CN111252786B - Method for removing organic matters of allyl ether byproduct salt - Google Patents
Method for removing organic matters of allyl ether byproduct salt Download PDFInfo
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- CN111252786B CN111252786B CN202010090206.3A CN202010090206A CN111252786B CN 111252786 B CN111252786 B CN 111252786B CN 202010090206 A CN202010090206 A CN 202010090206A CN 111252786 B CN111252786 B CN 111252786B
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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Abstract
The invention provides a method for removing organic matters of allyl ether byproduct salt, and particularly relates to the technical field of removing organic matters of allyl ether compound byproduct salt.
Description
[ technical field ]
The invention relates to the technical field of allyl ether compounds, in particular to the technical field of organic matters for removing byproduct salts of allyl ether compounds.
[ background art ]
The allyl ether compound is generally obtained by Williamson etherification reaction of polyhydric alcohol and allyl chloride in the presence of alkali metal oxide, has the performances of isomerization, oxygen bonding, polymerization and the like due to a plurality of allyl groups and 1 hydroxyl group, is often used as a polymer monomer or a cross-linking agent for preparing an acrylic polymer type thickening agent and a super absorbent resin, is widely used for graft synthesis of unsaturated polyester, polyurethane resin, epoxy resin and UV curing resin, is increasingly applied to the field of chemical green low-carbon coatings year by year, and is an important organic compound.
The Williamson etherification reaction has the advantages of low price and easy obtainment of raw materials and relatively mild reaction, and is subjected to a great deal of targeted research by industrial workers.
Zhejiang industrial university patent CN101343213B, Zhuhai Feiyang chemical company limited patent CN101200413B, China petrochemical Qilu petrochemical company patent CN1052970C, Nanjing Weier chemical company limited patent CN100410304C propose a preparation method of pentaerythritol triallyl ether, and do not mention a treatment process of a byproduct salt.
The preparation method of trimethylolpropane diallyl ether is proposed by a patent CN110156573A of Nantong Baichuan new material Co., Ltd, a patent CN102659532B of Guangdong petrochemical industry institute and a patent CN102040486B of Shandong province chemical research institute, and a treatment process of a byproduct salt is not mentioned.
After the synthesis reaction of the allyl ether is finished, a certain amount of water is added, the mixture is cooled, stood and layered, the organic phase at the upper layer is subjected to vacuum distillation to obtain an allyl ether product, and the water at the lower layer contains a large amount of sodium chloride, excessive sodium hydroxide, unreacted polyhydric alcohol and a phase transfer catalyst, and belongs to wastewater which is difficult to treat. Therefore, the production and synthesis of allyl ether need to perfect an organic matter removal method of byproduct salt, recover raw materials, recycle and make harmless, and the method accords with the development direction of the chemical industry towards green environmental protection.
[ summary of the invention ]
In order to overcome the defects of the prior art, the invention provides a method for removing organic matters of byproduct salt of allyl ether compounds, which reduces the content of the organic matters in the byproduct salt.
A method for removing organic matters of allyl ether byproduct salt is characterized by comprising the following steps:
s1: the brine for synthesizing the allyl ether is subjected to centrifugal filtration to obtain wet solid salt, the wet solid salt is preliminarily washed by synthesis reaction generated water, and washing liquid serving as alkaline water or layered water is returned to the reaction kettle for recycling;
and S2, preliminarily washing the solid salt washed in the step S1 by using a certain amount of raw material allyl chloride, and returning the washing liquid serving as the raw material allyl chloride to the stirring kettle to participate in synthesis.
S3: drying the solid salt washed by the S2, and returning the liquid obtained after condensing the drying gas as a raw material of allyl chloride to the stirring kettle for synthesis;
s4: the dried solid salt can be further calcined to completely remove organic matters, and neutralized and washed to obtain qualified industrial salt.
Further, the allyl ether includes trimethylol diallyl ether, pentaerythritol triallyl ether, and the like.
Further, in the step S1, the content of organic matters in the solid salt is 1.5-3%, the mass ratio of the solid salt to the water generated by the synthesis reaction is 100: 30-60%, and the content of the solid salt organic matter after washing is 0.9-3%.
Further, the mass ratio of the solid salt to the allyl chloride in the step S2 is 100: 200-500, and the content of the solid salt organic matter after washing is 0.1-1%.
Further, the drying method in the step S3 is ultrasonic drying or hot nitrogen drying.
Further, the content of the solid salt organic matter in the step S3 is 0-0.3%.
Further, the industrial salt in the S4 step meets the first grade standard of the GBT5462-2016 industrial salt standard.
The beneficial effects of the invention are as follows:
according to the technical scheme provided by the invention, the raw material allyl chloride and the synthesis water are used for washing the byproduct salt solid, so that the content of organic matters in the byproduct salt is reduced, the incompletely reacted materials are recovered, and then the organic matters are completely removed by calcination after drying, and finally the industrial salt byproduct is prepared.
[ description of the drawings ]
FIG. 1 is a schematic flow chart of an embodiment of the present invention.
[ detailed description of the invention ]
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
A method for producing organic matters by removing allyl ether byproduct salt comprises the following steps:
s1: the brine for synthesizing the allyl ether is centrifugally filtered to obtain wet solid salt, and the wet solid salt is preliminarily washed by the water generated by the synthesis reaction. The washing liquid is used as alkaline water or cooling stratified water to return to the reaction kettle for recycling.
S2, the solid salt washed in S1 is primarily washed with a certain amount of raw allyl chloride. The washing liquid is used as raw material allyl chloride and returns to the stirring kettle to participate in synthesis.
S3: and (3) drying the washed solid salt of S2, and returning the liquid obtained by condensing the drying gas as a raw material of allyl chloride to the stirring kettle to participate in synthesis. The dried solid salt can further remove organic matters through neutralization and calcination, and is dissolved and crystallized to obtain qualified industrial salt.
The allyl ether provided by the invention comprises compounds such as trihydroxymethyl diallyl ether, pentaerythritol triallyl ether and the like. After the synthesis reaction of the allyl ether is finished, a certain amount of water is added, the mixture is cooled, kept stand and layered, the organic phase at the upper layer is subjected to vacuum distillation to obtain an allyl ether product, the water at the lower layer contains a large amount of sodium chloride, excessive sodium hydroxide, unreacted polyhydric alcohol and a phase transfer catalyst, and the content of the solid salt organic matter is measured to be 1.5-3%, and the content of the sodium hydroxide is measured to be 8-13%.
In the step S1, water is used for recovering water-soluble compounds such as sodium hydroxide, pentaerythritol, phase transfer catalyst and the like, and the recovery mechanism is as follows:
solubility of sodium chloride and sodium hydroxide in water
According to the solubility curve, the sodium hydroxide has higher solubility in water compared with sodium chloride, and the higher the water temperature is, the higher the solubility is, and the solubility can be completely dissolved only by the same amount of water at the normal temperature of 20-30 ℃.
In order to recover the sodium hydroxide as much as possible, water in excess of the sodium hydroxide is needed for washing, and the mass ratio of the solid salt to the water is preferably 100: and 40-50, measuring that the content of the washed solid salt organic matter is 0.5-1.1%, the content of the sodium hydroxide is lower than 5%, and returning the obtained washing liquid L1 to the reaction kettle to be used as cooling layering water or alkali water for synthesis.
And step S2, allyl chloride is used for recovering pentaerythritol triallyl ether, trimethylol diallyl ether and intermediates, and the recovery mechanism is as follows:
solubility curve of pentaerythritol triallyl ether and trimethylolpropane diallyl ether in allyl chloride
| Temperature of | 0 | 10 | 20 | 30 | 40 |
| Pentaerythritol triallyl ether solubility (g) | Layering | 3.8 | 4.6 | 7.4 | 11.1 |
| Solubility (g) of trimethylolpropane diallyl ether | Layering | 5.4 | 6.7 | 8.9 | 13.5 |
The solubility curve shows that allyl chloride has lower solubility to pentaerythritol triallyl ether and trimethylol diallyl ether, and the solubility is not greatly increased with higher temperature.
In order to recover allyl ether as much as possible, the raw material allyl chloride is used in a large excess, and the mass ratio of the solid salt to the allyl chloride is preferably 100: 200-500%, wherein the content of the washed solid salt organic matter is 0.1-0.3%, and the obtained washing liquid L2 is used as an allyl chloride raw material and is returned to the reaction kettle to participate in synthesis.
Allyl chloride is colorless flammable liquid and has corrosive and pungent smells, so a closed drying process for isolating oxygen needs to be selected, and ultrasonic drying or hot nitrogen drying is preferred after washing. The ultrasonic drying temperature is 90-110 ℃, the drying time is 20min, the hot nitrogen temperature is 80-95 ℃, the drying time is 45min, the drying can be completed, the organic content of the solid salt after the drying is 0-0.1%, and the liquid obtained by condensation is used as the allyl chloride raw material and returns to the reaction kettle to participate in the synthesis.
And (3) further calcining the dried solid salt in a muffle furnace at 300-400 ℃, thoroughly removing organic matters, and then neutralizing and washing to obtain the qualified industrial salt.
As shown in fig. 1, a schematic flow chart of an embodiment of the present invention is shown.
Example 1
Taking 100g of byproduct salt of pentaerythritol triallyl ether in a production device, placing the byproduct salt in a three-necked bottle with stirring, adding 30g of water at the lower layer of a water separation tank, heating to 30 ℃, stirring for 30min, and filtering to obtain a filtrate L1:47.22g, a solid S1: 82.78 g;
100g of allyl chloride was further added, and the resulting solid S1 was washed with stirring at 30 ℃ for about 30min, filtered under a closed condition, and repeated 5 times. Filtrate L2:497.15g, solid S2: 85.63 g;
starting the refrigerating fluid to-15 ℃, controlling the nitrogen flow rate to be 50ml/min, heating the three-necked bottle to 90 ℃, and collecting a condensate L3: 5.02g, cooled to give solid S4: 80.61 g;
and putting the solid S4 into a crucible, calcining for 3 hours at 300 ℃ in a muffle furnace to obtain 80.41g of solid, neutralizing and washing with 43.6ml of 10% diluted hydrochloric acid, and drying to obtain the industrial salt.
The detection results are as follows:
example 2
Taking 100g of byproduct salt of pentaerythritol triallyl ether in a production device, putting the byproduct salt into a three-necked bottle with a stirrer, adding 50g of lower-layer water in a water separation tank, heating to 30 ℃, stirring for 30min, and filtering to obtain filtrate L1:78.71g and solid S1: 71.29 g;
100g of allyl chloride was further added, and the resulting solid S1 was washed with stirring at 30 ℃ for about 30min, filtered under a closed condition, and repeated 5 times. Filtrate L2:496.85g, solid S2: 74.44 g;
starting the refrigerating fluid to-15 ℃, controlling the nitrogen flow rate to be 50ml/min, heating the three-necked bottle to 90 ℃, and collecting a condensate L3: 5.01g, cooled to give solid S4: 69.43 g;
and putting the solid S4 into a crucible, calcining for 3 hours at 300 ℃ in a muffle furnace to obtain 69.34g of solid, neutralizing and washing with 8.9ml of 10% diluted hydrochloric acid, and drying to obtain the industrial salt.
The detection results are as follows:
example 3
Taking 100g of byproduct salt of trimethylolpropane diallyl ether in a production device, putting the byproduct salt into a three-necked bottle with a stirrer, adding 50g of lower-layer water in a water separation tank, heating to 30 ℃, stirring for 30min, and filtering to obtain filtrate L1:78.92g, solid S1: 71.08 g;
100g of allyl chloride was further added, and the resulting solid S1 was washed with stirring at 30 ℃ for about 30min, filtered under a closed condition, and repeated 5 times. Filtrate L2:495.89g, solid S2: 75.19 g;
starting the refrigerating fluid to-15 ℃, controlling the nitrogen flow rate to be 50ml/min, heating the three-necked bottle to 90 ℃, and collecting a condensate L3: 5.04g, cooled to give solid S4: 70.16 g;
and putting the solid S4 into a crucible, calcining for 3 hours at 300 ℃ in a muffle furnace to obtain 69.83g of solid, neutralizing and washing with 31.7ml of 10% diluted hydrochloric acid, and drying to obtain the industrial salt.
The detection results are as follows:
example 4
Taking 100g of byproduct salt of trimethylolpropane diallyl ether in a production device, putting the byproduct salt into a three-necked bottle with stirring, adding 30g of lower-layer water in a water separation tank, heating to 30 ℃, stirring for 30min, and filtering to obtain filtrate L1:47.35g, solid S1: 82.65 g;
100g of allyl chloride was further added, and the resulting solid S1 was washed with stirring at 30 ℃ for about 30min, filtered under a closed condition, and repeated 5 times. Filtrate L2:495.89g, solid S2: 86.76 g;
starting the refrigerating fluid to-15 ℃, controlling the nitrogen flow rate to be 50ml/min, heating the three-necked bottle to 90 ℃, and collecting a condensate L3: 5.09g, cooled to give S4 as a solid: 81.67 g;
and putting the solid S4 into a crucible, calcining for 3 hours at 300 ℃ in a muffle furnace to obtain 80.9g of solid, neutralizing and washing with 66.5ml of 10% dilute hydrochloric acid, and drying to obtain the industrial salt.
The detection results are as follows:
in the above embodiment, the raw material allyl chloride and the synthesis water are used to wash the by-product salt solid, so as to reduce the content of organic matters in the by-product salt, recover the incompletely reacted materials, and then completely remove the organic matters by calcination after drying. No foreign substances are introduced into the product, the operation is simple, no secondary pollution is generated, and the utilization rate of raw materials is improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment, and all technical solutions belonging to the principle of the present invention belong to the protection scope of the present invention. Modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles herein may be applied to other embodiments without departing from the spirit or scope of the invention.
Claims (5)
1. A method for removing organic matters of allyl ether byproduct salt is characterized by comprising the following steps:
s1: the brine for synthesizing the allyl ether is subjected to centrifugal filtration to obtain wet solid salt, the wet solid salt is preliminarily washed by synthesis reaction generated water, and washing liquid serving as alkaline water or layered water is returned to the reaction kettle for recycling; wherein the organic matter content of the solid salt is 1.5-3%, the mass ratio of the solid salt to the water generated by the synthesis reaction is 100: 30-60%, wherein the content of the solid salt organic matter after washing is 0.9-3%;
s2, preliminarily washing the solid salt washed in the step S1 by using a certain amount of raw material allyl chloride, and returning washing liquid serving as the raw material allyl chloride to the stirring kettle to participate in synthesis; wherein the mass ratio of the solid salt to the allyl chloride is 100: 200-500%, wherein the content of the solid salt organic matter after washing is 0.1-1%;
s3: drying the solid salt washed by the S2, and returning the liquid obtained after condensing the drying gas as a raw material of allyl chloride to the stirring kettle for synthesis;
s4: and (3) further calcining the dried solid salt to completely remove organic matters, and neutralizing and washing to obtain the qualified industrial salt.
2. The method of claim 1, wherein the method comprises the steps of: the allyl ether includes trimethylol diallyl ether or pentaerythritol triallyl ether.
3. The method of claim 1, wherein the method comprises the steps of: the drying method in the step S3 is ultrasonic drying or hot nitrogen drying.
4. The method of claim 1, wherein the method comprises the steps of: and in the step S3, the content of the solid salt organic matter is 0-0.3%.
5. The method of claim 1, wherein the method comprises the steps of: the industrial salt in the step S4 meets the first-grade standard of the GBT5462-2016 industrial salt standard.
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