CN101265158A - Method for producing 1,6-hexandiol - Google Patents
Method for producing 1,6-hexandiol Download PDFInfo
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- CN101265158A CN101265158A CNA2007100643167A CN200710064316A CN101265158A CN 101265158 A CN101265158 A CN 101265158A CN A2007100643167 A CNA2007100643167 A CN A2007100643167A CN 200710064316 A CN200710064316 A CN 200710064316A CN 101265158 A CN101265158 A CN 101265158A
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Abstract
The invention relates to a method of producing 1, 6-hexanediol, which is that solid acid catalysts that are adipate and methanol are pre-esterified at atmospheric pressure; the supernatant fluid of reaction products after pre-esterifying is delivered to a continuous esterifying tower to act the continuous esterifying reaction with methanol vapor under the action of a catalyst, and the temperature for the continuous esterifying reaction ranges from 70 DEG C to 15 DEG C; based on the quality of the adipate, the addition amount of a solid catalyst ranges from 1 to 10 percent; the molar ratio of the methanol and the adipate is 1 to 10:1, and a solid acid catalyst is strong acidic ion exchange resin; reactants act the hydrogenation reaction after purification by rectification, wherein, the molar ratio of the hydrogen and ester is 50 to 350:1, the temperature ranges from 150 to 250 DEG C, the pressure ranges from 2.5 to 10.0MPa, and the catalysts are copper oxide ranging from 25 to 60 percent, zinc oxide ranging from 25 to 60 percent and alumina ranging from 10 to 30 percent; the obtained crude methanol is performed through the purification by rectification to gain the 1, 6-hexanediol the purity quotient of which is 99.0 percent, and the waste methanol can be recycled after the rectification.
Description
Technical field:
The present invention relates to a kind of production 1, the method for 6-hexylene glycol.
Background technology:
1,6-hexylene glycol normal temperature is solid down, and 42 ℃ of fusing points, molecular weight are 118.18, density 0.965g/cm
31, the 6-hexylene glycol mainly is used as the raw material of new polyester, coating, tackiness agent, sealing agent and softening agent etc.With 1, the polyester polyol of 6-hexylene glycol preparation is used for polyurethane elastomer is carried out modification, the resin after the modification, and its physical strength, thermotolerance, water tolerance, scale resistance are all very excellent.And polyurethane elastomer can be widely used in fields such as synthetic rubber, synthon, synthetic leather.While 1,6-hexylene glycol carbochain is longer, and is flexible relatively large, can be used to prepare the novel polyester products with property.On the other hand, along with improving constantly of standard of living, people are also more and more higher to the requirement of environmental quality, can be increasing to the demand of environmentally friendly machine, and therefore make coating and adhesives industries develop to environmental protection, nontoxic, nuisanceless direction.1, the 6-hexylene glycol will be played a greater and greater role at water soluble resin coating for preparing environment-friendly type and polyurethane adhesive etc.
Pertinent literature Chinese patent (CN 1158234C) discloses a kind of from containing hexanodioic acid, 6 hydroxycaproic acid and a small amount of 1,4-cyclohexanediol mixture of carboxylic acids preparation 1, the method of 6-hexylene glycol, this mixture of carboxylic acids is to produce the oxidizing reaction of pimelinketone/hexalin and obtain by water extractive reaction mixture from the reaction of hexanaphthene and oxygen, wherein by sour esterification and hydrogenation reaction, contain cobalt and phosphoric acid salt mixture of carboxylic acids by employing as impurity, and make this mixture flow through cationite to remove these impurity, make esterification reaction mixture flow through anionite and realize this method then.This patent is raw materials used to be mixture, and there are the problems such as regeneration of exchanger in the Special attention will be given to preprocessing process.
Pertinent literature Chinese patent (CN 1089742C) discloses by containing hexanodioic acid, 6 hydroxycaproic acid and a small amount of 1,4-cyclohexanediol mixture of carboxylic acids preparation 1, the method of 6-hexylene glycol and 6-caprolactone, described mixture of carboxylic acids obtains as by product when using oxygen or oxygen-containing gas oxidizing ethyle alkyl to become pimelinketone/hexalin and water extractive reaction mixture, this method is that reactant esterification and hydrogenation are obtained hexylene glycol, and cyclisation 6 hydroxycaproic acid ester obtains caprolactone.
Summary of the invention:
The purpose of this invention is to provide a kind of hexanodioic acid and methanol esterification reaction production dimethyl adipate of utilizing, obtain 1 through hydrogenation again, the method for 6-hexylene glycol, the back 1 of purifying, the purity of 6-hexylene glycol can reach more than 99%, and methyl alcohol can be recycled.
This method may further comprise the steps:
(1). pre-esterification
Under normal pressure, add solid acid catalyst to intermittence in the esterifying kettle earlier, add hexanodioic acid and methyl alcohol then and carry out pre-esterification; The temperature of reaction of pre-esterification is 50～100 ℃;
(2). continuous esterification
Step (1) reaction product supernatant liquid is delivered to the top of continuous esterification tower, methanol vapor is changed into to entering the bottom of continuous esterification tower behind the steam, poor ester and methanol steam are done the adverse current continuous esterification in the catalyst section of continuous esterification tower, and the temperature of reaction of continuous esterification is 70～150 ℃; What the continuous esterification tower adopted is the vertical vertical tubular type structural response device of placing, inside reactor filling solid acid catalyst; The liquid reactor air speed is 0.1～0.9Kg/Kgh; The methyl alcohol air speed is 0.1～1.0Kg/Kgh; The length-to-diameter ratio of reactor is 3～40; The water that unreacted methanol and reaction produce is steamed by the continuous esterification cat head, through after the condensation, enters methanol distillation column, and the methanol loop after the rectification and purification is used;
Step (1), (2) are benchmark with the quality of hexanodioic acid, and the add-on of solid catalyst is 1～10%; Methyl alcohol and hexanodioic acid mol ratio are 1～10: 1, and solid acid catalyst is a strong acid ion exchange resin;
(3). the ester distillation
The reaction mass of step (2) is discharged from the bottom of continuous esterification tower and is entered thick ester jar and carry out the ester distillation, through batch fractionating or continuous rectification purified reaction product, finally obtains dimethyl adipate, and ester distillatory working pressure is 0～0.01Mpa (absolute pressure);
(4). shortening;
The dimethyl adipate that step (3) is obtained mixes with hydrogen through mixing tank, enters hydrogenator again behind preheater, carries out hydrogenation reaction in the presence of hydrogenation catalyst, and reaction product is separated through the laggard promoting the circulation of qi liquid of supercooler, and liquid enters thick alcohol jar; The mol ratio of hydrogen and dimethyl adipate is 50～350: 1; The catalyzer air speed is 0.01～0.5Kg dimethyl adipate/Kg catalyzer hour; The hydrogenation technique condition is 150～250 ℃ of temperature, pressure 2.5～10.0Mpa gauge pressure; The essentially consist of hydrogenation catalyst is that cupric oxide is 25～60wt%, and zinc oxide is 25～60wt%, and aluminum oxide is 10～30wt%;
(5). pure rectifying;
The thick alcohol that step (4) is obtained adopts the method for batch fractionating or continuous rectification to purify, and finally obtains 1, and 6-hexylene glycol product, the working pressure when batch fractionating or continuous rectification are 0～0.01Mpa absolute pressure.
It is 1 more than 99.0% that thick pure method by rectifying finally obtains purity, 6-hexylene glycol product.The useless methyl alcohol that produces in hydrogenation process can recycle through after the rectifying.
Description of drawings:
Fig. 1. hexanodioic acid of the present invention and methanol esterification produce 1, the process flow diagram of 6-hexylene glycol.
Mark
1. pre-esterifying kettle 2. head tanks 3. feedstock pumps 4. preheaters
5. methanol tank 6. methanol pump 7. vaporizers 8. continuous esterification towers
9. condenser 10. storage tanks 11. storage tanks 12. feedstock pumps
13. mixing tank 14. preheaters 15. compressors 16. hydrogenators
17. first separating tank, 18. storage tanks, 19. second separating tanks, 20. storage tanks
Embodiment
The following examples are to set forth rather than limit category of the present invention.
Further specify by the following examples:
With reference to the accompanying drawings technological process apparatus of the present invention is explained.Process flow diagram as shown in Figure 1.Technological operation is described as follows: add solid acid catalyst in the pre-esterifying kettle 1 of intermittent type earlier, the solid material hexanodioic acid is joined the intermittently pre-esterifying kettle 1 from charging opening, with the methanol pump charging methyl alcohol is joined from the material benzenemethanol relay tank and carry out pre-esterification reactor in the pre-esterifying kettle.Solid acid catalyst is stored in the still and repeatedly recycles in the normal running.Heat pre-esterifying kettle, methanol steam is back to after condensation in the pre-esterifying kettle in the reaction process.Pre-esterification reactor finishes, and behind sampling analysis, the reaction product supernatant liquid is delivered in the raw material storage tank 2.Through feedstock pump 3, after preheater 4 preheatings, enter the top of continuous esterification tower 8 from the raw material of head tank again.Through methanol pump 6, after vaporizer 7 becomes steam, enter the bottom of continuous esterification tower 8 from the methyl alcohol of methanol tank 5 again.Poor ester and methanol steam are done countercurrent reaction in the catalyst section of continuous esterification tower, reaction mass is discharged from the bottom of continuous esterification tower and is entered thick ester storage tank 11, unreacted methanol and the water that is produced are steamed by cat head, after condenser 9 condensations, enter methanol distillation column 10, enter methanol tank 5 by the methyl alcohol after the rectification and purification after qualified by analysis and recycle.Dimethyl adipate in the thick ester storage tank 11 is sent into mixing tank 13 through feedstock pump 12 and is mixed with hydrogen, behind preheater 14, enter hydrogenator 16 again and carry out hydrogenation reaction, reaction product is gone into first separating tank 17 through supercooler is laggard, after the gas-liquid separation, liquid enters thick pure storage tank 18, a part not lime set and recycle hydrogen enters second separating tank 19 again after cooling, mixing tank 13 is returned in compressed machine 15 circulations of hydrogen, and product enters storage tank 20.It is 1 more than 99.0% that thick pure method by rectifying finally obtains purity, 6-hexylene glycol product.The useless methyl alcohol that produces in hydrogenation process can recycle through after the rectifying.
Embodiment 2
In esterifying kettle, add solid acid catalyst, hexanodioic acid and methyl alcohol, normal pressure, heated and stirred is carried out pre-esterification reactor, and the catalyzer add-on is a benchmark with the quality of hexanodioic acid, and concrete outcome is as follows:
The pre-esterification experimental result of table 1 different catalysts add-on
| Catalyzer add-on % | Alcohol/sour mol ratio | Temperature ℃ | Reaction times h | Hexanodioic acid transformation efficiency % |
| 3 | 2.5 | 70～90℃ | 4 | 66.37 |
| 3 | 3.0 | 70～90℃ | 4 | 66.79 |
| 7 | 2.5 | 70～90℃ | 4 | 74.56 |
| 7 | 3.0 | 70～90℃ | 4 | 74.81 |
Embodiment 3
Utilize the product of embodiment 2 to carry out continuous esterification, normal pressure, under 70～150 ℃ of conditions, concrete outcome is as follows:
Table 2 different reactor length-to-diameter ratio continuous esterification experimental result
| The reactor length-to-diameter ratio | Liquid air speed Kg/Kgh | Methyl alcohol air speed Kg/Kgh | Hexanodioic acid transformation efficiency % |
| 30 | 0.41 | 0.42 | 99.83 |
| 30 | 0.60 | 0.65 | 99.72 |
| 8 | 0.41 | 0.42 | 99.27 |
| 8 | 0.60 | 0.65 | 99.23 |
Embodiment 4
Utilize the product of embodiment 2 to carry out continuous esterification, normal pressure, under 70～150 ℃ of conditions, the liquid air speed is 0.34Kg/Kgh, concrete outcome is as follows:
Table 3 liquid air speed is a 0.34Kg/Kgh continuous esterification experimental result
| Liquid air speed Kg/Kgh | Methyl alcohol air speed Kg/Kgh | Hexanodioic acid transformation efficiency % |
| 0.34 | 0.39 | 99.61 |
| 0.34 | 0.60 | 99.88 |
Utilize the product of embodiment 2 to carry out continuous esterification, normal pressure, under 70～150 ℃ of conditions, the methyl alcohol air speed is 0.37Kg/Kgh, concrete outcome is as follows:
Table 4 methyl alcohol air speed is a 0.37Kg/Kgh continuous esterification experimental result
| Liquid air speed Kg/Kgh | Methyl alcohol air speed Kg/Kgh | Hexanodioic acid transformation efficiency % |
| 0.34 | 0.37 | 99.59 |
| 0.60 | 0.37 | 99.20 |
Product to embodiment 3 carries out rectification and purification, carries out rectifying under working pressure 0～0.01MPa condition, and concrete outcome is as follows:
The product rectification and purification experimental result of table 5 embodiment 2
| Front-end volatiles % | Di adipate % | The residual % of still | Dimethyl adipate purity % |
| 5.89 | 87.87 | 6.24 | 99.91 |
Embodiment 7
Product to embodiment 2 carries out rectification and purification, carries out rectifying under working pressure 0～0.01MPa condition, and concrete outcome is as follows:
The product rectification and purification experimental result of table 6 embodiment 2
| Front-end volatiles % | Di adipate % | The residual % of still | Dimethyl adipate purity % |
| 27.77 | 39.28 | 32.95 | 99.73 |
Embodiment 8
Excessive methanol to embodiment 4 carries out Methanol Recovery, carries out rectifying under condition of normal pressure, and concrete outcome is as follows:
The excessive methanol of table 7 embodiment 4 carries out the rectifying experimental result
| Methyl alcohol % | Water % | The residual % of still | Methanol purity % |
| 82.05 | 10.34 | 7.61 | 99.72 |
Embodiment 9
Front-end volatiles to embodiment 7 carry out Methanol Recovery, carry out rectifying under condition of normal pressure, and concrete outcome is as follows:
The front-end volatiles of table 8 embodiment 7 carry out the rectifying experimental result
| Methyl alcohol % | Water % | The residual % of still | Methanol purity % |
| 35.81 | 52.86 | 11.33 | 99.58 |
Embodiment 10
To the residual pre-esterification reactor that carries out of the still of embodiment 7 and embodiment 8, normal pressure, heated and stirred, the catalyzer add-on is a benchmark with the quality of hexanodioic acid, concrete outcome is as follows:
The still of table 9 embodiment 7 and embodiment 8 is residual to carry out pre-esterification experimental result
| Catalyzer add-on % | Alcohol/sour mol ratio | Temperature ℃ | Reaction times h | Hexanodioic acid |
| 6 | 2.5 | 70～90℃ | 4 | 71.79 |
| 7 | 2.5 | 70～90℃ | 4 | 72.11 |
Utilize the ester rectifying product dimethyl adipate of embodiment 6 to carry out the shortening operation, concrete outcome is as follows:
The ester rectifying product dimethyl adipate hydrogenation experimental result of table 10 embodiment 6
| Hydrogen ester compares mol/mol | Air speed Kg/Kgh | Temperature ℃ | Pressure MPa | New hydrogen magnitude of recruitment % | Transformation efficiency % | Selectivity % |
| 160 | 0.15 | 200 | 3.0 | 3 | 100 | 96.12 |
| 200 | 0.30 | 230 | 6.0 | 5 | 100 | 99.17 |
Product to embodiment 11 carries out pure distillation operation, carries out pure rectifying under working pressure 0～0.01MPa (absolute pressure) condition, and concrete outcome is as follows:
The product of table 11 embodiment 11 carries out pure rectifying experimental result
| Front-end volatiles | Fusel % | 1,6-hexylene glycol % | The residual % of still | 1,6-hexylene glycol purity % | |
| 14.86 | 3.25 | 73.61 | 8.28 | 99.65 |
The methyl alcohol that embodiment 11 the is produced methanol rectification that give up is operated, the methanol rectification that under condition of normal pressure, gives up, and concrete outcome is as follows:
The methyl alcohol that table 12 embodiment 11 the produces methanol rectification experimental result of giving up
| Methyl alcohol % | The residual % of still | Methanol purity % |
| 92.05 | 7.95 | 99.83 |
To the methanol rectification operation of giving up of the front-end volatiles of embodiment 12, the methanol rectification that under condition of normal pressure, gives up, concrete outcome is as follows:
The front-end volatiles of the table 13 embodiment 12 methanol rectification experimental result of giving up
| Methyl alcohol % | The residual % of still | Methanol purity % |
| 86.13 | 13.87 | 99.77 |
Claims (6)
1. produce 1 for one kind, the method for 6-hexylene glycol is characterized in that: this method may further comprise the steps:
(1). pre-esterification
Under normal pressure, add solid acid catalyst to intermittence in the esterifying kettle earlier, add hexanodioic acid and methyl alcohol then and carry out pre-esterification; The temperature of reaction of pre-esterification is 50～100 ℃;
(2). continuous esterification
Step (1) reaction product supernatant liquid is delivered to the top of continuous esterification tower, methanol vapor is changed into to entering the bottom of continuous esterification tower behind the steam, poor ester and methanol steam are done the adverse current continuous esterification in the catalyst section of continuous esterification tower, and the temperature of reaction of continuous esterification is 70～15 ℃;
Step (1), (2) are benchmark with the quality of hexanodioic acid, and the add-on of solid catalyst is 1～10%; Methyl alcohol and hexanodioic acid mol ratio are 1～10: 1, and solid acid catalyst is a strong acid ion exchange resin;
(3). the ester distillation
The reaction mass of step (2) is discharged from the bottom of continuous esterification tower and is entered thick ester jar and carry out the ester distillation, through batch fractionating or continuous rectification purified reaction product, finally obtains dimethyl adipate, and ester distillatory working pressure absolute pressure is 0～0.01Mpa;
(4). shortening;
The dimethyl adipate that step (3) is obtained mixes with hydrogen through mixing tank, enters hydrogenator again behind preheater, carries out hydrogenation reaction in the presence of hydrogenation catalyst, and reaction product is separated through the laggard promoting the circulation of qi liquid of supercooler, and liquid enters thick alcohol jar; The mol ratio of hydrogen and dimethyl adipate is 50～350: 1; The catalyzer air speed is 0.01～0.5Kg dimethyl adipate/Kg catalyzer hour; The hydrogenation technique condition is 150～250 ℃ of temperature, pressure 2.5～10.0Mpa gauge pressure; The composition of hydrogenation catalyst is that cupric oxide is 25～60wt%, and zinc oxide is 25～60wt%, and aluminum oxide is 10～30wt%;
(5). pure rectifying;
The thick alcohol that step (4) is obtained adopts the method for batch fractionating or continuous rectification to purify, and finally obtains 1, and 6-hexylene glycol product, the working pressure when batch fractionating or continuous rectification are 0～0.01Mpa absolute pressure.
2. a kind of production 1 according to claim 1, the method for 6-hexylene glycol is characterized in that: the temperature of reaction of pre-esterification is 70～90 ℃.
3. a kind of production 1 according to claim 1, the method for 6-hexylene glycol is characterized in that: the add-on of solid catalyst is 3～7% of a hexanodioic acid quality.
4. a kind of production 1 according to claim 1, the method for 6-hexylene glycol is characterized in that: methyl alcohol and hexanodioic acid mol ratio are 2～5: 1.
5. a kind of production 1 according to claim 1, the method of 6-hexylene glycol, it is characterized in that: what the continuous esterification tower adopted is the vertical vertical tubular type structural response device of placing, inside reactor filling solid acid catalyst, and the liquid reactor air speed is 0.1～0.9Kg/Kgh; The methyl alcohol air speed is 0.1～1.0Kg/Kgh; The length-to-diameter ratio of reactor is 3～40.
6. a kind of production 1 according to claim 1, the method of 6-hexylene glycol is characterized in that: the water that step (2) unreacted methanol and reaction produce is steamed by the continuous esterification cat head, through after the condensation, enter methanol distillation column, the methanol loop after the rectification and purification is used.
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| CN101891610A (en) * | 2010-07-03 | 2010-11-24 | 潍坊市元利化工有限公司 | Continuous esterification production method for mixed dibasic acid dimethyl ester |
| CN101967082A (en) * | 2010-04-12 | 2011-02-09 | 宁波中化化学品有限公司 | Method for preparing 1,2-pentadiol |
| CN102320923A (en) * | 2011-07-15 | 2012-01-18 | 潍坊市元利化工有限公司 | Method for preparing dihydric alcohol by refining and separating dimethyl nylon acid |
| CN102320925A (en) * | 2011-07-15 | 2012-01-18 | 潍坊市元利化工有限公司 | Method for preparing mixed dihydric alcohol by hydrogenating dimethyl nylon acid |
| CN102351648A (en) * | 2011-09-09 | 2012-02-15 | 上海戊正工程技术有限公司 | Process for producing 1,6-hexanediol and coproducing epsilon-caprolactone |
| CN102659516A (en) * | 2012-05-23 | 2012-09-12 | 江苏省东泰精细化工有限责任公司 | Production method of hexanediol |
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| CN106748645A (en) * | 2016-12-10 | 2017-05-31 | 山东元利科技股份有限公司 | The method that one kind improves 1,6 hexylene glycol purity |
| CN107337579A (en) * | 2017-08-29 | 2017-11-10 | 华陆工程科技有限责任公司 | A kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol |
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| CN109748778A (en) * | 2017-11-01 | 2019-05-14 | 中国石油化工股份有限公司 | The method for producing 1,6- hexylene glycol |
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| CN1594252A (en) * | 2004-06-21 | 2005-03-16 | 沈阳工业大学 | Method for producing 1,6-hexanediol |
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| CN101891610A (en) * | 2010-07-03 | 2010-11-24 | 潍坊市元利化工有限公司 | Continuous esterification production method for mixed dibasic acid dimethyl ester |
| CN102320923A (en) * | 2011-07-15 | 2012-01-18 | 潍坊市元利化工有限公司 | Method for preparing dihydric alcohol by refining and separating dimethyl nylon acid |
| CN102320925A (en) * | 2011-07-15 | 2012-01-18 | 潍坊市元利化工有限公司 | Method for preparing mixed dihydric alcohol by hydrogenating dimethyl nylon acid |
| CN102320923B (en) * | 2011-07-15 | 2013-10-23 | 山东元利科技股份有限公司 | Method for preparing dihydric alcohol by refining and separating dimethyl nylon acid |
| CN102351648A (en) * | 2011-09-09 | 2012-02-15 | 上海戊正工程技术有限公司 | Process for producing 1,6-hexanediol and coproducing epsilon-caprolactone |
| CN102659516A (en) * | 2012-05-23 | 2012-09-12 | 江苏省东泰精细化工有限责任公司 | Production method of hexanediol |
| CN104557465A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and alkanol |
| CN106748645A (en) * | 2016-12-10 | 2017-05-31 | 山东元利科技股份有限公司 | The method that one kind improves 1,6 hexylene glycol purity |
| CN106748645B (en) * | 2016-12-10 | 2020-06-05 | 山东元利科技有限公司 | Method for improving purity of 1, 6-hexanediol |
| CN107337579A (en) * | 2017-08-29 | 2017-11-10 | 华陆工程科技有限责任公司 | A kind of method of serialization circulation liquid-phase hydrogenatin production hexylene glycol |
| CN107337579B (en) * | 2017-08-29 | 2024-04-12 | 华陆工程科技有限责任公司 | Method for producing hexanediol by continuous circulating liquid phase hydrogenation |
| CN109748778A (en) * | 2017-11-01 | 2019-05-14 | 中国石油化工股份有限公司 | The method for producing 1,6- hexylene glycol |
| CN109622045A (en) * | 2018-12-24 | 2019-04-16 | 徐州顺平生物科技有限公司 | A kind of Mg for Synthesis of diethyl adipate2+Loaded resin catalyst |
| CN110156562A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of synthesis technology of 1,6-HD |
| US11492316B1 (en) | 2021-06-07 | 2022-11-08 | Zhejiang Boju New Materials Co., Ltd. | Production method and production device of high-purity 1,6-hexanediol |
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