CN102442905B - The method of preparing dimethyl adipate by continuous esterification - Google Patents
The method of preparing dimethyl adipate by continuous esterification Download PDFInfo
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- CN102442905B CN102442905B CN201010511406.8A CN201010511406A CN102442905B CN 102442905 B CN102442905 B CN 102442905B CN 201010511406 A CN201010511406 A CN 201010511406A CN 102442905 B CN102442905 B CN 102442905B
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Abstract
The invention discloses a kind of method of preparing dimethyl adipate by continuous esterification, comprise: (1) adopts with the tubular reactor of inner member, to hexanodioic acid and carbinol mixture under catalyst-free condition, carry out pre-esterification, temperature 90 ~ 180 DEG C, pressure 0.05-3MPa; (2) pre-esterification product delivers to continuous catalyzing rectifying tower top, and dry methyl alcohol enters catalytic rectifying tower bottom after vaporization, and the material after pre-esterification reactor and methanol steam counter current contact in catalytic rectifying tower, carries out esterification further.Instant invention overcomes equipment corrosion and pollution problem that traditional technology utilizes sulfuric acid catalyst to bring, and pre-esterification cannot be continuous, catalyst consumption amount is large wait not enough.
Description
Technical field
The present invention relates to a kind of production method of 1,6-dimethyl adipate, particularly use solid acid to do the dimethyl adipate production method of catalyzer.
Background technology
1,6-dimethyl adipate is excellent cold resistant plasticizer, can give the low-temperature pliability energy that goods are excellent, and have must photo and thermal stability and water tolerance.1,6-dimethyl adipate or important organic synthesis raw material, chemical intermediate, can produce 1,6-hexylene glycol by hydrogenation.
At present, the report about 1,6-dimethyl adipate production method has: GB143069 discloses a kind of comparatively original processing method, uses the vitriol oil as catalyzer, adopts the method for tank reactor reaction distillation to dewater.Adopt inorganic liquid acid to be catalyzer, there is inorganic liquid acid to problem of environmental pollutions such as the corrosion of equipment and the three-protection design of reaction product.DE19610564 discloses a kind of multiple tank reactor series connection, and reaction carries out periodical operation under agitation, and the continuous industry of mass-producing is produced to adopt rhythmic reaction to be unfavorable for.WO99/62852 discloses a kind of Utilize Cyclohexane Oxidation By-Product hexanodioic acid and methanol esterification method, and use sulfuric acid is catalyzer, tubular reactor, and distillation dewaters, and obtains dimethyl adipate.Adopt fixed bed disclosed in CN200610112688.8, with hexanodioic acid and methyl alcohol for raw material, solid acid catalyst, fixed bed continuous esterification production of adipic acid dimethyl ester, raw material needs to enter flow reactor after pre-esterification process, pre-esterification reactor needs to add catalyzer, adds production cost.
As described in above-mentioned prior art, hexanodioic acid esterification reaction needed exists at catalyzer and carries out under suitable condition, esterifying catalyst is generally an acidic catalyst, as sulfuric acid, sodium pyrosulfate, molecular sieve, heteropolyacid, acidic resins etc., hexanodioic acid can be dissolved in ethanol, methyl alcohol equal solvent at typical condition, but esterification does not occur.
Summary of the invention
The object of the present invention is to provide a kind of method of hexanodioic acid continuous esterification, overcome in existing hexanodioic acid esterification production of adipic acid dimethyl ester process, pre-esterification can not continuous print problem.
The method of preparing dimethyl adipate by continuous esterification of the present invention comprises the following steps:
(1) hexanodioic acid and methyl alcohol are added in raw material mixing tank, head tank is the non-pressure vessel with stirring, hexanodioic acid and methyl alcohol are after being uniformly mixed, do not use catalyzer, squeeze in the tubular reactor with inner member by pump, tubular reactor temperature of reaction 90-180 DEG C, preferred 110-150 DEG C; Pressure 0.05-3MPa, preferred 0.5-1MPa, material is 0.2-6h in the inner reaction tube residence time, preferred 2-4h.
(2) cold material heat exchange in tubular reactor outlet streams and raw material mixing tank, after heat exchange, in head tank, mixing raw material temperature, not higher than 70 DEG C, is generally 40 ~ 70 DEG C, and the pre-esterification material after heat exchange cooling enters subsequent catalyst rectifying tower.
(3) catalytic rectifying tower top delivered to by the pre-esterification material after heat exchange cooling, and dry methyl alcohol enters catalytic rectifying tower bottom after vaporization, and the material after pre-esterification reactor and methanol steam counter current contact in esterification column, carries out esterification further.Temperature of reaction in catalytic rectifying tower is 70-150 DEG C, material air speed after pre-esterification reactor is the 0.1 ~ 2.0kg/kgh (ratio of weight to catalyst weight entering catalytic rectifying tower reaction mass per hour, as follows), methyl alcohol air speed is 0.1 ~ 10.0kg/kgh.The dimethyl adipate that catalytic distillation is obtained by reacting is discharged at the bottom of tower, and the water vapor that excessive methyl alcohol and stripping go out is discharged from tower top.
In the inventive method, pre-esterification reactor device used is the tubular reactor with inner member, and inner member is generally baffle, twisted blade.Tubular reactor can be single, also can be many series windings, also can be many and connect.Twisted blade angle selected by tubular reactor inner member is 0-180 degree, and the ratio range of individual blade and diameter (tubular reactor internal diameter) is L/D=0.5-2, and unit number is 1-100.In practice, the static mixer of any structure can be used.
In the inventive method, the dimethyl adipate of discharging at the bottom of catalytic rectifying tower can adopt the method for rectifying to purify further, and the moisture vapor methyl alcohol that catalytic distillation tower top is discharged can use by rectifying and dewatering Posterior circle further.Aforesaid method can adopt the method for this area routine.
Hexanodioic acid solid sends into raw material mixing tank by spiral fresh feed pump, methyl alcohol sends into head tank by methanol pump, raw material mixing tank is the container that normal pressure band stirs, inside there is coil heat exchanger, preliminary preheating is carried out to mixed serum, the outlet of raw material mixing tank is connected with fresh feed pump, fresh feed pump discharge port is connected with tubular reactor, tubular reactor can be single or multiple series winding or parallel connection, tubular reactor outlet is connected with reducing valve, reducing valve goes out to connect snakelike heat exchange tube, incoming stock mixing tank and wherein material-heat-exchanging, then be connected with catalytic rectifying tower upper feed inlet through esterification feed pump.
In the inventive method, in catalytic rectifying tower, highly acidic resin catalyzer can be used, specifically can select the commercially available highly acidic resin catalyst prod of this area routine.
Owing to adopting above technical scheme, the inventive method has following technique effect:
(1) pre-esterification reactor process is combined with catalytic distillation esterification reaction process, because pre-esterification process has carried out the esterification of certain transformation efficiency, therefore while raising hexanodioic acid transformation efficiency, reduce the reaction load of catalytic distillation esterification, decrease the consumption of highly acidic resin catalyzer, reduce process cost.
(2) employing is with the tubular reactor of inner member as pre-esterification reactor device, and solving pre-esterification cannot continuous print problem.Hexanodioic acid is slightly soluble in methyl alcohol, the pasty mixture of hexanodioic acid and methyl alcohol can not directly as catalytic distillation charging, pre-esterification must be carried out, and be equivalent to be with the tubular reactor of inner member the withstand voltage still stirred, be better than again withstand voltage still, withstand voltage still can not realize operate continuously, and tubular reactor can be continuous, by the length of adjustable pipe and the residence time of material, control level of response better.
(3) after pre-esterification temperature of charge more than 100 DEG C, temperature required higher than catalytic rectifying tower entrance, so utilize this strand of material and raw material heat exchange, pre-esterification temperature of charge can reach catalytic rectifying tower feed needs, improve pre-esterification feeding temperature simultaneously, eliminate raw material preheating process furnace, saved the energy, improve plant factor.
(4) the inventive method is compared with CN00610112688.8, simplifies pre-esterifying process step, because pre-esterification does not use catalyzer, has saved production cost, has eliminated catalyst filtration step, saved process cost.Show through research, not easily there is esterification at typical condition in hexanodioic acid and methyl alcohol, even the preliminary pre-esterification reactor that conversion requirements is not high also need carry out under catalyzer and suitable condition, therefore, those of ordinary skill in the art can not expect the pre-esterification process not using catalyzer.The present invention finds through large quantity research, under given conditions, as under suitable reaction pressure and temperature of reaction, the catalytic performance of hexanodioic acid self can be excited, realize certain esterification transformation efficiency, although along with the carrying out of reaction, hexanodioic acid content reduces, and the self-catalysis of pre-esterification reactor system is reduced, but has reached the requirement of pre-esterification reactor, therefore, the pre-esterification reactor process not using catalyzer can be realized completely.
Accompanying drawing explanation
Fig. 1 is adipic acid ester metallization processes experiment flow schematic diagram of the present invention.
Wherein: 1-raw material mixing tank, 2-fresh feed pump, 3-tubular reactor, 4-methanol tank, 5-reducing valve, 6-catalytic rectifying tower, 7-esterification feed pump, 8-methyl alcohol vaporizing device, 9-coil heat exchanger, 10-methyl alcohol tundish, 11-condenser, 12-methanol feeding pump.
Embodiment
The solution of the present invention and effect is further illustrated below in conjunction with accompanying drawing.
Shown in experimental technique flow process as of the present invention in Fig. 1, the equipment of use comprises raw material mixing tank 1, fresh feed pump 2, tubular reactor 3, methanol tank 4, pressurizing valve 5, catalytic rectifying tower 6 esterification feed pump 7, methyl alcohol vaporizing device 8, coil heat exchanger 9, methyl alcohol tundish 10, condenser 11, methyl alcohol tundish 10.
Hexanodioic acid and methyl alcohol exist at catalyst-free and carry out pre-esterification reactor under suitable processing condition in pre-esterification reactor device, pre-esterification reactor product enters catalytic rectifying tower top after decompression, further esterification is carried out with the methanol steam entered bottom catalytic distillation reaction tower, reaction product dimethyl adipate is discharged and is entered ester rectifying and purifying system at the bottom of catalytic rectifying tower, and the excessive methanol that catalytic distillation tower top is discharged and the water that stripping goes out enter methanol purification recovery system.
The present invention program and effect is further illustrated below by embodiment.
Embodiment 1
Pre-esterification reactor is tested
Methyl alcohol and hexanodioic acid is mixed by alcohol/sour mol ratio 3 ~ 5, pass through tubular reactor, pipe range 5m, internal diameter 1cm, 180 ° of twisted blades stagger 90 ° this tower ladder gram mixing tank arranged, under catalyst-free condition, hexanodioic acid and methyl alcohol generation pre-esterification reactor, experimental result is in table 1 (hexanodioic acid transformation efficiency is pressed liquid-phase chromatographic analysis result and calculated).
Table 1 embodiment 1 pre-esterification reactor result
Embodiment 2 pre-esterification reactor is tested
Methyl alcohol and hexanodioic acid is mixed by alcohol/sour mol ratio 3 ~ 5, pass through tubular reactor, pipe range 1m, internal diameter 1cm, 180 ° of twisted blades stagger 90 ° this tower ladder gram mixing tank arranged, and the reaction times is 2h, under catalyst-free condition, hexanodioic acid and methyl alcohol generation pre-esterification reactor, experimental result is in table 2 (hexanodioic acid transformation efficiency is pressed liquid-phase chromatographic analysis result and calculated).
Table 2 embodiment 2 pre-esterification reactor result
| Experiment sequence number | Molar ratio of alcohol to acid | Temperature of reaction, DEG C | Hexanodioic acid transformation efficiency, % |
| 1 | 3 | 120 | 84.2％ |
| 2 | 3 | 130 | 91.4％ |
| 3 | 3 | 140 | 95.6％ |
Comparative example 1
By the material proportion of embodiment experiment sequence number 1, under normal pressure 80 DEG C of conditions, be uniformly mixed 2 hours, obvious esterification does not occur.Add the resin catalyst of hexanodioic acid weight 5%, under 80 DEG C of condition of normal pressure, stirring and refluxing mixes 2 hours, and hexanodioic acid transformation efficiency is 70.1%.
Esterification experimental result under the different air speed of embodiment 3
The mixture after embodiment 1 pre-esterification reactor is utilized to carry out continuous esterification experiment, the DNW-type Ⅱ resin using Dandong Mingzhu Special Type Resin Co., Ltd. to produce is catalyzer, employing catalytic distillation reacts, and arranges 10 blocks of column plates, every block column plate is uniformly distributed resin catalyst in catalytic rectifying tower.Operation pressure is normal pressure, and column bottom temperature is 120 DEG C, and tower top temperature is 95 DEG C, and reaction result is at different conditions in table 3.
Table 3 catalytic distillation esterification condition and result
Claims (8)
1. a method for preparing dimethyl adipate by continuous esterification, is characterized in that comprising the following steps:
(1) hexanodioic acid and methyl alcohol are added in raw material mixing tank, head tank is the non-pressure vessel with stirring, hexanodioic acid and methyl alcohol are after being uniformly mixed, do not use catalyzer, squeeze in the tubular reactor with inner member by pump, tubular reactor temperature of reaction is 110-180 DEG C, and pressure is 0.5-3MPa, and material is 0.2-6h in the inner reaction tube residence time;
(2) cold material heat exchange in tubular reactor outlet streams and raw material mixing tank, after heat exchange, in head tank, mixing raw material temperature is not higher than 70 DEG C, and the pre-esterification material after heat exchange cooling enters subsequent catalyst rectifying tower;
(3) catalytic rectifying tower top delivered to by the pre-esterification material after heat exchange cooling, dry methyl alcohol enters catalytic rectifying tower bottom after vaporization, material after pre-esterification reactor and methanol steam counter current contact in esterification column, carry out esterification further, the dimethyl adipate that catalytic distillation is obtained by reacting is discharged at the bottom of tower, and the water vapour that excessive methyl alcohol and stripping go out is discharged from tower top; Temperature of reaction wherein in catalytic rectifying tower is 70-150 DEG C, and the material air speed after pre-esterification reactor is 0.1 ~ 2.0kg/kgh, and methyl alcohol air speed is 0.1 ~ 10.0kg/kgh; Highly acidic resin catalyzer is used in catalytic rectifying tower.
2. in accordance with the method for claim 1, it is characterized in that: tubular reactor temperature of reaction is 110-150 DEG C, pressure is 0.5-1MPa, and material is 2-4h in the inner reaction tube residence time.
3. in accordance with the method for claim 1, it is characterized in that: after heat exchange, in head tank, mixing raw material temperature is 40 ~ 70 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: pre-esterification reactor device is the tubular reactor with inner member, inner member is baffle or twisted blade.
5. according to the method described in claim 1 or 4, to it is characterized in that: tubular reactor is single, or many series windings, or many and connect.
6. in accordance with the method for claim 4, it is characterized in that: twisted blade angle selected by tubular reactor inner member is 0-180 degree, the ratio range of individual blade and diameter is L/D=0.5-2, and unit number is 1-100.
7. in accordance with the method for claim 1, it is characterized in that: tubular reactor is static mixer.
8. in accordance with the method for claim 1, it is characterized in that: the dimethyl adipate of discharging at the bottom of catalytic rectifying tower adopts the method for rectifying to purify further, the further rectifying and dewatering Posterior circle of containing water vapor methyl alcohol that catalytic distillation tower top is discharged uses.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342638B (en) * | 2013-07-31 | 2015-01-14 | 山东兰典生物科技股份有限公司 | Preparation method of dibutyl succinate |
| CN104557536B (en) * | 2013-10-24 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of preparation method of monomethyl succinate |
| CN103694215B (en) * | 2013-12-10 | 2016-05-11 | 安徽丰原发酵技术工程研究有限公司 | A kind of continuity is prepared method and the device of DXPE |
| CN105435726A (en) * | 2015-12-09 | 2016-03-30 | 安徽华业香料股份有限公司 | Continuous reaction device special for synthesizing gamma-lactone |
| CN106220499B (en) * | 2016-08-03 | 2018-05-04 | 中国石油大学(华东) | A kind of device and method for producing dimethyl adipate |
| CN106242970B (en) * | 2016-08-03 | 2018-09-21 | 中国石油大学(华东) | A kind of device and method producing dimethyl adipate |
| CN109748791B (en) * | 2017-11-01 | 2021-08-03 | 中国石油化工股份有限公司 | Energy-saving method for producing dimethyl adipate |
| CN109748790B (en) * | 2017-11-01 | 2021-08-03 | 中国石油化工股份有限公司 | Method for producing dimethyl adipate |
| CN111320543B (en) * | 2018-12-13 | 2022-08-12 | 中国石油化工股份有限公司 | Method for producing dimethyl adipate from adipic acid |
| KR20220067352A (en) * | 2020-11-17 | 2022-05-24 | 주식회사 엘지화학 | Method for preparing diester-based material |
| CN113443983B (en) * | 2021-07-30 | 2022-02-22 | 浙江工业大学 | Production method of dimethyl sebacate |
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| CN101134725A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method and equipment for continuous esterification production of adipic acid dimethyl ester |
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