CN101875651A - Production method of 3-methyl sulfolane - Google Patents
Production method of 3-methyl sulfolane Download PDFInfo
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- CN101875651A CN101875651A CN 200910011315 CN200910011315A CN101875651A CN 101875651 A CN101875651 A CN 101875651A CN 200910011315 CN200910011315 CN 200910011315 CN 200910011315 A CN200910011315 A CN 200910011315A CN 101875651 A CN101875651 A CN 101875651A
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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 80 DEG 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 provides a kind of production method of 3-methyl sulfolane.
The object of the present invention is achieved like this: will have stirring earlier; heating; the pressure of cooling infrastructure is that the stainless steel chemical combination reactor of 10Mpa cleans up; dry; through nitrogen replacement; under the nitrogen protection condition, drop into hydroquinone of polymerization retarder; the weight of Resorcinol is the 0.18%-0.27% of reaction mass total amount; add sulfur dioxide liquid and isoprene then successively; the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0; heating while stirring; when being raised to 80 ℃, temperature stops heating; 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); restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet; obtain thick alkene sulfone; the water of weights such as adding and thick alkene sulfone dilutes; be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate; under the nitrogen protection condition, add Raney's nickel catalyst; the weight of Raney's nickel is the 4%-10% of the raw material gross weight that drops in the combination reaction still; in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction; hydrogen pressure is generally 2.0Mpa; controlled temperature is below 70 ℃; available water coolant and logical hydrogen amount 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 promptly obtain the 3-methyl sulfolane.
Advantage of the present invention is: because the at high temperature easy autohemagglutination of isoprene, an amount of hydroquinone of polymerization retarder and control combination reaction temperature in raw material and synthetic combination reaction, have all been added, 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 the molecular formula and the structural formula of 3-methyl sulfolane;
Fig. 2 is the reaction mechanism of producing the 3-methyl sulfolane with method of the present invention.
Embodiment:
To have stirring earlier; heating; the pressure of cooling infrastructure is that the stainless steel chemical combination reactor of 10Mpa cleans up; dry; through nitrogen replacement; under the nitrogen protection condition, drop into hydroquinone of polymerization retarder; the weight of Resorcinol is the 0.18%-0.27% of reaction mass total amount; add sulfur dioxide liquid and isoprene then successively; the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0; heating while stirring; when being raised to 80 ℃, temperature stops heating; 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); restir is 20 minutes when treating that temperature rise is slowly with without water for cooling also not temperature rise; obtain thick alkene sulfone; the water of weights such as adding and thick alkene sulfone dilutes; be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate; under the nitrogen protection condition, add Raney's nickel catalyst; the weight of Raney's nickel is to drop into the 4%-10% of raw material gross weight in the combination reaction still; in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction; hydrogen pressure is generally 2.0Mpa; controlled temperature is below 70 ℃; available water coolant and logical hydrogen amount 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 promptly obtain the 3-methyl sulfolane.
Experimental installation: chemical combination adopts the reactor of 1 liter stainless steel, pressure 10Mpa, band 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. Gray Si 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, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, when being raised to 80 ℃, temperature stops heating, 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtain thick alkene sulfone, adopt chemical process (bromine valency assay method) to detect alkene sulfone content, alkene sulfone yield 82.3%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 17.4 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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 UOP608) to detect the purity of thick 3-methyl sulfolane, the hydrogenation degree of depth reaches 81.6%, and resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 241 grams.
Embodiment 2
At first drop into hydroquinone of polymerization retarder 0.8 gram, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, stop 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtains thick alkene sulfone, alkene sulfone yield 82.5%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 30.5 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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 91.8%, and resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 272 grams.
Embodiment 3
At first drop into hydroquinone of polymerization retarder 0.8 gram, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, stop 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtains thick alkene sulfone, alkene sulfone yield 82.6%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 43.4 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, stop 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtains thick alkene sulfone, alkene sulfone yield 91.2%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 17.4 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, stop 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtains thick alkene sulfone, alkene sulfone yield 91.1%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 30.5 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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%, and resultant after filtration, dehydration, rectifying obtains 3-methyl sulfolane 299 grams.
Embodiment 6
At first drop into hydroquinone of polymerization retarder 1.2 grams, add sulfur dioxide liquid 230 grams and isoprene 204 grams then successively, heating while stirring, stop 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), restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet, obtains thick alkene sulfone, alkene sulfone yield 87%; The water of weights such as adding and thick alkene sulfone dilutes, be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate, add Raney's nickel catalyst 43.4 grams simultaneously, in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction, hydrogen pressure is generally 2.0Mpa, controlled temperature is below 70 ℃, available water coolant and logical hydrogen amount 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: in the combination reaction still, drop into hydroquinone of polymerization retarder under the nitrogen protection condition; add sulfur dioxide liquid and isoprene then successively; the mol ratio of sulfur dioxide liquid and isoprene is 1.2: 1.0; heating while stirring; when being raised to 80 ℃, temperature stops heating; because the material reaction temperature can continue to rise; this moment, water was lowered the temperature to it; temperature is controlled at 90 ℃-100 ℃; restir is 20 minutes when treating that temperature rise does not heat up slowly with without water for cooling yet; obtain thick alkene sulfone; the water of weights such as adding and thick alkene sulfone dilutes; be moved in the hydrogenation reaction kettle again after filtering out flocculent precipitate; under the nitrogen protection condition, add Raney's nickel catalyst; in reactor, feed High Purity Hydrogen after the stirring again and carry out hydrogenation reaction; hydrogen pressure is generally 2.0Mpa; controlled temperature is below 70 ℃; available water coolant and logical hydrogen amount controlled temperature; reaction ends when hydrogen supply pressure 3.0Mpa stops water-cooled and no longer heats up also, and resultant after filtration; dehydration; rectifying gets final product.
2. according to the production method of the described 3-methyl sulfolane of 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 claim 1 or 2 described 3-methyl sulfolanes, 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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| CN 200910011315 CN101875651B (en) | 2009-04-28 | 2009-04-28 | Production method of 3-methyl sulfolane |
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| CN101875651B CN101875651B (en) | 2013-05-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013189384A (en) * | 2012-03-12 | 2013-09-26 | Sumitomo Seika Chem Co Ltd | Method for producing sulfolene compound and method for producing sulfolane compound |
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| CN1246307C (en) * | 2003-12-15 | 2006-03-22 | 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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| JP2013189384A (en) * | 2012-03-12 | 2013-09-26 | Sumitomo Seika Chem Co Ltd | Method for producing sulfolene compound and method for producing sulfolane compound |
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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. |