CN105439990A - Method for recovering ether solvents from Grignard reaction residues - Google Patents
Method for recovering ether solvents from Grignard reaction residues Download PDFInfo
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- CN105439990A CN105439990A CN201510899507.XA CN201510899507A CN105439990A CN 105439990 A CN105439990 A CN 105439990A CN 201510899507 A CN201510899507 A CN 201510899507A CN 105439990 A CN105439990 A CN 105439990A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/36—Bromides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for recovering ether solvents from Grignard reaction residues and belongs to the technical of solvent recovery. According to the method, the Grignard reaction residues are heated between -0.1 MPa and 0 MPa to the temperature of 160 DEG C or above, and condensation is performed to collect the solvents. The method is carried out on a condition without water and oxygen, and there is no need to perform pretreatment such as dissolution on the Grignard reaction residues; the pressure condition is limited between -0.1 MPa and 0 MPa, so that the ether solvents in the Grignard reaction residues can be separated easily at about 140 DEG C; when the temperature is raised to 160 DEG C or above, the Grignard reaction residues are almost completely dissolved, gas state ether solvents are condensed to obtain high-purity and low-water-content ether solvents. The effective content of the ether solvents recovered through condensation can reach 99.9% or above; the water content of the ether solvents is below 0.03% (300 ppm); the effective content of anhydrous magnesium halide can reach 98% or above; the recovery rate of the ether solvents can reach 98% or above.
Description
Technical field
The present invention relates to a kind of method reclaiming ether solvent from Grignard reaction waste residue, belong to solvent recuperation technical field.
Background technology
Grignard reaction (Grignardreaction) was in 1899 by the VictorGrignard invention doing postgraduate at that time in Lyons, France university, and therefore he obtained Nobel chemistry Prize then in 1912.100 for many years, and grignard reaction is organic chemical reactions, and particularly adopted in name reaction have one of organic chemical reactions of essential industry productive value.
Grignard reaction must using water content lower than the ether of 600ppm as solvent, in ether solvent, MAGNESIUM METAL and halohydrocarbons reaction generate alkyl magnesium halide, and are dissolved in ether solvent, and this organo-magnesium compound is referred to as Grignard reagent.Grignard reagent is one of reagent be most widely used in organic synthesis, chemical reaction can be there is in it with halides, aldehyde, ketone, ester, nitrile etc., alkyl in the reaction in Grignard reagent enters the corresponding position of the compound reacted with it, and carbochain is increased, the title complex (grignard reaction waste residue) of by-product magnesium halide and ether simultaneously.Containing a large amount of ether in the title complex of magnesium halide and ether, if do not reclaim, can strengthen production cost, the ether solvents simultaneously wasted also pollutes the environment.
Summary of the invention
The object of the present invention is to provide a kind of novel method reclaiming ether solvent from Grignard reaction waste residue.
Technical scheme of the present invention:
A kind of method reclaiming ether solvent from Grignard reaction waste residue:
Grignard reaction waste residue is heated to more than 160 DEG C under the condition of-0.1MPa ~ 0MPa, and ether solvent is collected in condensation.
Method of the present invention is carried out under anhydrous and oxygen-free condition, without the need to carrying out the pre-treatments such as dissolving to Grignard reaction waste residue; Grignard reaction waste residue in a heated condition solution joins generation magnesium halide solid and gaseous state ether solvent, and gaseous state ether solvent obtains the extremely low ether solvent of high purity, water content after condensation.Its effective content of ether solvent that gained is reclaimed in condensation of the present invention can reach more than 99.9%, and below, anhydrous magnesium halide effective content can reach more than 98% to ether solvent water content 0.03% (300ppm); The rate of recovery of ether solvent can reach more than 98%.
Grignard reaction waste residue of the present invention refers to the title complex that magnesium halide and ether are formed.Under normal circumstances, direct heating Grignard reaction waste residue, is also difficult to the fit key between magnesium halide and ether solvent is ruptured (that is, being difficult to ether solvent is separated) at about 140 DEG C, even if temperature is increased to 160 DEG C, also can only separates a part of ether.The present invention passes through, and pressure condition is defined as-0.1MPa ~ 0MPa, thus the ether solvent in Grignard reaction waste residue can easily be separated at about 140 DEG C.For tetrahydrofuran (THF) magnesium halide Grignard reaction waste residue, under normal heating condition, when Heating temperature reaches 160 DEG C, Grignard reaction waste residue is difficult to solution and joins, and is not almost recovered to tetrahydrofuran (THF); And when being heated to 140 DEG C under the condition of anhydrous and oxygen-free ,-0.1MPa, Grignard reaction waste residue and solution allot a large amount of tetrahydrofuran (THF), and when temperature is increased to more than 160 DEG C Grignard reaction waste residue almost completely solution join, the magnesium halide content of gained solid materials is 98.21%, and the ether solvent rate of recovery in Grignard reaction waste residue can reach 98%.
Aforesaid method, preferably, is heated to 160-300 DEG C.
In the present invention, described ether solvent can be ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, tertbutyl ether, isopropyl ether, methyl tert-butyl ether or glycol dimethyl ether; Magnesium halide can be magnesium chloride, magnesium bromide or magnesium iodide.
Aforesaid method, preferably, pressure condition is-0.09MPa ~-0.06MPa.Solution of the present invention join process inherently one produce the process of a large amount of gas, too low system pressure requirements equipment will have enough rates of air sucked in required, can improve equipment requirements on the contrary, increases facility investment.Therefore the suitable requirement of working pressure to operational condition and equipment is all useful, must get a rational scope.
Major advantage of the present invention:
1. the present invention is with the Grignard reaction waste residue of high organism, high magnesium halide content for raw material, joining, the operation such as condensation achieves ethers and magnesium halide in Grignard reaction waste residue is separated completely, achieving and turning waste into wealth through adding pyrolysis.
2. the present invention's system when reclaiming the ether solvent in Grignard reaction waste residue does not need to introduce water, obtains the anhydrous magnesium halide of content more than 98% simultaneously, and the processing scheme that also can produce the waste water of magnesium halide containing after comparatively reclaiming ether solvent is more advanced, clean.
3. the present invention does not need through rectifying purifying when reclaiming the ether solvent in Grignard reaction waste residue, also reclaims simultaneously and obtains highly purified anhydrous magnesium halide, have good economic benefit and social benefit.
4. the rate of recovery of its effective content of ether solvent, anhydrous magnesium halide effective content, ether solvent all increases, and ether solvent water content declines.
In the present invention, if no special instructions, described percentage ratio is mass percent.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.It is to be understood that following explanation is only to explain the present invention, its content is not limited.
Embodiment 1
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 51.6% after measured) of tetrahydrofuran (THF) in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, open the salt solution of spiral coil cooling tube on Rotary Evaporators, start rotavapor under vacuum pump regulation system pressure is-0.09MPa, start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 12h at this temperature when temperature of charge reaches 160 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 262.7g, recording its content of magnesium chloride is 98.21%; Obtain tetrahydrofuran (THF) liquid 238.0g, record its gas phase normalizing content 99.98%, use Karl_Fischer method to record its moisture for 181ppm.The tetrahydrofuran (THF) rate of recovery is 98.33%.
Embodiment 2
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 51.6% after measured) of tetrahydrofuran (THF) in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, open the salt solution of spiral coil cooling tube on Rotary Evaporators, start rotavapor under vacuum pump regulation system pressure is-0.08MPa, start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 11h at this temperature when temperature of charge reaches 180 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 263.2g, recording its content of magnesium chloride is 98.04%; Obtain tetrahydrofuran (THF) liquid 238.2g, record its gas phase normalizing content 99.97%, use Karl_Fischer method to record its moisture for 163ppm.The tetrahydrofuran (THF) rate of recovery is 98.46%.
Embodiment 3
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 51.6% after measured) of tetrahydrofuran (THF) in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.03MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 4h at this temperature when temperature of charge reaches 280 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 262.4g, recording its content of magnesium chloride is 98.33%; Obtain tetrahydrofuran (THF) liquid 228.5g, record its gas phase normalizing content 99.94%, use Karl_Fischer method to record its moisture for 144ppm.The tetrahydrofuran (THF) rate of recovery is 98.25%.
Embodiment 4
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 44.1% after measured) of 2-methyltetrahydrofuran in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.05MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 7h at this temperature when temperature of charge reaches 240 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 224.3g, recording its content of magnesium chloride is 98.26%; Obtain 2-methyltetrahydrofuran liquid 275.5g, record its gas phase normalizing content 99.96%, use Karl_Fischer method to record its moisture for 156ppm.The rate of recovery of 2-methyltetrahydrofuran is 98.54%.
Embodiment 5
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 44.1% after measured) of 2-methyltetrahydrofuran in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.06MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 9h at this temperature when temperature of charge reaches 220 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 224.9g, recording its content of magnesium chloride is 98.13%; Obtain 2-methyltetrahydrofuran liquid 274.8g, record its gas phase normalizing content 99.92%, use Karl_Fischer method to record its moisture for 167ppm.The rate of recovery of 2-methyltetrahydrofuran is 98.24%.
Embodiment 6
Take 500g and contain the dry Grignard reaction waste residue (wherein content of magnesium chloride is 44.1% after measured) of 2-methyltetrahydrofuran in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.01MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 24h at this temperature when temperature of charge reaches 160 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 223.4g, recording its content of magnesium chloride is 98.56%; Obtain 2-methyltetrahydrofuran liquid 274.4g, record its gas phase normalizing content 99.90%, use Karl_Fischer method to record its moisture for 179ppm.The rate of recovery of 2-methyltetrahydrofuran is 98.06%.
Embodiment 7
Take 500g and contain the dry Grignard reaction waste residue (wherein magnesium bromide content is 62.7% after measured) of isopropyl ether in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.07MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 11h at this temperature when temperature of charge reaches 200 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 319.7g, recording its magnesium bromide content is 98.16%; Obtain isopropyl ether liquid 183.3g, record its gas phase normalizing content 99.94%, use Karl_Fischer method to record its moisture for 192ppm.The rate of recovery of isopropyl ether is 98.23%.
Embodiment 8
Take 500g and contain the dry Grignard reaction waste residue (wherein magnesium bromide content is 62.7% after measured) of isopropyl ether in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.04MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 5h at this temperature when temperature of charge reaches 260 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 319.9g, recording its magnesium bromide content is 98.07%; Obtain isopropyl ether liquid 183.4g, record its gas phase normalizing content 99.98%, use Karl_Fischer method to record its moisture for 132ppm.The rate of recovery of isopropyl ether is 98.32%.
Embodiment 9
Take 500g and contain the dry Grignard reaction waste residue (wherein magnesium bromide content is 62.7% after measured) of isopropyl ether in the single port flask of 1000ml drying, this single port flask is mounted on dry Rotary Evaporators, the salt solution of spiral coil cooling tube on unlatching Rotary Evaporators, starts rotavapor under vacuum pump and regulation system pressure is-0.02MPa.Start Rotary Evaporators, use constant temperature oil bath heated material, keep adding pyrolysis reactant ligand 3h at this temperature when temperature of charge reaches 300 DEG C.Stop heating and being cooled to normal temperature, obtain solid materials 319.4g, recording its magnesium bromide content is 98.23%; Obtain isopropyl ether liquid 183.9g, record its gas phase normalizing content 99.95%, use Karl_Fischer method to record its moisture for 151ppm.The rate of recovery of isopropyl ether is 98.57%.
Claims (8)
1. from Grignard reaction waste residue, reclaim a method for ether solvent, it is characterized in that,
Grignard reaction waste residue is heated to more than 160 DEG C under the condition of-0.1MPa ~ 0MPa, and ether solvent is collected in condensation.
2. method according to claim 1, is characterized in that, carries out under anhydrous and oxygen-free condition.
3. method according to claim 1 and 2, is characterized in that, pressure condition is-0.09MPa ~-0.06MPa.
4. method according to claim 3, is characterized in that, is heated to 160-300 DEG C.
5. method according to claim 4, is characterized in that, described ether solvent is ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, tertbutyl ether, isopropyl ether, methyl tert-butyl ether or glycol dimethyl ether.
6. method according to claim 5, is characterized in that, described magnesium halide is magnesium chloride, magnesium bromide or magnesium iodide.
7. method according to claim 1 and 2, is characterized in that, Heating temperature improves with vacuum tightness and reduces.
8. method according to claim 7, is characterized in that,
180 DEG C are heated under-0.08MPa condition;
Or, under-0.07MPa condition, be heated to 200 DEG C;
Or, under-0.06MPa condition, be heated to 220 DEG C;
Or, under-0.05MPa condition, be heated to 240 DEG C;
Or, under-0.04MPa condition, be heated to 260 DEG C;
Or, under-0.03MPa condition, be heated to 280 DEG C;
Or, under-0.02MPa condition, be heated to 300 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510899507.XA CN105439990A (en) | 2015-12-09 | 2015-12-09 | Method for recovering ether solvents from Grignard reaction residues |
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| CN201510899507.XA CN105439990A (en) | 2015-12-09 | 2015-12-09 | Method for recovering ether solvents from Grignard reaction residues |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008409A (en) * | 2016-06-08 | 2016-10-12 | 泰山医学院 | Recovery method for tetrahydrofuran used as Grignard reaction solvent |
| CN111454234A (en) * | 2020-04-30 | 2020-07-28 | 绍兴华威化工有限公司 | Recovery process of Grignard reaction solvent |
| CN114437001A (en) * | 2022-01-19 | 2022-05-06 | 上海天汉环境资源有限公司 | Method for recovering tetrahydrofuran in wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008409A (en) * | 2016-06-08 | 2016-10-12 | 泰山医学院 | Recovery method for tetrahydrofuran used as Grignard reaction solvent |
| CN111454234A (en) * | 2020-04-30 | 2020-07-28 | 绍兴华威化工有限公司 | Recovery process of Grignard reaction solvent |
| CN114437001A (en) * | 2022-01-19 | 2022-05-06 | 上海天汉环境资源有限公司 | Method for recovering tetrahydrofuran in wastewater |
| CN114437001B (en) * | 2022-01-19 | 2023-12-26 | 上海天汉环境资源有限公司 | Recovery method of tetrahydrofuran in wastewater |
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