CN101875651B - Production method of 3-methyl sulfolane - Google Patents
Production method of 3-methyl sulfolane Download PDFInfo
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- CN101875651B CN101875651B CN 200910011315 CN200910011315A CN101875651B CN 101875651 B CN101875651 B CN 101875651B CN 200910011315 CN200910011315 CN 200910011315 CN 200910011315 A CN200910011315 A CN 200910011315A CN 101875651 B CN101875651 B CN 101875651B
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Abstract
The invention discloses a production method of 3-methyl sulfolane, relating to an organic solvent capable of being used for aromatic hydrocarbon extraction and mainly aiming to solve the problem that the commercialization of the 3-methyl sulfolane is not realized at home and abroad at present. The production method comprises the steps of: putting a polymerization inhibitor hydroquinone into a combination reaction kettle in the presence of nitrogen protection, then sequentially adding sulfur dioxide liquid and isoprene, heating while stirring, stopping heating when the temperature raises to 80DEG C, cooling by using water, controlling the temperature to be within 90-100 DEG C, continuing stirring for 20 minutes when stopping heating so as to obtain crude alkene, adding water for diluting, filtering flocculent precipitates and then immigrating into a hydrogenation reaction kettle, simultaneously adding a Raney nickel catalyst, introducing high-purity hydrogen into the reaction kettle for hydrogenation reaction, controlling the temperature to be below 70 DEG C, stopping water cooling and heating to terminate the reaction when the hydrogen supply pressure is 3.0 MPa, and filtering, dehydrating and rectifying a product.
Description
Technical field:
The present invention relates to a kind of organic solvent that can be used for aromatic hydrocarbons extraction.
Background technology:
The 3-methyl sulfolane is used for the organic solvent of aromatic hydrocarbons extraction, can improve the selectivity of counterweight aromatic hydrocarbons extraction, but at present at home and abroad the 3-methyl sulfolane do not realize commercialization.
Summary of the invention:
Technical problem to be solved by this invention is to provide a kind of production method of 3-methyl sulfolane.
the object of the present invention is achieved like this: first will be with stirring, heating, the pressure of cooling infrastructure is that the stainless steel chemical combination reactor of 10Mpa cleans up, dry, through nitrogen replacement, drop into hydroquinone of polymerization retarder under the nitrogen protection condition, the weight of Resorcinol is the 0.18%-0.27% of reaction mass total amount, then add successively sulfur dioxide liquid and isoprene, the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add Raney's nickel catalyst under the nitrogen protection condition, the weight of Raney's nickel is the 4%-10% of the raw material gross weight that drops in the combination reaction still, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute.Resultant after filtration, dehydration, rectifying namely obtain the 3-methyl sulfolane.
Advantage of the present invention is: due to isoprene easy autohemagglutination at high temperature, all added appropriate hydroquinone of polymerization retarder and controlled the combination reaction temperature in raw material and synthetic combination reaction, thereby reduced the generation of isoprene autopolymer, product purity can reach more than 99%, and yield can reach 76%.
Description of drawings:
Fig. 1 is molecular formula and the structural formula of 3-methyl sulfolane;
Fig. 2 produces the reaction mechanism of 3-methyl sulfolane with method of the present invention.
Embodiment:
first will be with stirring, heating, the pressure of cooling infrastructure is that the stainless steel chemical combination reactor of 10Mpa cleans up, dry, through nitrogen replacement, drop into hydroquinone of polymerization retarder under the nitrogen protection condition, the weight of Resorcinol is the 0.18%-0.27% of reaction mass total amount, then add successively sulfur dioxide liquid and isoprene, the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), stirred again 20 minutes during slowly with without water for cooling also not temperature rise until temperature rise, obtain thick alkene sulfone, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add Raney's nickel catalyst under the nitrogen protection condition, the weight of Raney's nickel is to drop into the 4%-10% of raw material gross weight in the combination reaction still, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute.Resultant after filtration, dehydration, rectifying namely obtain the 3-methyl sulfolane.
Experimental installation: chemical combination adopts 1 liter stainless steel, pressure 10Mpa, with the reactor of stirring, heating, cooling infrastructure; Hydrogenation reaction adopts the reactor of 2 liter stainless steels, pressure 10Mpa, band stirring, water cooling facility.
Experiment starting material: isoprene: purity 〉=99%; Sulfurous gas: purity 〉=99.5%, colourless; Hydrogen: purity 〉=99.9%; Raney's nickel is that U.S.'s Grace chemical company is produced; Resorcinol: chemical pure; Experimental water: deionized water.
All experiments must clean up reactor before feeding intake, drying, and through nitrogen replacement, experiment feeds intake under the nitrogen protection condition.
Embodiment 1:
at first drop into hydroquinone of polymerization retarder 0.8 gram, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, adopt chemical process (bromine valency assay method) to detect alkene sulfone content, alkene sulfone yield 82.3%, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 17.4 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, adopt vapor-phase chromatography (adopting by reference U0P608) to detect the purity of thick 3-methyl sulfolane, the hydrogenation degree of depth reaches 81.6%, resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 241 grams.
Embodiment 2
at first drop into hydroquinone of polymerization retarder 0.8 gram, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, alkene sulfone yield 82.5%, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 30.5 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, the hydrogenation degree of depth reaches 91.8%, resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 272 grams.
Embodiment 3
At first drop into hydroquinone of polymerization retarder 0.8 gram, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, alkene sulfone yield 82.6%; Add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 43.4 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, and the hydrogenation degree of depth reaches 92.2%; Resultant after filtration, dehydration, rectifying obtain 3-methyl sulfolane 273 grams.
Embodiment 4
At first drop into hydroquinone of polymerization retarder 1.2 grams, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, alkene sulfone yield 91.2%; Add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 17.4 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, and the hydrogenation degree of depth reaches 81.7%; Resultant after filtration, dehydration, rectifying obtain 3-methyl sulfolane 268 grams.
Embodiment 5
at first drop into hydroquinone of polymerization retarder 1.2 grams, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, alkene sulfone yield 91.1%, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 30.5 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, the hydrogenation degree of depth reaches 92%, resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 299 grams.
Embodiment 6
At first drop into hydroquinone of polymerization retarder 1.2 grams, then add successively sulfur dioxide liquid 230 grams and isoprene 204 grams, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃ (this moment, reacting kettle inner pressure was 2.5-3.0Mpa), until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, alkene sulfone yield 87%; Add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add simultaneously Raney's nickel catalyst 43.4 grams, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlling temperature is below 70 ℃, available water coolant and logical hydrogen amount are controlled temperature, when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, show that reaction ends, the general reaction times is 30-40 minute, and the hydrogenation degree of depth reaches 92%; Resultant after filtration, dehydration, rectifying obtain 3-methyl sulfolane 305 grams.
Claims (3)
1.3-the production method of methyl sulfolane, it is characterized in that: drop into hydroquinone of polymerization retarder in the combination reaction still under the nitrogen protection condition, then add successively sulfur dioxide liquid and isoprene, the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0, heating while stirring, stopped heating when temperature is raised to 80 ℃, because the material reaction temperature can continue to rise, this moment, water was lowered the temperature to it, temperature is controlled at 90 ℃-100 ℃, until temperature rise slowly and stirred again 20 minutes when also not heating up without water for cooling, obtain thick alkene sulfone, add the water with weights such as thick alkene sulfones to dilute, be moved into again in hydrogenation reaction kettle after filtering out flocculent precipitate, add Raney's nickel catalyst under the nitrogen protection condition, pass into High Purity Hydrogen in the reactor again after stirring and carry out hydrogenation reaction, hydrogen pressure is 2.0MPa, controlling temperature is below 70 ℃, control temperature with water coolant and logical hydrogen amount, reaction ends when hydrogen supply pressure 3.0MPa stops water-cooled and no longer heats up also, resultant after filtration, dehydration, rectifying gets final product.
2. according to the production method of 3-methyl sulfolane claimed in claim 1, it is characterized in that: the weight of Resorcinol is the 0.18%-0.27% of reaction mass total amount.
3. according to the production method of the described 3-methyl sulfolane of claim 1 or 2, it is characterized in that: the weight of Raney's nickel is the 4%-10% of the raw material gross weight that drops in the combination reaction still.
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| CN 200910011315 CN101875651B (en) | 2009-04-28 | 2009-04-28 | Production method of 3-methyl sulfolane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546469A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Method for producing sulfolane by hydrogenation of sulfolene |
| CN1696081A (en) * | 2004-05-14 | 2005-11-16 | 佟庆杰 | Method for removing hydroquinone from chemical products |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546469A (en) * | 2003-12-15 | 2004-11-17 | 南开大学 | Method for producing sulfolane by hydrogenation of sulfolene |
| CN1696081A (en) * | 2004-05-14 | 2005-11-16 | 佟庆杰 | Method for removing hydroquinone from chemical products |
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| Title |
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| JP特开平7-17970A 1995.01.20 |
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Effective date of registration: 20230906 Address after: No. 35 Wansheng Fifth Street, Hongwei District, Liaoyang City, Liaoning Province, 111003 Patentee after: Liaoning Guanghua Chemical Co.,Ltd. Address before: 111000 no.168-19, Qingnian Street, Baita District, Liaoyang City, Liaoning Province Patentee before: LIAOYANG GUANGHUA CHEMICAL Co.,Ltd. |
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