CN113788740B - Method for recovering methanol and ethanol from fusel oil containing water - Google Patents
Method for recovering methanol and ethanol from fusel oil containing water Download PDFInfo
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- CN113788740B CN113788740B CN202111093299.6A CN202111093299A CN113788740B CN 113788740 B CN113788740 B CN 113788740B CN 202111093299 A CN202111093299 A CN 202111093299A CN 113788740 B CN113788740 B CN 113788740B
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- tower
- ethanol
- methanol
- recovery tower
- dehydration
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 222
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000001760 fusel oil Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 89
- 230000018044 dehydration Effects 0.000 claims abstract description 43
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000012797 qualification Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- VLOVSFJPGNJHMU-UHFFFAOYSA-N ethanol;methanol;hydrate Chemical compound O.OC.CCO VLOVSFJPGNJHMU-UHFFFAOYSA-N 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02P20/10—Process efficiency
Abstract
The invention discloses a method for recovering methanol and ethanol from fusel oil. The core step is that the azeotropic phenomenon of ethanol and water can be destroyed by using enough methanol found in the research of the rectification separation flow of the three systems of methanol-ethanol-water. Raw material water-containing fusel oil flows into a dehydration tower T1, and tower top steam is partially condensed by a dehydration tower condenser C1 to separate fusel oil; the bottom of the dehydration tower T1 flows into a dehydration tower reboiler H1 to flow out as wastewater; the material flow of the condenser C1 at the top of the dehydration tower enters a methanol recovery tower T2 for separation; the bottom flow of the methanol recovery tower T2 contains ethanol and higher alcohols, and flows into an ethanol recovery tower T3 through a methanol recovery tower reboiler H2; the vapor at the top of the ethanol recovery tower T3 is condensed by the ethanol recovery tower condenser C3 and then partially reflows, and part of the vapor is taken as ethanol product to flow out of the boundary region. According to the invention, refined methanol and absolute ethanol are separated successively, the steam consumption of unit product is 0.2-2, and the obvious energy-saving effect of the fusel oil recovery process flow can be realized.
Description
Technical Field
The invention belongs to the field of chemical separation processes, and particularly relates to a method for recovering methanol and ethanol from aqueous fusel oil.
Background
Fusel oil generated in the methanol rectifying device belongs to dangerous chemicals and cannot be directly delivered from factories, so that the fusel oil is required to be recycled, qualified water discharge is ensured, and environmental pollution is reduced. The process includes the steps of preparing alcohol, isopropanol and waste water. In 2001, chemical engineering report shows that methanol, ethanol and water can form ternary system of methanol-ethanol-water through chemical treatment, so that the recovery problem of fusel oil can be the separation problem of ternary system. For ethanol-water systems, conventional rectification only yields 95 mass% ethanol. Common methods for preparing high-concentration ethanol include extractive distillation with ethylene glycol as extractant and azeotropic distillation with benzene as entrainer. All of these methods require the addition of a third component to the system. And when an extractant or an entrainer is added for separating the methanol-ethanol-water ternary system, the ternary system is changed into quaternary system rectification, the process is complex, and the investment is large. In fact, because methanol has no azeotropic phenomenon with water and ethanol, the existence of methanol can destroy the azeotropic phenomenon between ethanol and water, so that the preparation of high-concentration ethanol by adopting common rectification is possible. Therefore, if the methanol contained in the fusel oil system can be used as an entrainer and is economically feasible, the separation process can be greatly simplified, and the problem of recycling fusel oil is solved.
Disclosure of Invention
In order to solve the problem of the existing fusel oil recovery, the invention provides a method for recovering methanol and ethanol from the fusel oil containing water.
The technical scheme of the invention is as follows: a method for recovering methanol and ethanol from fusel oil, which relates to the following devices:
the device comprises three towers, namely a dehydration tower T1, a methanol recovery tower T2 and an ethanol recovery tower T3, a dehydration tower reboiler H1, a dehydration tower condenser C1, a methanol recovery tower reboiler H2, a methanol recovery tower condenser C2, an ethanol recovery tower reboiler H3 and an ethanol recovery tower condenser C3. The top of the dehydration tower T1 is connected with the middle lower part of the methanol recovery tower T2 through a pipeline, and the bottom of the methanol recovery tower T2 is connected with the middle lower part of the ethanol recovery tower T3 through a pipeline, and specifically comprises the following steps:
1) Raw material water-containing fusel oil flows into a dehydration tower T1, and tower top steam is partially condensed by a dehydration tower condenser C1 to separate fusel oil; the bottom of the dehydration tower T1 flows into a dehydration tower reboiler H1 to flow out as wastewater;
2) The material flow of the condenser C1 at the top of the dehydration tower enters a methanol recovery tower T2 for separation;
3) The steam at the top of the methanol recovery tower T2 is partially refluxed after being condensed by a condenser C2 of the methanol recovery tower, and a part of the steam is used as refined methanol product to flow out of the boundary zone; the bottom flow of the methanol recovery tower T2 contains ethanol and higher alcohols, and flows into an ethanol recovery tower T3 through a methanol recovery tower reboiler H2;
4) The vapor at the top of the ethanol recovery tower T3 is condensed by an ethanol recovery tower condenser C3 and then partially reflows, and part of the vapor is taken as an ethanol product to flow out of the boundary region; the bottom flow of the ethanol recovery tower T3 flows into an ethanol recovery tower reboiler H3, and high-carbon alcohol byproducts mainly comprising isopropanol are obtained at the bottom of the ethanol recovery tower.
The device of the invention utilizes the method that the azeotropic point of ethanol and water can be destroyed by methanol to recycle the fusel oil, and optimizes the separation effect of the tower by adjusting the tower plate number and the reflux ratio of the dehydration tower T1, the methanol recovery tower T2 and the ethanol recovery tower T3, thereby separating the methanol and the ethanol with certain precision.
The invention is characterized in that:
1) The feeding of the fusel oil containing water is not provided with a flowmeter or a regulating valve, and the waste water at the bottom of the dehydration tower T1 can be qualified only by controlling the steam quantity at the bottom of the tower and ensuring the bottom temperature to be more than 100 ℃. The temperature and pressure of the tower top are not greatly changed, the reflux ratio is in the range of 2-10, the temperature of the tower top is well controlled by the duty reflux, and the quality of methanol is ensured.
2) The azeotropic phenomenon between ethanol and water can be destroyed by utilizing the existence of a certain amount of methanol, the azeotropic point of ethanol and water disappears, and the azeotropic phenomenon does not occur between ethanol and isopropanol, so that the system can be separated by common rectification, high-concentration methanol and ethanol are obtained, and the methanol and the ethanol are directly separated out of a boundary area and sold as a product.
The operating pressure range of the dehydration tower T1 is 30-160kPa, and the reflux ratio is 2-10;
the operating pressure range of the methanol recovery tower T2 is 30-150kPa, and the reflux ratio is 2-10;
the operating pressure range of the ethanol recovery tower T3 is 20-150kPa, and the reflux ratio is 2-10.
Advantageous effects
1. By implementing the method, not only the refined methanol is recycled, but also the problem that fusel oil cannot be directly delivered is solved.
2. Most of methanol in the fusel oil system generated by methanol rectification can be used as entrainer to destroy the azeotropic phenomenon of ethanol and water, so that the ethanol is dehydrated, and the investment cost is reduced from the economic aspect.
3. Is suitable for new devices and technical transformation.
Drawings
FIG. 1 is a schematic diagram of the separation of methanol and ethanol from an aqueous fusel oil;
the system comprises a dehydration tower-T1, a methanol recovery tower-T2, an ethanol recovery tower-T3, a dehydration tower reboiler-H1, a dehydration tower condenser-C1, a methanol recovery tower reboiler-H2, a methanol recovery tower condenser-C2, an ethanol recovery tower reboiler-H3 and an ethanol recovery tower condenser-C3.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
example 1
As shown in fig. 1, a method for separating methanol and ethanol from fusel oil with water is as follows: the dehydration tower T1 is connected with the middle lower part of the methanol recovery tower T2 through the tower top, and the tower bottom of the methanol recovery tower T2 is connected with the middle lower part of the ethanol recovery tower T3 through a pipeline.
The process flow adopted by the invention comprises the following steps:
1) Raw material water-containing fusel oil flows into a dehydration tower T1, and tower top steam is partially condensed by a dehydration tower condenser C1 to separate fusel oil; the bottom material flow of the dehydration tower T1 flows into a dehydration tower reboiler H1 and flows out as wastewater;
2) The material flow of the condenser C1 at the top of the dehydration tower enters a methanol recovery tower T2 for separation;
3) The steam at the top of the methanol recovery tower T2 is partially refluxed after being condensed by a condenser C2 of the methanol recovery tower, and a part of the steam is used as refined methanol product to flow out of the boundary zone; the bottom flow of the methanol recovery tower T2 contains ethanol and higher alcohols, and flows into an ethanol recovery tower T3 through a methanol recovery tower reboiler H2;
4) The vapor at the top of the ethanol recovery tower T3 is condensed by an ethanol recovery tower condenser C3 and then partially reflows, and part of the vapor is taken as an ethanol product to flow out of the boundary region; the bottom flow of the ethanol recovery tower T3 flows into an ethanol recovery tower reboiler H3, and high-carbon alcohol byproducts mainly comprising isopropanol are obtained at the bottom of the ethanol recovery tower.
The operating pressure range of the dehydration tower T1 is 30Pa, and the reflux ratio is 2; the operating pressure range of the methanol recovery tower T2 is 30kPa, and the reflux ratio is 2; the ethanol recovery column T3 was operated at a pressure in the range of 25kPa and a reflux ratio of 2.5.
Example 2
The process flow is the same as above. The operating pressure range of the dehydration tower T1 is 50kPa, and the reflux ratio is 4; the operating pressure range of the methanol recovery tower T2 is 40kPa, and the reflux ratio is 5; the ethanol recovery column T3 was operated at a pressure ranging from 30kPa and a reflux ratio of 2.
Example 3
The process flow is the same as above. The operating pressure range of the dehydration tower T1 is 60kPa, and the reflux ratio is 5; the operating pressure range of the methanol recovery tower T2 is 70kPa, and the reflux ratio is 5.2; the operating pressure range of the ethanol recovery column T3 was 80kPa and the reflux ratio was 6.5.
Example 4
The process flow is the same as above. The operating pressure range of the dehydration tower T1 is 110kPa, and the reflux ratio is 8.5; the operating pressure range of the methanol recovery tower T2 is 100kPa, and the reflux ratio is 9; the ethanol recovery column T3 was operated at a pressure in the range of 90kPa and a reflux ratio in the range of 7.
Example 5
The process flow is the same as above. The operating pressure range of the dehydration tower T1 is 150kPa, and the reflux ratio is 10; the operating pressure range of the methanol recovery tower T2 is 130kPa, and the reflux ratio is 9; the ethanol recovery column T3 was operated at a pressure in the range of 140kPa and a reflux ratio of 10.
Example 6
The process flow is the same as above. The operating pressure range of the dehydration tower T1 is 160kPa, and the reflux ratio is 9.5; the operating pressure range of the methanol recovery tower T2 is 150kPa, and the reflux ratio is 10; the ethanol recovery column T3 was operated at a pressure in the range of 150kPa and a reflux ratio of 9.
Compared with the existing industrial process, the steam consumption of the unit product of the process scheme is 0.2-2.0, and the index is a new choice for recycling fusel oil relatively.
Claims (2)
1. A process for recovering methanol and ethanol from an aqueous fusel oil comprising the steps of:
a dehydration column (T1), a dehydration column reboiler (H1), a dehydration column condenser (C1);
a methanol recovery column (T2), a methanol recovery column reboiler (H2), and a methanol recovery column condenser (C2);
an ethanol recovery tower (T3), an ethanol recovery tower reboiler (H3), an ethanol recovery tower condenser (C3);
wherein, the dehydration tower condenser (C1) is connected with the methanol recovery tower (T2), and the methanol recovery tower reboiler (H2) is connected with the ethanol recovery tower (T3);
the method comprises the following steps:
1) Raw material water-containing fusel oil flows into a dehydration tower (T1), and tower top steam is partially condensed by a dehydration tower condenser (C1) to separate fusel oil; the bottom of the dehydration tower (T1) flows into a dehydration tower reboiler (H1) to flow out as wastewater;
2) Feeding the material flow of the condenser (C1) at the top of the dehydration tower into a methanol recovery tower (T2) for separation;
3) The vapor at the top of the methanol recovery tower (T2) is condensed by a condenser (C2) of the methanol recovery tower and then partially reflows, and part of the vapor is taken as refined methanol product to flow out of the boundary area; the bottom flow of the methanol recovery tower (T2) contains ethanol and higher alcohols, and flows into an ethanol recovery tower (T3) through a reboiler (H2) of the methanol recovery tower;
4) The vapor at the top of the ethanol recovery tower (T3) is condensed by an ethanol recovery tower condenser (C3) and then partially reflows, and part of the vapor is taken as ethanol product to flow out of the boundary region; the bottom flow of the ethanol recovery tower (T3) flows into an ethanol recovery tower reboiler (H3), and high-carbon alcohol byproducts mainly comprising isopropanol are obtained at the bottom of the ethanol recovery tower;
the methanol is firstly extracted from the tower top of the methanol recovery tower (T2) and the precision reaches the American federal standard AA level of industrial methanol, the tower bottom product contains 80-95% of ethanol and 5-20% of higher alcohols, the absolute ethanol is extracted from the tower top through the ethanol recovery tower (T3), the precision can reach more than 99.5%, and the higher alcohols mainly including isopropanol are separated from the tower bottom;
the bottom temperature of the dehydration tower (T1) is more than or equal to 100 ℃, so that the qualification of the wastewater at the bottom of the tower is ensured;
the operating pressure range of the dehydration tower (T1) is 30-160kPa, and the reflux ratio is 2-10;
the operating pressure range of the methanol recovery tower (T2) is 30-150kPa, and the reflux ratio is 2-10.
2. A method for recovering methanol and ethanol from aqueous fusel oil according to claim 1, characterized in that the operating pressure of the ethanol recovery column (T3) ranges from 20 to 150kPa and the reflux ratio ranges from 2 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111093299.6A CN113788740B (en) | 2021-09-17 | 2021-09-17 | Method for recovering methanol and ethanol from fusel oil containing water |
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| CN202111093299.6A CN113788740B (en) | 2021-09-17 | 2021-09-17 | Method for recovering methanol and ethanol from fusel oil containing water |
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| CN113788740A CN113788740A (en) | 2021-12-14 |
| CN113788740B true CN113788740B (en) | 2024-03-29 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628930A (en) * | 2017-10-19 | 2018-01-26 | 青岛科技大学 | A kind of heat pump separation of extractive distillation methanol, the energy saving technique of isopropyl alcohol and water |
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- 2021-09-17 CN CN202111093299.6A patent/CN113788740B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628930A (en) * | 2017-10-19 | 2018-01-26 | 青岛科技大学 | A kind of heat pump separation of extractive distillation methanol, the energy saving technique of isopropyl alcohol and water |
Non-Patent Citations (1)
| Title |
|---|
| 甲醇乙醇水三元系精馏分离流程研究;白润生;化学工程;第29卷(第3期);8-10 * |
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