CN110156562A - A kind of synthesis technology of 1,6-HD - Google Patents
A kind of synthesis technology of 1,6-HD Download PDFInfo
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- CN110156562A CN110156562A CN201910583592.7A CN201910583592A CN110156562A CN 110156562 A CN110156562 A CN 110156562A CN 201910583592 A CN201910583592 A CN 201910583592A CN 110156562 A CN110156562 A CN 110156562A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The present invention relates to organic compound preparation technical fields, specifically disclose one kind 1, the synthesis technology of 6- hexylene glycol, comprising the following steps: the synthesis of raw material dimethyl adipate, reaction solution configuration, hydrogenation reaction device are passed through hydrogen emptying, catalyst reduction, reaction solution reaction, carry out rectifying to the hexylene glycol prepared.The present invention has the characteristics that step is few, simple to operate, safer；Using Cu-Co-Ni catalyst, have the characteristics that with service life length, stable reaction, safe；The conversion ratio of synthesis technology dimethyl adipate of the present invention is 99.6% or more close to very, and hexylene glycol purity of the selectivity of hexylene glycol after 97% or more, rectifying is 98.7% or more；Excessive methanol used in the present invention is able to achieve recycling, solves the environmental issue of post-processing while reducing production cost, so that the technique has certain market competitiveness.
Description
Technical field
The present invention relates to organic compound preparation technical field, the synthesis technology of specifically a kind of 1,6- hexylene glycol.
Background technique
1,6- hexylene glycol is a kind of linear aliphatic Novel Dual alcohol, and English name 1,6-Hexanediol, abridge HDO, point
Son amount is 118.18,42 DEG C of fusing point, 250 DEG C of boiling point, is white solid under room temperature, is dissolved in ethyl alcohol, ethyl acetate and water, does not dissolve in
Toluene equal solvent.
It can be formed different types of with excellent physical and chemical properties with organic acid, isocyanates, anhydride reaction
Derivative, the low melting point and biodegradable polyesters of modified synthesis are used for food casing, high-grade fibers, electrical insulating material；
For high-performance polyurethane elastomer, there is excellent crystallinity and higher mechanical strength, for producing rubber, elastomer, people
Make leather, automobile parts；For polyester plasticizer, have the function of high resistance to volatilization, lower temperature resistance, water resistance and oil resistivity；Separately
Outside, coating and adhesive develop towards nontoxic, nuisanceless direction, the rings such as the water-soluble resin coating of production and polyurethane adhesive
Product is protected, 90% relies on import, and market development prospect is also very wide.
House journal, the U.S. is introduced: first step benzene ring hydrogenation uses Pd/Rh/Al2O3 catalyst, and the second component is added
(the VIIIth B metal, such as Ni, Ru, Pt) raising hydrogenation activity, 140~220 DEG C of reaction temperature, 5.0~17MPa of pressure；Second
Step ester group add hydrogen use Cu-Cr catalyst, copper zinc catalyst or the manganese containing co-catalyst copper-aluminium catalyst, reaction temperature 200~
260 DEG C, 3.1~6.9MPa of pressure.
The patent introduction of commercial firm, South Korea: using in molding copper chromite catalyst, cyclohexanedicarboxyester ester is hydrogenated and is prepared
CHDM, 225~280 DEG C of reaction temperature, hydrogen presses 18.5~30MPa；The first step adds hydrogen to deposit in the ruthenium catalyst being supported on alumina
Under, by aromatic dicarboxylic acid dialkyl ester hydro-reduction, 120~180 DEG C of reaction temperature, hydrogen presses 3~10MPa.
The current country 1,6- hexylene glycol importation dependence is excessively high and producing deficiency needs status obvious, and domestic production capacity rate of expansion
Still relatively slowly.The application market of the current country's 1,6- hexylene glycol is limited, mainly related with the selling at exorbitant prices of product, 1,6- oneself two
The price of the nearly 40,000/t of alcohol product will be higher by nearly 5 times of ethylene glycol or more, fancy price constrain significantly the product at home in it is low
The application of shelves product, is only applied in the expensive goods of part at present.As the rapid development of China's economic, especially downstream are answered
With being continuously increased for field, 1,6 one hexylene glycol demand will have very big growth space.
Summary of the invention
The object of the present invention is to provide a kind of synthesis technologies of 1,6 hexylene glycols, have high income, product purity height, raw material
The advantages that energy recycling, production operation are conveniently, experiment condition is safer.
In order to solve the above technical problems, the present invention provides the synthesis technologies of one kind 1,6- hexylene glycol, comprising the following steps:
The synthesis of S1, raw material dimethyl adipate: adipic acid and methanol and hexamethylene are added in reactor, are added dense
Sulfuric acid flows into oil water separator after taking water out of cooling in 105 DEG C or so progress back flow reactions, hexamethylene；Thiacyclohexane and water are in oil
Stratification in separator, thiacyclohexane enter reactor by upper return and are esterified, and water is discharged by lower part；
Thiacyclohexane after the completion of esterification carries out vacuum distillation and removes extra methanol and hexamethylene, during esterification crude product passes through again
Dimethyl adipate finished product is obtained with after washing, vacuum distillation；
S2, reaction solution configuration: the dimethyl adipate prepared is uniformly mixed to obtain reaction solution with methanol configuration, is put into
Reaction solution sample introduction tank is stand-by；
S3, hydrogenation reaction device are passed through hydrogen emptying: catalyst is added in the catalyst reaction column of hydrogenation reaction device,
It is passed through hydrogen and emptying half an hour is carried out to hydrogenation reaction device, then adjusting pressure is 2MPa pressure maintaining 4 hours；
S4, catalyst reduction: the reaction pressure of adjustment hydrogenation reaction device is 2MPa, hydrogen flowing quantity 200/min, reaction
Temperature is 250 DEG C, carries out reduction reaction to catalyst, reacts 5 hours；
S5, reaction solution reaction: after catalyst reduction, heating is closed under hydrogen circulation state, after cooling catalyst, is pressed
It is passed through hydrogen according to the hydrogen ester molar ratio of 200:1 and guarantees pressure 4.7-5MPa, at 225 DEG C of temperature, by the resulting reaction solution air speed of S2
It is sent in catalyst reaction column, carries out hydrogenation reaction and hexylene glycol is made；
S6, rectifying is carried out to the hexylene glycol prepared: collects 1,6 ethylene glycol, reflux ratio when temperature reaches 195 DEG C or more
It for 1:4, is recycled after the unreacted raw material of the leading portion that 195 DEG C of temperature and the collection of other by-products, collects stream than being 1:1.
Further, the molar ratio of adipic acid described in S1 and methanol is 1:3.5.
Specifically, the additional amount of the concentrated sulfuric acid described in S1 is 1-2g.
Further, the mass ratio of dimethyl adipate described in S2 and methanol is 1:4.
Further, catalyst described in S3 is that Cu-Co-Ni adds hydrogen mixed catalyst.
Specifically, air speed described in S5 is 0.17/h.
The beneficial effects of the present invention are:
(1) conversion ratio of synthesis technology dimethyl adipate of the present invention is 99.6% or more close to very, oneself two
Hexylene glycol purity of the selectivity of alcohol after 97% or more, rectifying is 98.7% or more.
(2) excessive methanol used in the present invention is able to achieve recycling, solves post-processing while reducing production cost
Environmental issue, so that the technique has certain market competitiveness.
(3) present invention uses Cu-Zn-Al catalyst, has the characteristics that with service life length, stable reaction, safe.
(4) present invention has the characteristics that step is few, simple to operate, reaction pressure is lower safer.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1:
The synthesis of S1, raw material dimethyl adipate
Adipic acid and methanol are added in reactor with the molar ratio of 1:3.5 and water entrainer hexamethylene, it is dense that 1.5g is added
Sulfuric acid makees catalyst, and in 105 DEG C or so progress back flow reactions, hexamethylene azeotrope with water takes water out of, after condenser pipe cooling
Flow into oil water separator；Thiacyclohexane and the water stratification in oil water separator, water are discharged by lower part, and thiacyclohexane is by upper return
Enter reactor to be esterified；
Thiacyclohexane after the completion of esterification carries out vacuum distillation and removes extra methanol and hexamethylene, during esterification crude product passes through again
Dimethyl adipate finished product is obtained with after washing, vacuum distillation；
S2, reaction solution configuration:
The dimethyl adipate prepared is reacted with methanol as what the proportion configuration 10000g mixing of quality 1:4 shook up
It is stand-by to be put into reaction solution sample introduction tank for liquid；
S3, hydrogenation reaction device are passed through hydrogen emptying:
Catalyst is added in the catalyst reaction column of hydrogenation reaction device, after the installation of catalyst reaction column, connects and adds
Hydrogen reaction unit power supply opens pressure and flow controller, is passed through hydrogen with 120/min and carries out emptying half to hydrogenation reaction device
Hour, then adjusting pressure is 2MPa pressure maintaining 4 hours, to check the air-tightness of hydrogenation reaction device；
S4, catalyst reduction:
The reaction pressure for adjusting hydrogenation reaction device is 2MPa, and hydrogen flowing quantity 200/min, reaction temperature is 250 DEG C, right
Catalyst carries out reduction reaction, reacts 5 hours；
S5, reaction solution reaction:
After catalyst reduction, heating is closed under hydrogen circulation state, after cooling catalyst, according to the hydrogen ester of 200:1
Molar ratio is passed through hydrogen and guarantees pressure 4.7-5MPa, and sets reaction temperature as 225 DEG C, opens heating and 50 DEG C of heat preservation settings,
Reactor is allowed to start to warm up to 225 DEG C, after temperature reaches, being passed through peristaltic pump, that the resulting reaction solution air speed of S2 is sent to catalyst is anti-
Ying Zhuzhong carries out hydrogenation reaction and hexylene glycol is made；
S6, rectifying is carried out to the hexylene glycol prepared:
1,6 ethylene glycol are collected when temperature reaches 195 DEG C or more, the purity of reflux ratio 1:4, the hexylene glycol after collection are
98.7%, it is recycled after the unreacted raw material of the leading portion that 195 DEG C of temperature and the collection of other by-products, collects stream than being 1:1.
Embodiment 2:
The synthesis of S1, raw material dimethyl adipate
Adipic acid and methanol are added in reactor with the molar ratio of 1:3.5 and water entrainer hexamethylene, it is dense that 1.5g is added
Sulfuric acid makees catalyst, and in 105 DEG C or so progress back flow reactions, hexamethylene azeotrope with water takes water out of, after condenser pipe cooling
Flow into oil water separator；Thiacyclohexane and the water stratification in oil water separator, water are discharged by lower part, and thiacyclohexane is by upper return
Enter reactor to be esterified；
Thiacyclohexane after the completion of esterification carries out vacuum distillation and removes extra methanol and hexamethylene, during esterification crude product passes through again
Dimethyl adipate finished product is obtained with after washing, vacuum distillation；
S2, reaction solution configuration:
The dimethyl adipate prepared is mixed into the reaction solution shaken up by the proportion configuration 5000g of quality 1:4 with methanol,
It is stand-by to be put into reaction solution sample introduction tank；
S3, hydrogenation reaction device are passed through hydrogen emptying:
Catalyst is added in the catalyst reaction column of hydrogenation reaction device, after the installation of catalyst reaction column, connects and adds
Hydrogen reaction unit power supply opens pressure and flow controller, is passed through hydrogen with 120/min and carries out emptying half to hydrogenation reaction device
Hour, then adjusting pressure is 2MPa pressure maintaining 4 hours, to check the air-tightness of hydrogenation reaction device；
S4, catalyst reduction:
The reaction pressure for adjusting hydrogenation reaction device is 2MPa, and hydrogen flowing quantity 200/min, reaction temperature is 250 DEG C, right
Catalyst carries out reduction reaction, reacts 5 hours；
S5, reaction solution reaction:
After catalyst reduction, heating is closed under hydrogen circulation state, after cooling catalyst, according to the hydrogen ester of 200:1
Molar ratio is passed through hydrogen and guarantees pressure 4.7-5MPa, and sets reaction temperature as 225 DEG C, opens heating and 50 DEG C of heat preservation settings,
Reactor is allowed to start to warm up to 225 DEG C, after temperature reaches, being passed through peristaltic pump, that the resulting reaction solution air speed of S2 is sent to catalyst is anti-
Ying Zhuzhong carries out hydrogenation reaction and hexylene glycol is made；
S6, rectifying is carried out to the hexylene glycol prepared:
1,6 ethylene glycol are collected when temperature reaches 195 DEG C or more, the purity of reflux ratio 1:4, the hexylene glycol after collection are
98.9%, it is recycled after the unreacted raw material of the leading portion that 195 DEG C of temperature and the collection of other by-products, collects stream than being 1:1.
Embodiment 3:
The synthesis of S1, raw material dimethyl adipate
Adipic acid and methanol are added in reactor with the molar ratio of 1:3.5 and water entrainer hexamethylene, it is dense that 1.5g is added
Sulfuric acid makees catalyst, and in 105 DEG C or so progress back flow reactions, hexamethylene azeotrope with water takes water out of, after condenser pipe cooling
Flow into oil water separator；Thiacyclohexane and the water stratification in oil water separator, water are discharged by lower part, and thiacyclohexane is by upper return
Enter reactor to be esterified；
Thiacyclohexane after the completion of esterification carries out vacuum distillation and removes extra methanol and hexamethylene, during esterification crude product passes through again
Dimethyl adipate finished product is obtained with after washing, vacuum distillation；
S2, reaction solution configuration:
The dimethyl adipate prepared is mixed into the reaction solution shaken up by the proportion configuration 3000g of quality 1:4 with methanol,
It is stand-by to be put into reaction solution sample introduction tank；
S3, hydrogenation reaction device are passed through hydrogen emptying:
Catalyst is added in the catalyst reaction column of hydrogenation reaction device, after the installation of catalyst reaction column, connects and adds
Hydrogen reaction unit power supply opens pressure and flow controller, is passed through hydrogen with 120/min and carries out emptying half to hydrogenation reaction device
Hour, then adjusting pressure is 2MPa pressure maintaining 4 hours, to check the air-tightness of hydrogenation reaction device；
S4, catalyst reduction:
The reaction pressure for adjusting hydrogenation reaction device is 2MPa, and hydrogen flowing quantity 200/min, reaction temperature is 250 DEG C, right
Catalyst carries out reduction reaction, reacts 5 hours；
S5, reaction solution reaction:
After catalyst reduction, heating is closed under hydrogen circulation state, after cooling catalyst, according to the hydrogen ester of 200:1
Molar ratio is passed through hydrogen and guarantees pressure 4.7-5MPa, and sets reaction temperature as 225 DEG C, opens heating and 50 DEG C of heat preservation settings,
Reactor is allowed to start to warm up to 225 DEG C, after temperature reaches, being passed through peristaltic pump, that the resulting reaction solution air speed of S2 is sent to catalyst is anti-
Ying Zhuzhong carries out hydrogenation reaction and hexylene glycol is made；
S6, rectifying is carried out to the hexylene glycol prepared:
1,6 ethylene glycol are collected when temperature reaches 195 DEG C or more, the purity of reflux ratio 1:4, the hexylene glycol after collection are
98.7%, it is recycled after the unreacted raw material of the leading portion that 195 DEG C of temperature and the collection of other by-products, collects stream than being 1:1.
Above disclosed is only presently preferred embodiments of the present invention, cannot limit the right of the present invention with this certainly
Range, therefore equivalent changes made in accordance with the claims of the present invention, are still within the scope of the present invention.
Claims (6)
1. one kind 1, the synthesis technology of 6- hexylene glycol, which comprises the following steps:
The synthesis of S1, raw material dimethyl adipate: adipic acid and methanol and hexamethylene are added in reactor, and the concentrated sulfuric acid is added
In 100 DEG C of -110 DEG C of progress back flow reactions, hexamethylene flows into oil water separator after taking water out of cooling；Thiacyclohexane and water are in grease
Stratification in separator, thiacyclohexane enter reactor by upper return and are esterified, and water is discharged by lower part；
Thiacyclohexane after the completion of esterification carries out vacuum distillation and removes extra methanol and hexamethylene, esterification crude product is neutralized again,
Dimethyl adipate finished product is obtained after washing, vacuum distillation；
S2, reaction solution configuration: the dimethyl adipate prepared is uniformly mixed to obtain reaction solution with methanol configuration, is put into reaction
Liquid sample introduction tank is stand-by；
S3, hydrogenation reaction device are passed through hydrogen emptying: catalyst is added in the catalyst reaction column of hydrogenation reaction device, is passed through
Hydrogen carries out emptying half an hour to hydrogenation reaction device, then adjusting pressure is 2MPa pressure maintaining 4 hours, checks air-tightness；
S4, catalyst reduction: the reaction pressure of adjustment hydrogenation reaction device is 2MPa, hydrogen flowing quantity 200/min, reaction temperature
It is 280 DEG C, reduction 5 hours is carried out to catalyst；
S5, reaction solution reaction: after catalyst reduction, closing heating under hydrogen circulation state, after cooling catalyst, according to
The hydrogen ester molar ratio of 200:1 is passed through hydrogen and guarantees pressure 4.7-5MPa, and at 225 DEG C of temperature, the resulting reaction solution of S2 is passed through stream
Amount pump air speed is sent in catalyst reaction column, carries out hydrogenation reaction and hexylene glycol is made；
S6, rectifying is carried out to the hexylene glycol prepared: collects 1,6 ethylene glycol when temperature reaches 195 DEG C or more, reflux ratio 1:
4。
2. a kind of synthesis technology of 1,6- hexylene glycol according to claim 1, which is characterized in that adipic acid described in S1 and
The molar ratio of methanol is 1:3.5.
3. a kind of synthesis technology of 1,6- hexylene glycol according to claim 1, which is characterized in that the concentrated sulfuric acid described in S1
Additional amount is 1-2g.
4. a kind of synthesis technology of 1,6- hexylene glycol according to claim 1, which is characterized in that adipic acid two described in S2
The mass ratio of methyl esters and methanol is 1:4.
5. a kind of synthesis technology of 1,6- hexylene glycol according to claim 1, which is characterized in that catalyst described in S3 is
Cu-Co-Ni mixed catalyst.
6. a kind of synthesis technology of 1,6- hexylene glycol according to claim 1, which is characterized in that air speed described in S5 is
0.17/h。
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