206 B CN 109232206B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
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Abstract
The invention belongs to the field of comprehensive utilization of chemical waste resources, and particularly relates to a method for preparing cyclohexanone by using cyclohexanol distillation residual liquid. The technical solution of the invention is as follows: (1) adding boric acid and a drying agent into the cyclohexanol distillation residual liquid to protect the 1, 1' -dihydroxyl dicyclohexyl in the cyclohexanol distillation residual liquid; (2) adding an oxidant and a catalyst into the cyclohexanol distillation residual liquid to convert dicyclohexyl ether into cyclohexanone; (3) then adding calcium hypochlorite or ceric ammonium nitrate into the reaction liquid to convert the 1, 1' -dihydroxy dicyclohexyl borate into cyclohexanone; (4) the cyclohexanone is refined by a rectifying device, and the content is 99.7 percent.
Description
Technical Field
The invention belongs to the field of chemical waste resource comprehensive utilization, and relates to a method for preparing cyclohexanone by using cyclohexanol distillation residual liquid.
Background
Cyclohexanone is a colorless oily liquid at room temperature, formula C6H10O, molecular weight 98.14, melting point-47 ℃, boiling point 155 ℃, flash point 46 ℃, saturated vapor pressure 1330 Pa (25 ℃), relative density (water =1)0.95, refractive index n 20/D1.450, has a peppermint oil and acetone-like odor, is slightly water soluble, has a water solubility of 150 g/L (10 ℃), is miscible with most organic solvents. Cyclohexanone is an important chemical raw material, is a main intermediate for preparing nylon, caprolactam and adipic acid, and is heavyIndustrial solvents are used as solvents, initiators for oxidation reactions, paints containing nitrocellulose, vinyl chloride polymers and copolymers thereof, or methacrylate polymers; is an excellent solvent for pesticides such as organophosphorus pesticide and a plurality of analogues, and is used as a viscous solvent of piston type aviation lubricating oil, and a solvent of grease, wax and rubber; it is used as leveling agent for dyeing and fading filament, degreasing agent for polishing metal, and wood coloring paint.
In the production process of cyclohexanol, the distillation tower residual liquid is a byproduct in the industrial production process of cyclohexanol, which accounts for about 3% of the product amount of cyclohexanol, the production scale of cyclohexanol is 200 million tons per year in China at present, the quantity of the distillation tower residual liquid byproduct is about 6 million tons per year, the main components of the distillation tower residual liquid are dicyclohexyl ether and 1,1 '-dihydroxydicyclohexyl (the content of the main components of the distillation tower residual liquid is 76.28% of dicyclohexyl ether, 11.63% of 1, 1' -dihydroxydicyclohexyl and 12.09% of other impurities), and the combined analysis diagram of gas chromatography-mass spectrometry of the distillation tower residual liquid is shown in the attached figure 2).
Disclosure of Invention
The invention aims at the current situation that the high-risk chemical waste is easy to cause serious environmental pollution, and provides a method for preparing cyclohexanone by using cyclohexanol distillation residual liquid. The technical scheme adopted by the invention is that 1,1 ' -dihydroxyl dicyclohexyl in cyclohexanol distillation residual liquid is protected by boric acid, different oxidants are added twice to prepare cyclohexanone through oxidation, and the cyclohexanone with the purity of 99.7% is obtained through the distillation process, so that the problem of accumulation and storage of chemical wastes is fundamentally solved, the cyclohexanone products with high added value are comprehensively utilized as resources, the cyclohexanone products with high added value can be prepared, the national policy of ' resource, reduction and harmless ' treatment of industrial wastes is met, and the economic, social and environmental benefits are obvious.
The object of the invention can be achieved by the following technical measures:
the method for preparing cyclohexanone by using cyclohexanol distillation residual liquid comprises the following steps:
a. adding boric acid and a drying agent into the cyclohexanol distillation residual liquid to protect the 1, 1' -dihydroxyl dicyclohexyl in the cyclohexanol distillation residual liquid; the addition amount of the boric acid is 3.6-7.2% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the drying agent is 6.5-28% of the mass of the cyclohexanol distillation residual liquid;
b. adding an oxidant and a catalyst into the cyclohexanol distillation residual liquid to convert dicyclohexyl ether into cyclohexanone; the addition amount of the oxidant is 14-20% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the catalyst is 4-10% of the mass of the cyclohexanol distillation residual liquid;
c. adding calcium hypochlorite or ceric ammonium nitrate into the reaction liquid to convert the 1, 1' -dihydroxydicyclohexyl borate into cyclohexanone; the addition amount of the calcium hypochlorite is 8-20% of the mass of the cyclohexanol rectification residual liquid; the addition amount of the ammonium ceric nitrate is 3-20% of the mass of the cyclohexanol distillation residual liquid;
d. the cyclohexanone with the content of 99.7 percent is purified by a rectifying device, and can be used as a raw material to be directly used for preparing caprolactam and adipic acid or used as a solvent and a trigger of an oxidation reaction.
The content of dicyclohexyl ether in the cyclohexanol distillation residual liquid is 70-90%, and the content of 1, 1' -dihydroxy dicyclohexyl is 10-30%.
The drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate or anhydrous calcium chloride; the oxidant is sodium hypochlorite or hydrogen peroxide; the catalyst is sodium chloride or potassium chloride.
The invention has the following beneficial effects:
the invention adopts a one-pot stepwise oxidation method to convert dicyclohexyl ether and 1, 1' -dihydroxydicyclohexyl into cyclohexanone, and has simple process and low energy consumption; after separation and purification, the purity of the cyclohexanone reaches more than 99.7 percent, the cyclohexanone can be directly sold as a commodity, and the cyclohexanol distillation residual liquid is recycled, so that the cyclohexanone has remarkable economic, social and environmental benefits.
Drawings
FIG. 1 is a technical scheme of the present invention.
FIG. 2 is a gas chromatography-mass spectrometry analysis chart of a cyclohexanol distillation column residue.
FIG. 3 is a gas chromatography-mass spectrometry analysis chart for cyclohexanone production according to the present invention.
FIG. 4 is an infrared spectrum of cyclohexanone produced by the present invention.
Detailed Description
The invention will be further described with reference to the following examples (FIG. 1):
as shown in figure 1, the method for preparing cyclohexanone from cyclohexanol distillation tower raffinate comprises the following steps:
a. adding boric acid and a drying agent into the cyclohexanol distillation residual liquid to protect the 1, 1' -dihydroxyl dicyclohexyl in the cyclohexanol distillation residual liquid; the addition amount of the boric acid is 3.6-7.2% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the drying agent is 6.5-28% of the mass of the cyclohexanol distillation residual liquid;
b. adding an oxidant and a catalyst into the cyclohexanol distillation residual liquid to convert dicyclohexyl ether into cyclohexanone; the addition amount of the oxidant is 14-20% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the catalyst is 4-10% of the mass of the cyclohexanol distillation residual liquid;
c. adding calcium hypochlorite or ceric ammonium nitrate into the reaction liquid to convert the 1, 1' -dihydroxydicyclohexyl borate into cyclohexanone; the addition amount of the calcium hypochlorite is 8-20% of the mass of the cyclohexanol rectification residual liquid; the addition amount of the ammonium ceric nitrate is 3-20% of the mass of the cyclohexanol distillation residual liquid;
d. the cyclohexanone with the content of 99.7 percent is purified by a rectifying device, and can be used as a raw material to be directly used for preparing caprolactam and adipic acid or used as a solvent and a trigger of an oxidation reaction.
The content of dicyclohexyl ether in the cyclohexanol distillation residual liquid is 70-90%, and the content of 1, 1' -dihydroxy dicyclohexyl is 10-30%.
The drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate or anhydrous calcium chloride; the oxidant is sodium hypochlorite or hydrogen peroxide; the catalyst is sodium chloride or potassium chloride.
The cyclohexanone prepared and purified by the method has the content of 99.70 percent, and is colorless and transparent liquid; the diagram of the prepared cyclohexanone by GC-MS is shown in FIG. 3.
Example 1
Adding 80 kg of cyclohexanol distillation residual liquid (76.28% of dicyclohexyl ether, 11.63% of 1, 1' -dihydroxy dicyclohexyl and 12.09% of other impurities), 2.9 kg of boric acid and 5.21 kg of anhydrous calcium chloride into a reaction kettle, stirring at room temperature for 2 h, filtering out a drying agent, adding 37.94 kg of hydrogen peroxide (30% by mass) and 3.92 kg of sodium chloride, stirring at room temperature for 6 h for reaction, separating, adding 6.71 kg of calcium hypochlorite into an organic phase, stirring at room temperature for 6 h, separating, drying the organic layer with anhydrous calcium chloride, and filtering; mixing the water phases, extracting with ethyl acetate, drying the organic layer with anhydrous calcium chloride, and filtering; the organic phase is separated and purified by a rectifying tower after being concentrated to obtain 72.53 kg of cyclohexanone, and the content of the cyclohexanone is 99.70 percent by GC-MS analysis; IR (ATR, cm)−1):2935.66, 2862.36, 1705.07, 1448.54, 1346.31, 1338.6, 1311.59, 1265.3, 1220.94, 1118.71, 1051.2, 1018.41, 991.41, 908.47, 864.11, 750.31, 651.94；MS(EI) m/z: 98 [M+] (50), 83 (10), 69 (35), 55 (100)。
Example 2
Adding 80 kg of cyclohexanol distillation residual liquid (76.28% of dicyclohexyl ether, 11.63% of 1, 1' -dihydroxy dicyclohexyl and 12.09% of other impurities) into a reaction kettle, stirring at room temperature for 2 h, filtering to remove a drying agent, adding 41.73 kg of hydrogen peroxide (30% by mass) and 4.31 kg of sodium chloride, stirring at room temperature for 6 h for reaction, separating, adding 7.38 kg of calcium hypochlorite into an organic phase, stirring at room temperature for 6 h, separating, drying the organic layer with anhydrous calcium chloride, and filtering; mixing the water phases, extracting with ethyl acetate, drying the organic layer with anhydrous calcium chloride, and filtering; the organic phase is separated and purified by a rectifying tower after being concentrated to obtain 72.86 kg of cyclohexanone, and the content of the cyclohexanone is 99.72 percent by GC-MS analysis; IR (ATR, cm)−1):2935.66, 2862.36, 1705.07, 1448.54, 1346.31, 1338.6, 1311.59, 1265.3, 1220.94, 1118.71, 1051.2, 1018.41, 991.41, 908.47, 864.11, 750.31, 651.94；MS(EI) m/z: 98 [M+] (50), 83 (10), 69 (35), 55 (100)。
Example 3
Towards the reactionAdding 80 kg of cyclohexanol distillation residual liquid (76.28 percent of dicyclohexyl ether, 11.63 percent of 1, 1' -dihydroxy dicyclohexyl and 12.09 percent of other impurities), 2.9 kg of boric acid and 5.21 kg of anhydrous calcium chloride into a kettle, stirring at room temperature for 2 hours, filtering out a drying agent, adding 37.94 kg of hydrogen peroxide (30 percent by mass) and 3.92 kg of sodium chloride, stirring at room temperature for 6 hours for reaction, separating, adding 2.76 kg of ammonium ceric nitrate into an organic phase, stirring at room temperature for 6 hours, separating, drying an organic layer by using anhydrous calcium chloride, and filtering; mixing the water phases, extracting with ethyl acetate, drying the organic layer with anhydrous calcium chloride, and filtering; after the organic phase is concentrated, 72.08 kg of cyclohexanone is obtained by separation and purification of a rectifying tower, and the content of the cyclohexanone is 99.71 percent by GC-MS analysis; IR (ATR, cm)−1):2935.66, 2862.36, 1705.07, 1448.54, 1346.31, 1338.6, 1311.59, 1265.3, 1220.94, 1118.71, 1051.2, 1018.41, 991.41, 908.47, 864.11, 750.31, 651.94；MS(EI) m/z: 98 [M+] (50), 83 (10), 69 (35), 55 (100)。
Analysis of economic benefits
Because the cyclohexanol rectifying tower waste liquid mainly contains dicyclohexyl ether, 1' -dihydroxy dicyclohexyl and other components, if a common rectifying process is adopted, the tower precision requirement is too high, the load is too large, the treatment cost is high, the investment is large, and the rectifying tower waste liquid comes from the bottom of a rectifying tower, all the components are basically balanced, and the rectifying separation difficulty is large; if the extraction recovery technology is adopted, the process is complex, the price of the extracting agent is too high, and the loss amount is large. By adopting the patent technology and a partial protection strategy, the dicyclohexyl ether and the 1, 1' -dihydroxydicyclohexyl are converted into the cyclohexanone by adopting a one-pot step-by-step oxidation method, the process is simple, and the energy consumption is low; the purity of the separated and purified cyclohexanone reaches more than 99.7 percent, the cyclohexanone can be directly sold as a commodity, and the cyclohexanol distillation residual liquid is recycled and comprehensively utilized, so that the cyclohexanone has remarkable economic, social and environmental benefits.
The waste liquid volume of a rectifying tower of a 20-ten-thousand-ton/year cyclohexanol production device is about 600 tons, wherein the content of dicyclohexyl ether is 76.28 percent, and the content of 1, 1' -dihydroxy dicyclohexyl is 11.63 percent; the loss of dicyclohexyl ether is 458 tons/year, the loss of 1,1 '-dihydroxydicyclohexyl is 70 tons/year, the yield of the conversion of dicyclohexyl ether and 1, 1' -dihydroxydicyclohexyl into cyclohexanone according to the patent technology is 95 percent, 99.70 percent of 562 tons of cyclohexanone can be recovered, the current selling price of cyclohexanone is 1.5 ten thousand yuan/ton, and the total value is 843 ten thousand yuan.
Claims (2)
1. A method for preparing cyclohexanone by using cyclohexanol distillation raffinate is characterized in that: the method comprises the following steps:
a. adding boric acid and a drying agent into the cyclohexanol distillation residual liquid to protect the 1, 1' -dihydroxyl dicyclohexyl in the cyclohexanol distillation residual liquid; the addition amount of the boric acid is 3.6-7.2% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the drying agent is 6.5-28% of the mass of the cyclohexanol distillation residual liquid;
b. adding an oxidant and a catalyst into the cyclohexanol distillation residual liquid to convert dicyclohexyl ether into cyclohexanone; the addition amount of the oxidant is 14-20% of the mass of the cyclohexanol distillation residual liquid; the addition amount of the catalyst is 4-10% of the mass of the cyclohexanol distillation residual liquid;
c. adding calcium hypochlorite or ceric ammonium nitrate into the reaction liquid to convert the 1, 1' -dihydroxydicyclohexyl borate into cyclohexanone; the addition amount of the calcium hypochlorite is 8-20% of the mass of the cyclohexanol rectification residual liquid; the addition amount of the ammonium ceric nitrate is 3-20% of the mass of the cyclohexanol distillation residual liquid;
d. purifying cyclohexanone by a rectifying device, wherein the content of the cyclohexanone is 99.7 percent;
wherein the cyclohexanol distillation raffinate consists of 76.28% of dicyclohexyl ether, 11.63% of 1, 1' -dihydroxy dicyclohexyl and 12.09% of other impurities;
the oxidant is sodium hypochlorite or hydrogen peroxide; the catalyst is sodium chloride or potassium chloride;
the cyclohexanone is used as a raw material for directly preparing caprolactam and adipic acid or used as a solvent and a trigger of an oxidation reaction.
2. The method for preparing cyclohexanone from cyclohexanol distillation residue as set forth in claim 1, wherein: the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate or anhydrous calcium chloride.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147499A (en) * | 1995-10-10 | 1997-04-16 | 肖藻生 | Prepn of cyclohexanol and cyclohexanone |
| CN1253938A (en) * | 1998-11-12 | 2000-05-24 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
| CN102627525A (en) * | 2012-03-31 | 2012-08-08 | 肖藻生 | Preparation process for preparing hexamethylene and cyclohexanone by cyclohexane oxidation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147499A (en) * | 1995-10-10 | 1997-04-16 | 肖藻生 | Prepn of cyclohexanol and cyclohexanone |
| CN1253938A (en) * | 1998-11-12 | 2000-05-24 | 肖藻生 | Method for preparing cyclohexanol and cyclohexanone |
| CN102627525A (en) * | 2012-03-31 | 2012-08-08 | 肖藻生 | Preparation process for preparing hexamethylene and cyclohexanone by cyclohexane oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 环己醇精馏塔塔底液中环己醇的回收;魏新军等;《河南化工》;20150710;第32卷;第41-43页 * |
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Effective date of registration: 20230920 Address after: 467000 the development zone of the east section of Jianshe Road, Pingdingshan, Henan. Patentee after: HENAN SHENMA NYLON CHEMICAL Co.,Ltd. Patentee after: HENAN CHEMICAL INDUSTRY RESEARCH INSTITUTE Co.,Ltd. Address before: 467000 nylon company in Pingdingshan Development Zone, Henan Province Patentee before: PINGDINGSHAN SHENMA WANLI CHEMICAL Co.,Ltd. Patentee before: HENAN CHEMICAL INDUSTRY RESEARCH INSTITUTE Co.,Ltd. |
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