CN108516934B - Production process for producing cyclohexyl formate through bulkhead reaction rectification - Google Patents
Production process for producing cyclohexyl formate through bulkhead reaction rectification Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 86
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 84
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 60
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000019253 formic acid Nutrition 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 30
- 239000007791 liquid phase Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005192 partition Methods 0.000 claims description 9
- 238000005485 electric heating Methods 0.000 claims description 7
- 238000000066 reactive distillation Methods 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WZRXFPOWHQQSRJ-UHFFFAOYSA-N cyclohexyloxyboronic acid Chemical compound OB(O)OC1CCCCC1 WZRXFPOWHQQSRJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a production process for producing cyclohexyl formate by bulkhead reaction rectification, which comprises the following steps: (1) adding 50 weight percent of cyclohexyl formate, 25 weight percent of cyclohexanol and 25 weight percent of formic acid into a tower kettle of a main rectifying tower, adding cyclohexanol into a tower kettle of an auxiliary rectifying tower, wherein the liquid level of the tower kettle reaches 70 percent, starting a reboiler I and a reboiler II, and controlling the pressure in the tower to be 10-15 kPa; (2) when the temperature of the tower bottom of the main rectifying tower reaches 90-100 ℃, cyclohexanol and formic acid are added into the main rectifying tower to react under the action of a solid acid catalyst, water is removed from the tower top, the cyclohexanol is recovered, cyclohexyl formate is extracted from the tower bottom of the main rectifying tower, and the cyclohexanol is extracted from the tower bottom of the auxiliary rectifying tower and is recovered and reused. The method has the advantages of simple process, reduction of production devices, saving of production cost, solving of the problems of complex process, high energy consumption and low yield of the original process for producing the cyclohexyl formate by directly reacting the formic acid and the cyclohexanol, and high purity of the obtained cyclohexyl formate.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a production process for producing cyclohexyl formate through bulkhead reaction rectification.
Background
Cyclohexyl formate is a liquid at room temperature. It is popular because it is commonly used as synthetic perfume and as dispersant in paints and inks, with good results. Because the molecule of the compound contains reductive aldehyde group, the compound is usually synthesized by multiple steps by taking boric acid, cyclohexanol and formic acid as raw materials. The synthetic route is reported a lot in the last decade, but is mostly an improvement in terms of conditions. The synthesis of the compound is generally that boric acid reacts with cyclohexanol to obtain boric acid cyclohexyl ester, and then formic acid is used for acid substitution reaction, or phosgene is firstly used, and then HCONMe is used2And (3) reacting. These reaction conditions are complicated or raw materials are not readily available, and the flow is long and the yield is low. The prior method for synthesizing cyclohexyl formate by one-step reaction of formic acid and cyclohexanol. However, the common synthesis process has the defects of too large acid-alcohol ratio of reaction raw materials, long reaction time, easy dehydration of cyclohexanol to cyclohexene in the reaction, long purification process of subsequent products and the like.
Disclosure of Invention
The invention aims to solve the problems of complex process, high energy consumption and low yield of the original process for producing the cyclohexyl formate by directly reacting the formic acid and the cyclohexanol, and provides a production process for producing the cyclohexyl formate by dividing wall reaction rectification.
In order to achieve the purpose, the technical scheme of the invention is as follows: a production process for producing cyclohexyl formate by bulkhead reaction rectification is characterized by comprising the following steps:
(1) adding 50 weight percent of cyclohexyl formate, 25 weight percent of cyclohexanol and 25 weight percent of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, enabling liquid levels of the two towers to reach 70%, starting a reboiler I and a reboiler II, and controlling the pressure in the bulkhead reactive rectifying tower to be 10-15 kPa;
(2) when the temperature of the tower bottom of the main rectifying tower reaches 90-100 ℃, cyclohexanol and formic acid are added into the main rectifying tower and react under the action of a solid acid catalyst, a reflux liquid phase flows into the auxiliary rectifying tower from a second tower plate of the bulkhead reactive rectifying tower from top to bottom, water is removed from the tower top of the bulkhead reactive rectifying tower, cyclohexanol is recovered, cyclohexyl formate is extracted from the tower bottom of the main rectifying tower, and cyclohexanol is extracted from the tower bottom of the auxiliary rectifying tower and recycled;
a main rectifying tower and an auxiliary rectifying tower are arranged in the bulkhead reaction rectifying tower, the main rectifying tower and the auxiliary rectifying tower are separated by a vertical partition plate, a transverse plate is arranged at the bottom of the auxiliary rectifying tower, two tower plates are arranged at the upper part of the bulkhead reaction rectifying tower, the top of the vertical partition plate is connected with the tower plates, and the bottom of the vertical partition plate is connected with the transverse plate;
the main rectifying tower comprises from bottom to top: the device comprises a main rectifying tower kettle, a stripping section, a reaction section and a rectifying section, wherein theta ring-shaped packing is filled in the stripping section and the rectifying section, a solid acid catalyst is filled in the reaction section, feed ports are formed in the upper end and the lower end of the reaction section, cyclohexanol is fed from the feed port in the upper end of the reaction section, formic acid is fed from the feed port in the lower end of the reaction section, the main rectifying tower kettle is connected with a reboiler I, one end of the reboiler I is connected with a liquid phase outlet of the main rectifying tower kettle, and the other end of the reboiler I is connected with a gas phase inlet of the main rectifying tower kettle;
the auxiliary rectifying tower comprises from bottom to top: the auxiliary rectifying tower kettle is connected with a reboiler II, one end of the reboiler II is connected with a liquid phase outlet of the auxiliary rectifying tower kettle, and the other end of the reboiler II is connected with a gas phase inlet of the auxiliary rectifying tower kettle;
the gas phase outlet at the top of the reaction rectifying tower of the bulkhead is sequentially connected with a condenser, a reflux tank, a heat exchanger and a liquid-liquid phase separator, one end of the reflux tank connected with the heat exchanger is also connected with the liquid phase inlet at the top of the reaction rectifying tower of the bulkhead, the liquid-liquid phase separator comprises a water phase outlet and an oil phase outlet, and the oil phase outlet is connected with a feed inlet at the upper end of the reaction section; and a kettle extraction outlet of the auxiliary rectifying tower is connected with a feed inlet at the upper end of the reaction section.
Further, the method comprises the following steps of; and an electric heating wire is wound outside the bulkhead reactive distillation tower for heat preservation.
Further, the method comprises the following steps of; the step (2) is specifically as follows: when the temperature of the tower bottom of the main rectifying tower reaches 90-100 ℃, adding formic acid and cyclohexanol into the reaction section according to the molar ratio of cyclohexanol to formic acid of 1.0-3.0:1, stopping feeding when the next door reaction rectifying tower starts to reflux, enabling a reflux liquid phase to flow into the secondary rectifying tower from a second tower plate counted from top to bottom of the next door reaction rectifying tower, fully refluxing for 30min, feeding cyclohexanol and formic acid again, simultaneously, the top of the bulkhead reaction rectifying tower, the main rectifying tower kettle and the auxiliary rectifying tower kettle start to be extracted, the reflux ratio of the top of the tower is controlled to be 0.5-1.6, the liquid levels of the main rectifying tower kettle and the auxiliary rectifying tower kettle are both 50%, the liquid level of a reflux tank is 50%, a mixture of water and cyclohexanol extracted from the top of the tower is cooled to 40 ℃ through a heat exchanger, the mixture enters a liquid-liquid phase separator for separation, a water phase is removed, an oil phase returns to the upper end of the reaction section for feeding, and cyclohexanol extracted from the auxiliary rectifying tower kettle returns to the upper end of the reaction section for feeding.
Further, the method comprises the following steps of; the solid acid catalyst is a molecular sieve or a cation exchange resin.
The invention has the beneficial effects that: the invention adopts the process of bulkhead reaction rectification to produce the cyclohexyl formate, the formic acid and the cyclohexanol react to synthesize the cyclohexyl formate in one step, the solid acid is used as the catalyst, the reaction and the rectification are combined and completed by one tower, the process is simple, the production device is reduced, the production cost is saved, the problems of complex process, high energy consumption and low yield of the original process for producing the cyclohexyl formate by directly reacting the formic acid and the cyclohexanol are solved, and the purity of the obtained cyclohexyl formate is high.
Drawings
FIG. 1 is a schematic diagram of a divided wall reactive distillation column apparatus for producing cyclohexyl formate in accordance with an embodiment of the present invention.
Wherein: 1. a reboiler I; 2. a reboiler II; 3. a stripping section; 4. a reaction section; 5. a rectifying section; 6. a secondary rectification column; 7. a condenser; 8. a reflux tank; 9. a heat exchanger; 10. liquid-liquid phase separator.
Detailed Description
As shown in FIG. 1, the device for producing the bulkhead reactive distillation column of the cyclohexyl formate comprises a bulkhead reactive distillation column;
a main rectifying tower and an auxiliary rectifying tower 6 are arranged inside the bulkhead reaction rectifying tower, the main rectifying tower and the auxiliary rectifying tower 6 are separated by a vertical partition plate, a transverse plate is arranged at the bottom of the auxiliary rectifying tower 6, two tower plates are arranged at the upper part of the bulkhead reaction rectifying tower, the top of the vertical partition plate is connected with the tower plates, and the bottom of the vertical partition plate is connected with the transverse plate;
the main rectifying tower comprises from bottom to top: the device comprises a main rectifying tower kettle, a stripping section 3, a reaction section 4 and a rectifying section 5, wherein theta ring-shaped packing is filled in the stripping section 3 and the rectifying section 5, a solid acid catalyst is filled in the reaction section 4, feed inlets are formed in the upper end and the lower end of the reaction section 4, cyclohexanol is fed from the feed inlet at the upper end of the reaction section 4, formic acid is fed from the feed inlet at the lower end of the reaction section 4, the main rectifying tower kettle is connected with a reboiler I1, one end of the reboiler I1 is connected with a liquid phase outlet of the main rectifying tower kettle, and the other end of the reboiler I1 is connected with a gas phase inlet of the main rectifying tower kettle;
the auxiliary rectifying tower 6 comprises from bottom to top: the device comprises an auxiliary rectifying tower kettle and a rectifying section, wherein the auxiliary rectifying tower kettle is connected with a reboiler II 2, one end of the reboiler II 2 is connected with a liquid phase outlet of the auxiliary rectifying tower kettle, and the other end of the reboiler II is connected with a gas phase inlet of the auxiliary rectifying tower kettle;
the gas phase outlet at the top of the reaction rectifying tower of the next door is sequentially connected with a condenser 7, a reflux tank 8, a heat exchanger 9 and a liquid-liquid phase separator 10, one end of the reflux tank 8 connected with the heat exchanger 9 is also connected with a liquid phase inlet at the top of the reaction rectifying tower of the next door, the liquid-liquid phase separator 10 comprises a water phase outlet and an oil phase outlet, and the oil phase outlet is connected with a feed inlet at the upper end of the reaction section 4; the bottom extraction port of the auxiliary rectifying tower is connected with the feed inlet at the upper end of the reaction section 4;
and an electric heating wire is wound outside the bulkhead reactive distillation tower for heat preservation.
Example 1
A production process for producing cyclohexyl formate by bulkhead reaction rectification comprises the following steps:
(1) adding 50% by weight of cyclohexyl formate, 25% by weight of cyclohexanol and 25% by weight of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, wherein the liquid levels of the two towers reach 70%, adding a certain amount of zeolite into the main rectifying tower kettle and the auxiliary rectifying tower kettle to prevent bumping, starting a reboiler I1 and a reboiler II 2, starting an electric heating wire switch to preserve heat, and controlling the pressure in the bulkhead reactive rectifying tower to be 15 kPa;
(2) when the temperature of a tower kettle of a main rectifying tower reaches 100 ℃, formic acid is added into a feed inlet at the lower end of a reaction section 4, cyclohexanol is added into a feed inlet at the upper end of the reaction section 4, the total cyclohexanol is fed at 5mol/h, the feeding amount of the formic acid is 5mol/h, the feeding temperature is room temperature, the reaction is carried out under the action of a catalyst molecular sieve, the feeding is stopped when a bulkhead reactive rectifying tower starts to reflux, a reflux liquid phase flows into an auxiliary rectifying tower 6 from a second tower plate which is counted from top to bottom of the bulkhead reactive rectifying tower, the cyclohexanol and the formic acid are fed again after the total reflux is carried out for 30min, simultaneously, the tower top, the tower kettle of the main rectifying tower and the tower kettle of the auxiliary rectifying tower start to extract, the reflux ratio of the tower top is controlled to be 0.5, the liquid levels of the tower kettle of the main rectifying tower and the auxiliary rectifying tower are 50%, the liquid level of a reflux tank 8 is 50%, a mixture of water and the, removing the water phase, and returning the oil phase to the upper end of the reaction section 4 for feeding; the cyclohexanol extracted from the tower bottom of the secondary rectification tower returns to the upper end of the reaction section 4 for feeding; and (3) taking out the cyclohexyl formate from the tower bottom of the main rectifying tower.
When the production system reaches a steady state, the composition of the bottom of the main rectifying tower is shown in table 1, and the composition of the produced water at the top of the tower is shown in table 2. The formic acid conversion was 99.51%.
TABLE 1 Main rectifying column tank composition
TABLE 2 composition of the overhead Water
Example 2
A production process for producing cyclohexyl formate by bulkhead reaction rectification comprises the following steps:
(1) adding 50% by weight of cyclohexyl formate, 25% by weight of cyclohexanol and 25% by weight of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, wherein the liquid levels of the two towers reach 70%, adding a certain amount of zeolite into the main rectifying tower kettle and the auxiliary rectifying tower kettle to prevent bumping, starting a reboiler I1 and a reboiler II 2, starting an electric heating wire switch to preserve heat, and controlling the pressure in the bulkhead reactive rectifying tower to be 10 kPa;
(2) when the temperature of a tower kettle of a main rectifying tower reaches 90 ℃, formic acid is added into a feed inlet at the lower end of a reaction section 4, cyclohexanol is added into a feed inlet at the upper end of the reaction section 4, the total cyclohexanol feed is 9mol/h, the feed amount of the formic acid is 5mol/h, the feed temperature is room temperature, the reaction is carried out under the action of catalyst cation exchange resin, the feed is stopped when a bulkhead reactive rectifying tower starts to reflux, a reflux liquid phase flows into an auxiliary rectifying tower 6 from the second tower plate from top to bottom of the bulkhead reactive rectifying tower, the cyclohexanol and the formic acid are fed again after the total reflux is carried out for 30min, the tower top, the tower kettle of the main rectifying tower and the tower kettle of the auxiliary rectifying tower start to extract, the reflux ratio of the tower top is controlled to be 1.0, the liquid levels of the tower kettle of the main rectifying tower and the tower kettle of the auxiliary rectifying tower are 50%, the liquid level of a reflux tank 8 is 50%, a, the mixture enters a liquid-liquid phase separator 10 for separation, a water phase is removed, and an oil phase returns to the upper end of the reaction section 4 for feeding; the cyclohexanol extracted from the tower bottom of the secondary rectification tower returns to the upper end of the reaction section 4 for feeding; and (3) taking out the cyclohexyl formate from the tower bottom of the main rectifying tower.
When the production system reached a steady state, the composition of the main rectifying tower bottom was as shown in table 3, and the composition of the overhead produced water was as shown in table 4. The conversion of formic acid was 99.63%.
TABLE 3 main rectifying column bottom composition
TABLE 4 composition of the overhead Water
Example 3
A production process for producing cyclohexyl formate by bulkhead reaction rectification comprises the following steps:
(1) adding 50% by weight of cyclohexyl formate, 25% by weight of cyclohexanol and 25% by weight of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, wherein the liquid levels of the two towers reach 70%, adding a certain amount of zeolite into the main rectifying tower kettle and the auxiliary rectifying tower kettle to prevent bumping, starting a reboiler I1 and a reboiler II 2, starting an electric heating wire switch to preserve heat, and controlling the pressure in the bulkhead reactive rectifying tower to be 15 kPa;
(2) when the temperature of a tower kettle of a main rectifying tower reaches 90 ℃, formic acid is added into a feed inlet at the lower end of a reaction section 4, cyclohexanol is added into a feed inlet at the upper end of the reaction section 4, the total cyclohexanol is fed at 10mol/h, the feeding amount of the formic acid is 5mol/h, the feeding temperature is room temperature, the reaction is carried out under the action of a catalyst molecular sieve, the feeding is stopped when a bulkhead reactive rectifying tower starts to reflux, a reflux liquid phase flows into an auxiliary rectifying tower 6 from a second tower plate which is counted from top to bottom of the bulkhead reactive rectifying tower, the cyclohexanol and the formic acid are fed again after the total reflux is carried out for 30min, simultaneously, the tower top, the tower kettle of the main rectifying tower and the tower kettle of the auxiliary rectifying tower start to extract, the reflux ratio of the tower top is controlled to be 0.5, the liquid levels of the tower kettle of the main rectifying tower and the auxiliary rectifying tower are both 50%, the liquid level of a reflux tank 8 is 50%, a mixture of water and, removing the water phase, and returning the oil phase to the upper end of the reaction section 4 for feeding; the cyclohexanol extracted from the tower bottom of the secondary rectification tower returns to the upper end of the reaction section 4 for feeding; and (3) taking out the cyclohexyl formate from the tower bottom of the main rectifying tower.
When the production system reached a steady state, the composition of the main rectifying tower bottom was as shown in table 5, and the composition of the overhead produced water was as shown in table 6. The formic acid conversion was 99.47%.
TABLE 5 Main rectifying column bottom composition
TABLE 6 composition of the overhead Water
Example 4
A production process for producing cyclohexyl formate by bulkhead reaction rectification comprises the following steps:
(1) adding 50% by weight of cyclohexyl formate, 25% by weight of cyclohexanol and 25% by weight of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, wherein the liquid levels of the two towers reach 70%, adding a certain amount of zeolite into the main rectifying tower kettle and the auxiliary rectifying tower kettle to prevent bumping, starting a reboiler I1 and a reboiler II 2, starting an electric heating wire switch to preserve heat, and controlling the pressure in the bulkhead reactive rectifying tower to be 10 kPa;
(2) when the temperature of a tower kettle of a main rectifying tower reaches 90 ℃, formic acid is added into a feed inlet at the lower end of a reaction section 4, cyclohexanol is added into a feed inlet at the upper end of the reaction section 4, the total cyclohexanol is fed at 15mol/h, the feeding amount of the formic acid is 5mol/h, the feeding temperature is room temperature, the reaction is carried out under the action of a catalyst cation exchange resin, the feeding is stopped when a bulkhead reactive rectifying tower starts to reflux, a reflux liquid phase flows into an auxiliary rectifying tower 6 from a second tower plate which is arranged from top to bottom of the bulkhead reactive rectifying tower, the cyclohexanol and the formic acid are fed again after the total reflux is carried out for 30min, the tower top, the tower kettle of the main rectifying tower and the tower kettle of the auxiliary rectifying tower begin to extract, the reflux ratio of the tower top is controlled to be 1.6, the liquid levels of the tower kettle of the main rectifying tower and the auxiliary rectifying tower are 50%, the liquid level of a reflux tank 8 is controlled, the mixture enters a liquid-liquid phase separator 10 for separation, a water phase is removed, and an oil phase returns to the upper end of the reaction section 4 for feeding; the cyclohexanol extracted from the tower bottom of the secondary rectification tower returns to the upper end of the reaction section 4 for feeding; and (3) taking out the cyclohexyl formate from the tower bottom of the main rectifying tower.
When the production system reached a steady state, the composition of the main rectifying column bottom was as shown in table 7, and the composition of the overhead produced water was as shown in table 8. The formic acid conversion was 99.62%.
TABLE 7 main rectification column bottom composition
TABLE 8 composition of the overhead Water
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (4)
1. A production process for producing cyclohexyl formate by bulkhead reaction rectification is characterized by comprising the following steps:
(1) adding 50 weight percent of cyclohexyl formate, 25 weight percent of cyclohexanol and 25 weight percent of formic acid into a main rectifying tower kettle of a bulkhead reactive rectifying tower, adding cyclohexanol into an auxiliary rectifying tower kettle, enabling liquid levels of the two towers to reach 70%, starting a reboiler I and a reboiler II, and controlling the pressure in the bulkhead reactive rectifying tower to be 10-15 kPa;
(2) when the temperature of the tower bottom of the main rectifying tower reaches 90-100 ℃, cyclohexanol and formic acid are added into the main rectifying tower and react under the action of a solid acid catalyst, a reflux liquid phase flows into the auxiliary rectifying tower from a second tower plate of the bulkhead reactive rectifying tower from top to bottom, water is removed from the tower top of the bulkhead reactive rectifying tower, the cyclohexanol is recovered, cyclohexyl formate is extracted from the tower bottom of the main rectifying tower, and cyclohexanol is extracted from the tower bottom of the auxiliary rectifying tower and recovered for reuse;
a main rectifying tower and an auxiliary rectifying tower are arranged in the bulkhead reaction rectifying tower, the main rectifying tower and the auxiliary rectifying tower are separated by a vertical partition plate, a transverse plate is arranged at the bottom of the auxiliary rectifying tower, two tower plates are arranged at the upper part of the bulkhead reaction rectifying tower, the top of the vertical partition plate is connected with the tower plates, and the bottom of the vertical partition plate is connected with the transverse plate;
the main rectifying tower comprises from bottom to top: the distillation tower comprises a main distillation tower kettle, a stripping section, a reaction section and a rectification section, wherein the stripping section and the rectification section are filled with materialsθThe reaction section is filled with a solid acid catalyst, the upper end and the lower end of the reaction section are provided with feed inlets, cyclohexanol is fed from the feed inlet at the upper end of the reaction section, formic acid is fed from the feed inlet at the lower end of the reaction section, the tower kettle of the main rectifying tower is connected with a reboiler I, one end of the reboiler I is connected with a liquid phase outlet of the tower kettle of the main rectifying tower, and the other end of the reboiler I is connected with a gas phase inlet of the tower kettle of the main rectifying tower;
the auxiliary rectifying tower comprises from bottom to top: the auxiliary rectifying tower kettle is connected with a reboiler II, one end of the reboiler II is connected with a liquid phase outlet of the auxiliary rectifying tower kettle, and the other end of the reboiler II is connected with a gas phase inlet of the auxiliary rectifying tower kettle;
the gas phase outlet at the top of the reaction rectifying tower of the bulkhead is sequentially connected with a condenser, a reflux tank, a heat exchanger and a liquid-liquid phase separator, one end of the reflux tank connected with the heat exchanger is also connected with the liquid phase inlet at the top of the reaction rectifying tower of the bulkhead, the liquid-liquid phase separator comprises a water phase outlet and an oil phase outlet, and the oil phase outlet is connected with a feed inlet at the upper end of the reaction section; and a kettle extraction outlet of the auxiliary rectifying tower is connected with a feed inlet at the upper end of the reaction section.
2. The production process according to claim 1, characterized in that: and an electric heating wire is wound outside the bulkhead reactive distillation tower for heat preservation.
3. The production process according to claim 1, wherein the step (2) is specifically: when the temperature of the tower bottom of the main rectifying tower reaches 90-100 ℃, adding formic acid and cyclohexanol into the reaction section according to the molar ratio of cyclohexanol to formic acid of 1.0-3.0:1, stopping feeding when the next door reaction rectifying tower starts to reflux, enabling a reflux liquid phase to flow into the secondary rectifying tower from a second tower plate counted from top to bottom of the next door reaction rectifying tower, fully refluxing for 30min, feeding cyclohexanol and formic acid again, simultaneously, the top of the bulkhead reaction rectifying tower, the main rectifying tower kettle and the auxiliary rectifying tower kettle start to be extracted, the reflux ratio of the top of the tower is controlled to be 0.5-1.6, the liquid levels of the main rectifying tower kettle and the auxiliary rectifying tower kettle are both 50%, the liquid level of a reflux tank is 50%, a mixture of water and cyclohexanol extracted from the top of the tower is cooled to 40 ℃ through a heat exchanger, the mixture enters a liquid-liquid phase separator for separation, a water phase is removed, an oil phase returns to the upper end of the reaction section for feeding, and cyclohexanol extracted from the auxiliary rectifying tower kettle returns to the upper end of the reaction section for feeding.
4. The production process according to claim 1, characterized in that: the solid acid catalyst is a molecular sieve or a cation exchange resin.
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| CN112569620B (en) * | 2021-01-09 | 2022-04-01 | 福州大学 | Process system for preparing cyclopentyl methyl ether by using bulkhead reaction rectifying tower |
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| CN101362692A (en) * | 2008-09-24 | 2009-02-11 | 中国石油大学(华东) | Technology method for producing isopropyl trifluoroacetate and apparatus |
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| GB294396A (en) * | 1927-09-19 | 1928-07-26 | Ig Farbenindustrie Ag | Improved process for the manufacture and production of formates |
| CN101367724A (en) * | 2008-09-18 | 2009-02-18 | 中国石油大学(华东) | Method and apparatus for synthesis of isopropyl acetate |
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