CN108707065B - Method and device for extracting dicyclohexyl ether from cyclohexanol rectification residual liquid - Google Patents
Method and device for extracting dicyclohexyl ether from cyclohexanol rectification residual liquid Download PDFInfo
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- CN108707065B CN108707065B CN201810910229.7A CN201810910229A CN108707065B CN 108707065 B CN108707065 B CN 108707065B CN 201810910229 A CN201810910229 A CN 201810910229A CN 108707065 B CN108707065 B CN 108707065B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
A method and a device for extracting dicyclohexyl ether from cyclohexanol rectification residual liquid belong to the field of chemical waste comprehensive utilization. The invention is realized by using a device which consists of a distillation kettle, two sections of cavity type rectifying towers, a condenser, a dicyclohexyl ether storage tank and a vacuum pump and adopting the following steps: a. adding cyclohexanol into distillation still, gradually heating to 125-3‑1.5×103Pa; b. then controlling the temperature of the distillation kettle to be 125-135 ℃, controlling the temperature of the top of the two-section cavity type rectifying tower to be 90-105 ℃, carrying out rectification separation by adopting an intermittent total reflux method, and finishing the rectification operation when the temperature of the top of the rectifying tower exceeds 105 ℃; c. the dicyclohexyl ether vapor extracted from the top of the two sections of cavity type rectifying towers enters a condenser for cooling to form liquid, and finally enters a dicyclohexyl ether storage tank; d. and (4) putting the high-chroma heavy components left in the distillation kettle into a collecting barrel for sealing and storing.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of chemical wastes, and relates to a method for extracting dicyclohexyl ether from cyclohexanol rectification residual liquid.
Background
Dicyclohexyl ether of the formula C12H22O, molecular weight 182.30248, melting point-3.6 ℃, boiling point 242.5 ℃, flash point 93.9 ℃, vapor pressure 0.0526 mmHg (25 ℃), relative density (water =1)0.92, refractive index 1.473,
is slightly soluble in water. Mainly used as organic synthesis raw materials, high boiling point solvents and the like.
In the production process of cyclohexanol, the distillation tower residual liquid is a byproduct in the industrial production process of cyclohexanol, and accounts for about 3% of the product amount of cyclohexanol, the production scale of cyclohexanol in China at present is 200 ten thousand tons per year, the quantity of the distillation tower residual liquid is about 6 ten thousand tons per year, and the distillation tower residual liquid belongs to high-risk chemical wastes, is difficult to treat, has high cost and is easy to cause serious environmental pollution.
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 extracting dicyclohexyl ether from cyclohexanol rectification residual liquid. The invention not only can comprehensively utilize resources of chemical wastes, but also can prepare dicyclohexyl ether products with high added value, meets the national policy requirements of 'recycling, reducing and harmless' treatment of industrial wastes, and has obvious economic, social and environmental benefits.
The object of the invention can be achieved by the following technical measures:
the method for extracting dicyclohexyl ether from cyclohexanol distillation residual liquid is characterized by comprising the following steps: the method comprises the following steps:
a. adding cyclohexanol into distillation still, gradually heating to 125-3-1.5×103Pa；
b. Then controlling the temperature of the distillation kettle to be 125-135 ℃, controlling the temperature of the top of the two-section cavity type rectifying tower to be 90-105 ℃, carrying out rectification separation by adopting an intermittent total reflux method, and finishing the rectification operation when the temperature of the top of the two-section cavity type rectifying tower exceeds 105 ℃;
c. the dicyclohexyl ether vapor extracted from the top of the two sections of cavity type rectifying towers enters a condenser for cooling to form liquid, and finally enters a dicyclohexyl ether storage tank;
d. and (4) putting the high-chroma heavy components (5-7%) left in the distillation kettle into a collecting barrel for sealing and storing.
The device suitable for the method comprises a distillation still, two sections of cavity type rectifying towers, a condenser, a dicyclohexyl ether storage tank and a vacuum pump which are sequentially connected from a feeding hole to a discharging hole through pipelines; the two sections of cavity type rectifying towers are arranged at the top of the distillation still, an outlet positioned at the top of the two sections of cavity type rectifying towers is connected with an inlet of a ring condenser, an outlet of the ring condenser is connected with a dicyclohexyl ether storage tank, and the dicyclohexyl ether storage tank is connected with a vacuum pump.
The condenser is in a shell and tube structure; the vacuum pump is of a liquid ring type.
The two sections of cavity type rectifying towers are two sections of filling towers with cavity type structures, and the filling form is Raschig rings; the height of the two sections of cavity type rectifying towers is 2700-; the first section of cavity is arranged at the upper part of the bottom filler, and the height is 350-450 mm; the second section cavity is arranged on the upper part of the middle layer filler, and the height is 300-350 mm.
The invention has the following beneficial effects:
the method adopts the two-section cavity type rectifying tower to extract the dicyclohexyl ether, the speed of ascending air is slowed down by the two cavities arranged at the stripping section of the rectifying tower, the difference of the air speed generated by the difference of the molecular weight and the boiling point of the dicyclohexyl ether and the high-chroma heavy component is fully utilized, the dicyclohexyl ether and the high-chroma heavy component are separated twice, the purity of the dicyclohexyl ether extracted from the top of the rectifying tower reaches more than 95 percent, and the cyclohexanol rectification residual liquid is recycled comprehensively, so that the method has remarkable economic, social and environmental benefits.
Drawings
FIG. 1 is a schematic block diagram of the apparatus of the present invention.
The number in the figure is 1, a distillation still 2, a two-section cavity type rectifying tower 3, a condenser 4, a dicyclohexyl ether storage tank 5 and a vacuum pump.
FIG. 2 is a chromatogram of the raffinate from the cyclohexanol distillation column.
FIG. 3 is the gas phase mass spectrum of the raffinate from the cyclohexanol distillation column.
As shown in fig. 2 and 3, the residual liquid of the cyclohexanol distillation tower is black brown liquid and comprises the following components: 90% of dicyclohexyl ether and 10% of high-chroma heavy components.
FIG. 4 is a gas chromatogram of dicyclohexyl ether extracted according to the present invention.
FIG. 5 is the gas-phase mass spectrum of dicyclohexyl ether extracted by the present invention.
As shown in FIGS. 4 and 5, the dicyclohexyl ether extracted by the method of the invention has a content of more than 95% and is a colorless transparent liquid.
Detailed Description
The invention will be further described with reference to the following examples (drawings):
as shown in figure 1, the device suitable for the method comprises a distillation still 1, a two-section cavity type rectifying tower 2, a condenser 3, a dicyclohexyl ether storage tank 4 and a vacuum pump 5 which are connected in sequence from a feed inlet to a discharge outlet through pipelines; the two-section cavity type rectifying tower 2 is arranged at the top of the distillation still 1, an outlet at the top of the rectifying and fractionating tower 2 is connected with an inlet of a cyclic condenser 3, an outlet of the cyclic condenser 3 is connected with a dicyclohexyl ether storage tank 4, and the dicyclohexyl ether storage tank 4 is connected with a vacuum pump 5.
The condenser 3 is in a shell and tube structure; the vacuum pump 5 is in a liquid ring type; the two-section cavity type rectifying tower 2 is a two-section cavity type structure packed tower, and the packing form is Raschig rings; the height of the two sections of cavity type rectifying towers 2 is 2700-; the first section of cavity is arranged at the upper part of the bottom filler, and the height is 350-450 mm; the second section cavity is arranged on the upper part of the middle layer filler, and the height is 300-350 mm.
The method for extracting dicyclohexyl ether from cyclohexanol distillation residual liquid is characterized by comprising the following steps: the method comprises the following steps:
a. adding cyclohexanol into distillation still, gradually heating to 125-3-1.5×103Pa；
b. Then controlling the temperature of the distillation kettle to be 125-135 ℃, controlling the temperature of the top of the two-section cavity type rectifying tower to be 90-105 ℃, carrying out rectification separation by adopting an intermittent total reflux method, and finishing the rectification operation when the temperature of the top of the rectifying tower exceeds 105 ℃;
c. the dicyclohexyl ether vapor extracted from the top of the two sections of cavity type rectifying towers enters a condenser for cooling to form liquid, and finally enters a dicyclohexyl ether storage tank;
d. and (4) putting the high-chroma heavy components (5-7%) left in the distillation kettle into a collecting barrel for sealing and storing.
The specific embodiment of the method of the invention is as follows:
example 1
The material amount and components of the cyclohexanol distillation residual liquid are as follows: 1800kg, of which dicyclohexyl ether 90%, high-chroma heavy components 9%, and the others 1%.
Adding cyclohexanol distillation residual liquid into a distillation still 1, gradually heating to 130 ℃, starting a liquid ring vacuum pump 5, maintaining the vacuum degree of a distillation system at 1.3 multiplied by 103Pa, controlling the tower top temperature of a two-section cavity type distillation tower at 99 ℃, performing distillation separation by adopting an intermittent total reflux method, stopping the distillation operation when the tower top temperature of the distillation tower is 105 ℃, and obtaining 1696.34 kg of dicyclohexyl ether extracted from the tower top of the two-section cavity type distillation tower, the content of the dicyclohexyl ether is 95.5 percent, and 103.66 kg of high-chroma heavy components at the bottom of the distillation still; and the dicyclohexyl ether steam extracted from the top of the two sections of hollow cavity type rectifying towers enters a condenser for cooling to form liquid, finally enters a dicyclohexyl ether storage tank, and the high-chroma heavy components left in the distillation kettle are put into a collecting barrel for sealing and storing.
Example 2
The material amount and components of the cyclohexanol distillation residual liquid are as follows: 1900kg, of which dicyclohexyl ether 90%, high-chroma heavy components 9%, others 1%.
Adding cyclohexanol distillation residual liquid into a distillation kettle, gradually heating to 130 ℃, starting a liquid ring vacuum pump, maintaining the vacuum degree of a distillation system at 1.36 multiplied by 103Pa, controlling the tower top temperature of two sections of cavity-type distillation towers at 101 ℃, performing distillation separation by adopting an intermittent total reflux method, stopping distillation operation when the tower top temperature of the distillation tower is 106 ℃, obtaining 1762.89 kg of dicyclohexyl ether extracted from the tower top of the two sections of cavity-type distillation towers, wherein the content of the dicyclohexyl ether is 97.1 percent, and the high-chroma heavy component at the bottom of the distillation kettle is 137.11 kg, finally entering a dicyclohexyl ether storage tank, and placing the residual high-chroma heavy component in the distillation kettle into a collection barrel for sealing.
Example 3
The material amount and components of the cyclohexanol distillation residual liquid are as follows: 1850kg, where dicyclohexyl ether 90%, high chroma heavy components 9%, others 1%.
Adding cyclohexanol distillation residual liquid into a distillation kettle, gradually heating to 130 ℃, starting a liquid ring vacuum pump, maintaining the vacuum degree of a distillation system at 1.42 multiplied by 103Pa, controlling the tower top temperature of a two-section cavity type distillation tower at 95 ℃, performing distillation separation by adopting an intermittent total reflux method, stopping distillation operation when the tower top temperature of the distillation tower is 107 ℃, obtaining 1721.82 kg of dicyclohexyl ether extracted from the tower top of the two-section cavity type distillation tower, the content of the dicyclohexyl ether is 96.7 percent, and 128.18kg of high-chroma heavy components at the bottom of the distillation kettle, finally entering a dicyclohexyl ether storage tank, and putting the residual high-chroma heavy components in the distillation kettle into a collection barrel for sealing.
Analysis of economic benefits
Because the residual liquid of the cyclohexanol distillation separation tower mainly contains high-chroma heavy components such as dicyclohexyl ether and 2- (2' -hydroxycyclohexyl) cyclohexanol, if a high-temperature reduced pressure distillation technology is adopted, the high-chroma heavy components in the residual liquid are evaporated too much (about 30%) along with the dicyclohexyl ether, and the purity of the dicyclohexyl ether is directly influenced; if a common rectification process is adopted, the requirement on the precision of the column is too high, the load is too large, the treatment cost and the investment are too much, the residual liquid of the rectification separation column comes from the bottom of the rectification separation column, all components are basically balanced, and the difficulty in rectification separation is very 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. This patent adopts two sections cavity formula rectifying column to draw dicyclohexyl ether, makes the rising air velocity slow down through setting up two cavitys at the rectifying column stripping section, and the difference of the produced air velocity of the molecular weight of make full use of dicyclohexyl ether and high chroma heavy ends and boiling point difference separates dicyclohexyl ether and high chroma heavy ends twice, and dicyclohexyl ether that the rectifying column top was adopted is colorless transparent liquid, and the purity reaches more than 95%.
The residual liquid amount 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 90 percent, the loss amount of the dicyclohexyl ether is 540 tons/year, the selling price of the dicyclohexyl ether (with the purity of 95 percent) is 2 ten thousand yuan/ton at present, and the total value is 1080 ten thousand yuan; the cost of environment-friendly entrusted treatment of the cyclohexanol distillation residual liquid is 200 yuan/ton, and the total cost per year is 12 ten thousand yuan; the two phases are combined to make the waste utilized and the economic benefit is 1092 ten thousand yuan per year.
Claims (2)
1. A device suitable for a method for extracting dicyclohexyl ether from cyclohexanol rectification raffinate is characterized in that: the distillation device comprises a distillation kettle (1), two sections of cavity type rectifying towers (2), a condenser (3), a dicyclohexyl ether storage tank (4) and a vacuum pump (5), wherein the distillation kettle (1), the two sections of cavity type rectifying towers, the dicyclohexyl ether storage tank and the vacuum pump are sequentially connected through a pipeline from a feeding port to a discharging port; the rectifying tower (2) is arranged at the top of the distillation kettle (1), an outlet positioned at the top of the rectifying tower (2) is connected with an inlet of the cyclic condenser (3), an outlet of the cyclic condenser (3) is connected with the dicyclohexyl ether storage tank (4), and the dicyclohexyl ether storage tank (4) is connected with the vacuum pump (5);
the two sections of cavity type rectifying towers (2) are two sections of cavity type structure packed towers, the packing form is Raschig rings, and the packing is divided into a bottom layer, a middle layer and an upper layer; the condenser (3) is of a shell and tube structure; the vacuum pump (5) is of a liquid ring type.
2. A method for using the apparatus for extracting dicyclohexyl ether from cyclohexanol distillation residue as set forth in claim 1, wherein: the method comprises the following steps:
a. adding cyclohexanol into distillation still, gradually heating to 125-3-1.5×103Pa；
b. Then controlling the temperature of the distillation kettle to be 125-135 ℃, controlling the temperature of the top of the two-section cavity type rectifying tower to be 90-105 ℃, carrying out rectification separation by adopting an intermittent total reflux method, and finishing the rectification operation when the temperature of the top of the two-section cavity type rectifying tower exceeds 105 ℃;
c. the dicyclohexyl ether steam extracted from the top of the rectifying tower enters a condenser to be cooled to form liquid, and finally enters a dicyclohexyl ether storage tank;
d. and (4) putting the high-chroma heavy components left in the distillation kettle into a collecting barrel for sealing and storing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN104817429A (en) * | 2015-04-10 | 2015-08-05 | 平顶山市神马万里化工股份有限公司 | Method for recovering cyclohexanol from bottom material fluid of cyclohexanol rectifying tower |
| CN205774212U (en) * | 2016-07-07 | 2016-12-07 | 湖南百利工程科技股份有限公司 | The device of removing impurities matter butylcyclohexyl ether in process of cyclohexanone production |
| CN107235831A (en) * | 2017-07-03 | 2017-10-10 | 郑州大学 | The method that dicyclohexyl ether is reclaimed from cyclohexanol rectifying column kettle liquid |
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- 2018-08-10 CN CN201810910229.7A patent/CN108707065B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN104817429A (en) * | 2015-04-10 | 2015-08-05 | 平顶山市神马万里化工股份有限公司 | Method for recovering cyclohexanol from bottom material fluid of cyclohexanol rectifying tower |
| CN205774212U (en) * | 2016-07-07 | 2016-12-07 | 湖南百利工程科技股份有限公司 | The device of removing impurities matter butylcyclohexyl ether in process of cyclohexanone production |
| CN107235831A (en) * | 2017-07-03 | 2017-10-10 | 郑州大学 | The method that dicyclohexyl ether is reclaimed from cyclohexanol rectifying column kettle liquid |
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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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