CN110002481B - Method for recovering magnesium chloride and co-producing tetrahydrofuran from Grignard reaction waste residues - Google Patents
Method for recovering magnesium chloride and co-producing tetrahydrofuran from Grignard reaction waste residues Download PDFInfo
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- CN110002481B CN110002481B CN201910339498.7A CN201910339498A CN110002481B CN 110002481 B CN110002481 B CN 110002481B CN 201910339498 A CN201910339498 A CN 201910339498A CN 110002481 B CN110002481 B CN 110002481B
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- magnesium chloride
- tetrahydrofuran
- chloride hexahydrate
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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
- C01F5/30—Chlorides
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for recovering magnesium chloride and coproducing tetrahydrofuran from Grignard reaction waste residueThe method comprises the following specific steps: step 1, dissolving: in general N2Under the protection condition, the complex waste residue is gradually added into the dissolved water, a small amount of hydrogen peroxide is added into the dissolved water, the trimethyl phosphorus can be oxidized into stable trimethyl phosphine oxide, and a small amount of unreacted trimethyl phosphorus can enter a tail gas spraying absorption device along with nitrogen to be oxidized and absorbed; step 2, rectifying and recovering tetrahydrofuran: rectifying the dissolved material to recover tetrahydrofuran, and then evaporating a small amount of water to reach a substrate crystallization state; step 3, slicing magnesium chloride hexahydrate: the temperature of the substrate is raised to a certain temperature and then reaches the solidification and crystallization conditions of magnesium chloride hexahydrate, and the magnesium chloride hexahydrate can be directly cooled and sliced. By adopting the technical scheme of the invention, the magnesium chloride in the waste residue of the Grignard reaction can be recovered, and simultaneously the tetrahydrofuran is co-produced, thereby increasing the recovery benefit.
Description
Technical Field
The invention relates to a method for recovering magnesium chloride and coproducing tetrahydrofuran from Grignard reaction waste residues, belonging to the field of solid waste resource utilization.
Background
In the field of fine chemical engineering, the grignard reaction is a reaction commonly used for producing chemical products, but during the grignard reaction, magnesium chloride solid pollutants are generated, the pollutants contain tetrahydrofuran and other substances, and if the treatment is not proper, serious pollution is generated to the environment.
Patent CN101638400B "a method for recovering tetrahydrofuran from grignard reaction waste residue magnesium chloride" describes a method for recovering tetrahydrofuran from grignard reagent, which comprises distilling and then rectifying to purify tetrahydrofuran product with purity up to 99.8% from waste residue. Although the method is good, the problem of solid waste pollution of magnesium chloride is not fundamentally solved.
In patent CN106745112A, "a preparation method for recovering magnesium chloride hexahydrate from grignard waste residue hydrolysate", a method for recovering magnesium chloride hexahydrate from grignard waste residue hydrolysate is introduced, which is complicated and inconvenient to operate.
At present, no more perfect treatment method for the magnesium chloride solid waste generated by the Grignard reaction exists in China.
Disclosure of Invention
The invention provides a method for recovering magnesium chloride and coproducing tetrahydrofuran from Grignard reaction waste residues aiming at the blank that no complete treatment mode exists for magnesium chloride solid waste generated by Grignard reaction in China. Not only solves the problem of solid waste pollution, but also obtains products with higher value, does not generate secondary pollution, creates higher economic benefit and meets the requirement of sustainable development.
The specific technical scheme of the invention is as follows:
a method for recovering magnesium chloride and coproducing tetrahydrofuran from Grignard reaction waste residues comprises the following steps:
(1) dissolving: in general N2Under the protection condition, adding the complex waste residue into the dissolving water gradually to dissolve;
(2) and (3) distilling and rectifying to recover tetrahydrofuran: heating and distilling the dissolved materials to evaporate a tetrahydrofuran aqueous solution; then rectifying and concentrating the tetrahydrofuran aqueous solution;
(3) magnesium chloride hexahydrate slices: and when the temperature of the substrate rises to 140-160 ℃ during distillation, the discharging condition of magnesium chloride hexahydrate is achieved, the material is discharged to a slicing machine, and the material can be directly cooled and sliced to obtain magnesium chloride hexahydrate (halogen slice).
Further, in the step (1), the dissolving process is carried out under a nitrogen atmosphere, so that the trimethyl phosphorus in the dissolving process is prevented from contacting with air to react.
Further, in the step (1), industrial-grade hydrogen peroxide is added into the dissolved water, the adding amount is controlled within the range of 0.5-5.0 wt.%, trimethyl phosphorus can be oxidized into stable trimethyl phosphine oxide, and a small amount of unreacted trimethyl phosphorus can enter a tail gas spraying and absorbing device along with nitrogen to be oxidized and absorbed;
further, in the step (1), a small amount of hydrogen peroxide is added into the dissolved water, so that organic matters in the dissolved water can be removed, and the purity of magnesium chloride is improved;
further, in the step (1), the adding speed of the waste residues is controlled to be 10-100 kg/min in the dissolving process, circulating water is introduced to the outside of the dissolving kettle for cooling, and the dissolving temperature is controlled to be below 40 ℃;
further, in the step (2), 93-94% of tetrahydrofuran and a small amount of middle distillate are obtained respectively, and the middle distillate can be applied to next batch of dissolved water;
further, in the step (3), the magnesium chloride hexahydrate product with purity of more than 98 percent and white appearance can be obtained after cooling and slicing.
Advantageous effects
In the dissolving process, hydrogen peroxide is added into the dissolved water, so that trimethyl phosphorus and other organic impurities doped in magnesium chloride are removed, and the dissolving process is carried out in a nitrogen atmosphere to prevent the trimethyl phosphorus from reacting with oxygen; controlling the adding rate of the waste residue in the dissolving process, and controlling the dissolving temperature not to exceed 40 ℃. By the method, the tetrahydrofuran with higher purity can be obtained while the magnesium chloride is recovered, so that the solid waste is treated, and the available magnesium chloride and tetrahydrofuran are recovered, secondary economic benefit is generated, and the method meets the requirement of green sustainable development.
Drawings
FIG. 1 is a process flow diagram of a method for recovering magnesium chloride and co-producing tetrahydrofuran from Grignard reaction waste residue.
FIG. 2 is a process flow diagram of example 1.
Detailed Description
The present invention will now be described in detail with reference to specific embodiments thereof, which are given by way of illustration only and are not to be construed as limiting the present invention. In the following examples, the concentrations are mass concentrations unless otherwise specified.
In the following examples, magnesium chloride hexahydrate was measured by ion chromatography, tetrahydrofuran content was measured by HPLC, and water content was measured by Karl Fischer method.
In the following examples, the Grignard reaction residue used was from a byproduct of chemical synthesis in a chemical plant, wherein MgCl was used240-60% of the total content, 40-50% of tetrahydrofuran, less than 1% of trimethylphosphorus and less than 10% of water.
Example 1: the experiment was carried out as follows:
1) dissolving: in general N2Under the protection condition, adding the complex waste residue into dissolved water at the adding rate of 10-100 kg/min, adding a small amount of hydrogen peroxide into the dissolved water, oxidizing trimethyl phosphorus into stable trimethyl phosphine oxide, and allowing a small amount of unreacted trimethyl phosphorus to enter a tail gas spraying absorption device along with nitrogen for oxidation absorption; controlling the adding rate of the waste residues in the dissolving process, and simultaneously introducing circulating water to the outside of the dissolving kettle to cool, wherein the dissolving temperature is controlled below 40 ℃;
2) rectifying and recovering tetrahydrofuran: rectifying the dissolved material to recover tetrahydrofuran, wherein the material starts to boil at a liquid phase temperature of 68-75 ℃ during rectification, and the fraction is collected at a gas phase temperature of 62-63 ℃, wherein the fraction is 94-96% of tetrahydrofuran; when the temperature of the liquid phase rises to 120-122 ℃, the temperature of the gas phase generally begins to rise rapidly, at the moment, fraction collection is switched, a small amount of water is continuously rectified to reach a substrate crystallization state, when the temperature of the liquid phase reaches 152 ℃, the material is magnesium chloride hexahydrate, rectification is finished, and heat preservation is carried out;
3) magnesium chloride hexahydrate slices: and (3) after the temperature of the substrate is raised to 152 ℃, the solidification and crystallization conditions of the magnesium chloride hexahydrate are achieved, the materials are discharged to a slicing machine, and the materials can be directly cooled and sliced to obtain the magnesium chloride hexahydrate (halogen slice).
By adopting the steps, the purity of the obtained magnesium chloride hexahydrate is as follows: 98.36 percent; the purity of tetrahydrofuran can reach: 96.32%, tetrahydrofuran water content: 3.39 percent.
Example 2
Three batches of experiments were carried out using the procedure described above, with the following experimental results:
the above examples are only a part of the specific embodiments of the present invention, and besides the above examples, the process disclosed by the present invention is also applicable to the treatment of other waste sulfuric acid with low organic content, and the effect is significant.
Claims (2)
1. A method for recovering magnesium chloride and coproducing tetrahydrofuran from Grignard reaction waste residues is characterized by comprising the following steps:
(1) dissolving: in general N2Under the protection condition, adding the complex waste residue into dissolved water at the adding rate of 10-100 kg/min, controlling the dissolving temperature below 40 ℃ in the dissolving process, adding 0.5-5 wt.% of industrial grade hydrogen peroxide into the dissolved water, and allowing a small amount of unreacted trimethyl phosphorus to enter a tail gas spraying absorption device along with nitrogen to be oxidized and absorbed;
(2) rectifying and recovering tetrahydrofuran: rectifying the dissolved materials to recover tetrahydrofuran, and then evaporating water to reach a substrate crystallization state;
(3) magnesium chloride hexahydrate slices: and raising the temperature of the substrate to 140-160 ℃, and directly cooling and slicing to obtain the magnesium chloride hexahydrate under the condition of solidification and crystallization of the magnesium chloride hexahydrate.
2. The method of claim 1, wherein: the concentration of tetrahydrofuran obtained after rectification can reach 93-94%.
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| CN201910339498.7A CN110002481B (en) | 2019-04-25 | 2019-04-25 | Method for recovering magnesium chloride and co-producing tetrahydrofuran from Grignard reaction waste residues |
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| CN201910339498.7A CN110002481B (en) | 2019-04-25 | 2019-04-25 | Method for recovering magnesium chloride and co-producing tetrahydrofuran from Grignard reaction waste residues |
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| CN110002481B true CN110002481B (en) | 2021-05-18 |
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| CN111454234A (en) * | 2020-04-30 | 2020-07-28 | 绍兴华威化工有限公司 | Recovery process of Grignard reaction solvent |
| CN111689506B (en) * | 2020-07-21 | 2022-09-16 | 河南华龙香料有限公司 | Method for recovering magnesium chloride and tetrahydrofuran from Grignard reaction wastewater |
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