CN111499609A - Preparation method of Kunlun musk - Google Patents
Preparation method of Kunlun musk Download PDFInfo
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- CN111499609A CN111499609A CN202010339453.2A CN202010339453A CN111499609A CN 111499609 A CN111499609 A CN 111499609A CN 202010339453 A CN202010339453 A CN 202010339453A CN 111499609 A CN111499609 A CN 111499609A
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- ethylene glycol
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- 241000402754 Erythranthe moschata Species 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 398
- 238000000034 method Methods 0.000 claims abstract description 59
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 47
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000003205 fragrance Substances 0.000 abstract description 5
- 235000019640 taste Nutrition 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000000047 product Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 19
- 239000002351 wastewater Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000498 cooling water Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002304 perfume Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- -1 cyclic ethylene ester Chemical class 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000972155 Moschus Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of Kunlun musk, which takes α, omega-tridecanedioic acid and ethylene glycol as raw materials, and prepares Kunlun musk through low-temperature polycondensation and low-temperature depolymerization reaction, wherein the polycondensation reaction only needs 170 ℃, titanium isopropoxide is used as a depolymerization catalyst, and an entrainer ethylene glycol is matched, and the depolymerization reaction temperature only needs 220-240 ℃, so that compared with the prior art, the method has the advantages of high yield, mild conditions, higher purity of the obtained Kunlun musk product than or equal to 99%, purer fragrance, no bad miscellaneous gases such as burnt taste and the like, and better quality.
Description
Technical Field
The invention relates to the field of a Kunlun musk production process, in particular to a preparation method of Kunlun musk.
Background
The musk is honored as the king of the perfume, and the fragrance is pure, strong and lasting, which is outstanding in the perfume family. At present, the annual output of synthesized musk type perfume in the world is more than 10000 tons, wherein 3000-4000 tons of high-grade macrocyclic musk is adopted.
Wherein, the Kunlun musk (n-tridecane diacid cyclic ethylene ester) is the main variety of macrocyclic musk, has strong fragrance fixing effect and good diffusivity, and can obtain obvious effect only by adding 1 percent of the Kunlun musk in the essence of high-grade perfume or high-grade cosmetics.
Kunlun musk is widely used as blending spice and can be used in cologne, cosmetics, shampoo, detergent and the like; it is also useful as a soap essence because it is stable in alkalinity.
At present, the synthetic preparation of kunlun musk generally falls into two main categories according to the difference of starting materials:
the first kind uses α, omega-tridecanedioic acid and glycol as raw materials, prepares the Kunlun musk through polycondensation reaction and depolymerization reaction;
the second kind is prepared with omega-undecylenic acid as material, and through addition to diethyl malonate, hydrolysis in sodium alkoxide solution, acidification with hydrochloric acid, decarboxylation at 140 deg.c, polycondensation and final heating catalytic depolymerization.
The second method has higher operation danger due to the complex types of the used chemical reagents and the involvement of flammable and explosive substances, namely sodium alcoholate, and is not basically adopted in the industry at present.
The first method mostly adopts α omega-tridecanedioic acid obtained by biological fermentation, the raw material source is easy to obtain, the process route is mature, the commonly adopted process method is that α omega-tridecanedioic acid and ethylene glycol are firstly subjected to polycondensation reaction, then depolymerization reaction is carried out to obtain crude Kunlun musk, and the crude Kunlun musk is rectified to obtain the finished Kunlun musk product.
However, in the current technology, the following problems still exist in the method: 1. the polycondensation reaction temperature is high, generally 180-200 ℃, and side reactions are easy to occur; 2. the polymerization degree is not controlled or is controlled roughly in the polycondensation reaction, so that the subsequent depolymerization reaction effect is influenced, and the product quality is influenced finally; 3. the depolymerization reaction catalyst has complex components, most of the depolymerization catalysts reported in the current literatures and patents are composite depolymerization catalysts, and the composite depolymerization catalysts comprise aluminum carbonate, p-toluenesulfonic acid, silicotungstomolybdic acid, anhydrous copper sulfate, water and the like, have complex components and have great influence on subsequent refining and purification of products; 4. the depolymerization temperature is high, the depolymerization temperature is usually 250-300 ℃, and the later depolymerization temperature is even increased to 300-325 ℃. The aroma of the Kunlun musk product obtained in the method has burnt flavor, and the quality of the Kunlun musk final product is seriously influenced.
Therefore, the production process of Kunlun musk still needs to be improved.
Disclosure of Invention
The invention mainly solves the technical problem of providing a preparation method of Kunlun musk, which can prepare high-quality Kunlun musk under the condition of low temperature.
The invention adopts α, omega-tridecanedioic acid and glycol as raw materials, and prepares the Kunlun musk through low-temperature polycondensation and low-temperature depolymerization reaction, and the synthetic route is as follows:
in order to solve the technical problems, the invention adopts a technical scheme that:
provides a preparation method of Kunlun musk, which comprises the following steps of:
(1) condensation reaction: mixing ethylene glycol and tridecanedioic acid in a sealable container, heating to 110-140 ℃ in the atmosphere of nitrogen or inert gas, and heating for 2-4 hours to 160-180 ℃;
(2) polymerization reaction: keeping the temperature unchanged, and vacuumizing for 2.5-3.5 hours to ensure that the vacuum degree in the container reaches 180-220 mmHg;
(3) and (3) polymerization degree adjustment: then vacuuming for 2.5-3.5 h to make the vacuum degree in the container reach 3-10 mmHg.
Further, in the step (1), the material is heated to 120 ℃ and then heated for 3 hours to 170 ℃.
Further, in the steps (2) and (3), the vacuumizing is carried out at a constant speed;
in the specific embodiment of the invention, the step (2) is vacuumized to 200mmHg, and the step (3) is vacuumized to 5 mmHg;
in a specific embodiment of the present invention, the rate of evacuation in step (2) is 3mmHg/min and the rate of evacuation in step (3) is 1 mmHg/min.
Further, ethylene glycol: the mass ratio of the tridecanedioic acid is (60-90): 120, further (66-81): 120, and further 81: 120.
in the existing process for synthesizing the Kunlun musk, the polycondensation reaction temperature is high, about 180-200 ℃, and cracking easily occurs to generate a byproduct during high-temperature depolymerization due to the influence of residual carboxyl acidity; meanwhile, the prior art has no method for effectively and accurately controlling the polymerization degree of the polyester, if the polymerization degree of the polyester is too large, the viscosity is too high, and the heat transfer in the depolymerization process is not facilitated; if the polymerization degree is too low, the residual carboxyl group and hydroxyl group are too large, water is likely to be generated during depolymerization to be unfavorable for depolymerization, and side reactions such as cracking are likely to occur due to the influence of the carboxyl group, and it is considered that the polymerization degree of the polycondensation reaction is preferably controlled to about 50.
Therefore, the polymerization degree of the polyester has important influence on the quality of a final product, and if the polymerization degree of the product can be better controlled, the product quality can be better improved, and the quality stability of the production process can be improved.
According to the invention, the vacuum pumping speed and the ethylene glycol recovery speed are controlled through a specific material ratio, and the polymerization degree of polyester obtained by polycondensation can be effectively controlled to be about 45-50 at a specific temperature.
Further, in the preparation method of the Kunlun musk, after the polycondensation step, the method also comprises a depolymerization step: and mixing the polyester obtained in the polycondensation step with a catalyst titanium isopropoxide, vacuumizing, heating to 210-230 ℃, and continuously adding an entrainer ethylene glycol into a depolymerization reaction system until the temperature of the depolymerization reaction system reaches 240-250 ℃.
Further, mixing the polyester obtained in the polycondensation step with a catalyst titanium isopropoxide, vacuumizing, heating to 220 ℃, and continuously adding an entrainer ethylene glycol into a depolymerization reaction system until the temperature of the depolymerization reaction system reaches 240 ℃.
Further, the dosage of the catalyst titanium isopropoxide is as follows: tridecanedioic acid: the mass ratio of titanium isopropoxide is (300-1000): 1, further (450 to 800): 1, further 480: 1.
further, the addition rate of the entrainer glycol is 0.05-0.2L, preferably 0.075-0.16L, and more preferably 0.1-0.16L per hour for every 1kg of the tridecanedioic acid.
The expression "0.05-0.2L ethylene glycol is added per hour per 1kg of tridecanedioic acid used" means that, taking 0.05L as an example, the addition flow rate of the entrainer ethylene glycol is increased by 0.05L/h in the depolymerization process per 1kg of tridecanedioic acid added in the raw material, and if 1000kg of tridecanedioic acid is used in the synthesis raw material, the addition flow rate of the entrainer ethylene glycol is 50L/h, and the rest is analogized in turn.
Further, the vacuumizing is to ensure that the vacuum degree in a reaction container is not more than 10mmHg, and preferably 2-6 mmHg.
Further, the catalyst titanium isopropoxide is mixed with the polyester in the form of glycol solution, and glycol in the mixed solution is recovered.
Further, in the preparation method of the Kunlun musk, after the steps of polycondensation and depolymerization, the method also comprises the step of rectification: rectifying crude Kunlun musk obtained by depolymerization; furthermore, the absolute pressure at the top of the rectifying tower is less than or equal to 50pa in the rectifying process.
The invention has the beneficial effects that:
(1) the polycondensation process adopts non-catalytic low-temperature polycondensation, the reaction temperature is less than or equal to 170 ℃, and compared with the prior art, the polycondensation process has the advantages of reducing production energy consumption and reducing side reactions.
(2) In the polycondensation process, the polymerization degree of the polycondensation reaction is controlled, and the polycondensation product with the polymerization degree of 45-50 can be effectively obtained.
(3) The titanium isopropoxide is used as a depolymerization catalyst, so that the components are simple, the source is wide, the using amount is small, the catalytic effect is good, the yield is high, the depolymerization temperature can be reduced to 220-240 ℃ by matching with the entrainer ethylene glycol, the temperature is greatly reduced compared with that of 300-325 ℃ in the prior art, the burnt taste of a Kunlun musk product can be effectively avoided, and the product quality is improved; meanwhile, the energy consumption is greatly reduced, and the production safety is improved.
(4) The invention takes α, omega-tridecanedioic acid and ethylene glycol as raw materials, the raw materials are easy to obtain, the Kunlun musk is prepared by adopting low-temperature polycondensation and low-temperature depolymerization, the process conditions are milder compared with the traditional Kunlun musk preparation method, the yield is high, the crude product yield can reach 95.8%, the purity of the obtained Kunlun musk product is more than or equal to 99%, the fragrance is purer, no bad miscellaneous gas such as burnt smell and the like exists, and the quality is better.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The tridecanedioic acid is α omega-tridecanedioic acid.
Example 1
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 170 ℃ within 3 hours, the top temperature is 120 ℃, about 225kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 200mmHg at the speed of 3mmHg/min, keeping the kettle temperature at 170 ℃ and the top temperature at about 128 ℃ in the process, and distilling about 330kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 5mmHg at the speed of 1mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and finishing the ethylene glycol recovery process for about 3 hours in the whole process. The polycondensation product (polyester) was measured to have a degree of polymerization of 46.
3. Preparation and addition of depolymerization catalyst
It was confirmed that at least 2000kg of ethylene glycol was present in the de-polymerization entrainer ethylene glycol feed storage tank.
35kg of new ethylene glycol (anhydrous requirement) is added into the head tank, and then 2.5kg of titanium isopropoxide is added; slowly adding the prepared titanium isopropoxide glycol solution into the reaction kettle through the head tank, wherein the adding time is about 5 minutes, after the solution is added, adding 24kg of glycol (requiring no water) to wash the pipeline, and taking care to avoid air from entering the whole process.
Vacuum-pumping to 5mmHg at 25mmHg/min by automatic control system, heating to 220 deg.C for 3 hr, and collecting ethylene glycol together with ethylene glycol recovered at the end of esterification when the temperature is reached.
4. Depolymerization reaction
Stopping stirring, starting a hot oil valve of the ethylene glycol evaporator, starting an ethylene glycol feeding pump, adjusting the flow rate of ethylene glycol to 120L/h, keeping the speed, feeding 240kg of ethylene glycol (about 2 hours), and if a feeding system and a reaction kettle are normal, adjusting the flow rate to 190L/h;
the valve of the discharging pump of the depolymerization receiver is switched, the material enters the depolymerization receiver, the Kunlun musk is on the upper layer, and the lower layer is entrainer glycol.
During the depolymerization process, the vacuum is preferably kept within the range of 2mmHg to 6 mmHg; if the vacuum drops to 10mmHg for some reason and there is a further trend, the feed valve of the ethylene glycol evaporator is closed, the ethylene glycol feed pump is stopped, the evaporator heating is closed, the cooling water condition of the vacuum system or the main cooling condenser is checked, and if the cooling water condition cannot be recovered, the relevant measures are taken immediately.
Along with the progress of depolymerization reaction, the temperature of the depolymerization kettle gradually rises, when the temperature of the depolymerization kettle reaches 240 ℃, the feeding of entrainer ethylene glycol is stopped, and the depolymerization reaction is finished.
Finally 1200kg of crude kunlun musk is obtained, the content is 95.8%, and the yield is 95.8% (the yield is the mass of the crude kunlun musk/the mass of the added dibasic acid).
Example 2
1. Feeding material
210kg of ethylene glycol is firstly put into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 170 ℃ within 3 hours, the top temperature is 120 ℃, about 225kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 200mmHg at the speed of 3mmHg/min, keeping the kettle temperature at 170 ℃ and the top temperature of about 128 ℃ in the process, and distilling out about 200kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 5mmHg at the speed of 1mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and finishing the ethylene glycol recovery process for about 3 hours in the whole process. The polycondensation product was measured to have a degree of polymerization of 42.
3. Preparation and addition of depolymerization catalyst
It was confirmed that at least 2000kg of ethylene glycol was present in the de-polymerization entrainer ethylene glycol feed storage tank.
25kg of new ethylene glycol (anhydrous requirement) is added into the head tank, and then 1.5kg of titanium isopropoxide is added; slowly adding the prepared titanium isopropoxide glycol solution into a reaction kettle through a head tank, wherein the adding time is about 5 minutes, after the solution is added, adding 24kg of glycol (requiring no water) to wash a pipeline, and intentionally avoiding air from entering the whole process;
vacuum-pumping to 5mmHg at 25mmHg/min by automatic control system, heating to 220 deg.C for 3 hr, and collecting ethylene glycol together with ethylene glycol recovered at the end of esterification when the temperature is reached.
4. Depolymerization reaction
Stopping stirring, starting a hot oil valve of the ethylene glycol evaporator, starting an ethylene glycol feeding pump, adjusting the flow rate of ethylene glycol to 90L/h, keeping the speed, adding 180kg of ethylene glycol (about 2 hours), and if a feeding system and a reaction kettle are normal, adjusting the flow rate to 160L/h;
the valve of the discharging pump of the depolymerization receiver is switched, the material enters the depolymerization receiver, the Kunlun musk is on the upper layer, and the lower layer is entrainer glycol.
During the depolymerization process, the vacuum is preferably kept within the range of 2mmHg to 6 mmHg; if the vacuum drops to 10mmHg for some reason and there is a further trend, the feed valve of the ethylene glycol evaporator is closed, the ethylene glycol feed pump is stopped, the evaporator heating is closed, the cooling water condition of the vacuum system or the main cooling condenser is checked, and if the cooling water condition cannot be recovered, the relevant measures are taken immediately.
Along with the progress of depolymerization reaction, the temperature of the depolymerization kettle gradually rises, when the temperature of the depolymerization kettle reaches 240 ℃, the feeding of entrainer ethylene glycol is stopped, and the depolymerization reaction is finished.
Finally obtaining 1080kg of crude Kunlun musk product with the content of 95.2 percent and the yield of 85.7 percent.
Example 3
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is increased from 138 ℃ to 180 ℃ within 3 hours, the top temperature is 125 ℃, about 230kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 200mmHg at the speed of 3mmHg/min, keeping the kettle temperature at 180 ℃ and the top temperature at about 130 ℃ in the process, and distilling about 330kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 3mmHg at the speed of 1mmHg/min by an automatic control system, keeping the kettle temperature at 180 ℃ in the process, and finishing the ethylene glycol recovery process for about 3 hours in the whole process. The polycondensation product was measured to have a degree of polymerization of 60.
3. Preparation and addition of depolymerization catalyst
It was confirmed that at least 2000kg of ethylene glycol was present in the de-polymerization entrainer ethylene glycol feed storage tank.
30kg of new ethylene glycol (requiring no water) is added into the head tank, and then 2.0kg of titanium isopropoxide is added; slowly adding the prepared titanium isopropoxide glycol solution into a reaction kettle through a head tank, wherein the adding time is about 5 minutes, after the solution is added, adding 24kg of glycol (requiring no water) to wash a pipeline, and intentionally avoiding air from entering the whole process;
vacuum-pumping to 5mmHg at 25mmHg/min by automatic control system, heating to 220 deg.C for 3 hr, and collecting ethylene glycol together with ethylene glycol recovered at the end of esterification when the temperature is reached.
4. Depolymerization reaction
Stopping stirring, starting a hot oil valve of the ethylene glycol evaporator, starting an ethylene glycol feeding pump, adjusting the flow rate of ethylene glycol to 100L/h, keeping the speed, adding 200kg of ethylene glycol (about 2 hours), and if a feeding system and a reaction kettle are normal, adjusting the flow rate to 170L/h;
the valve of a discharge pump of the depolymerization receiver is switched, the material enters the depolymerization receiver, the Kunlun musk is at the upper layer, and the entrainer glycol is at the lower layer;
during the depolymerization process, the vacuum is preferably kept within the range of 2mmHg to 6 mmHg; if the vacuum drops to 10mmHg for some reason and there is a further trend, the feed valve of the ethylene glycol evaporator is closed, the ethylene glycol feed pump is stopped, the evaporator heating is closed, the cooling water condition of the vacuum system or the main cooling condenser is checked, and if the cooling water condition cannot be recovered, the relevant measures are taken immediately.
Along with the progress of depolymerization reaction, the temperature of the depolymerization kettle gradually rises, when the temperature of the depolymerization kettle reaches 240 ℃, the feeding of entrainer ethylene glycol is stopped, and the depolymerization reaction is finished.
1036kg of crude Kunlun musk product with the content of 95.5 percent and the yield of 82.5 percent is finally obtained.
Example 4
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 170 ℃ within 3 hours, the top temperature is 120 ℃, about 225kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 220mmHg at the speed of 3.5mmHg/min, keeping the kettle temperature at 170 ℃ and the top temperature of about 120 ℃ in the process, and distilling about 320kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 10mmHg at the speed of 1.4mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and treating the whole process for about 2.5 hours to finish glycol recovery. The polycondensation product (polyester) was measured to have a degree of polymerization of 35.
3. Preparation and addition of depolymerization catalyst
It was confirmed that at least 2000kg of ethylene glycol was present in the de-polymerization entrainer ethylene glycol feed storage tank.
35kg of new ethylene glycol (anhydrous requirement) is added into the head tank, and then 2.5kg of titanium isopropoxide is added; slowly adding the prepared titanium isopropoxide glycol solution into the reaction kettle through the head tank, wherein the adding time is about 5 minutes, after the solution is added, adding 24kg of glycol (requiring no water) to wash the pipeline, and taking care to avoid air from entering the whole process.
Vacuum-pumping to 5mmHg at 25mmHg/min by automatic control system, heating to 230 deg.C for 3 hr, and collecting ethylene glycol together with ethylene glycol recovered at the end of esterification when the temperature is reached.
4. Depolymerization reaction
Stopping stirring, starting a hot oil valve of the ethylene glycol evaporator, starting an ethylene glycol feeding pump, adjusting the flow rate of ethylene glycol to 120L/h, keeping the speed, feeding 240kg of ethylene glycol (about 2 hours), and if a feeding system and a reaction kettle are normal, adjusting the flow rate to 190L/h;
the valve of the discharging pump of the depolymerization receiver is switched, the material enters the depolymerization receiver, the Kunlun musk is on the upper layer, and the lower layer is entrainer glycol.
During the depolymerization process, the vacuum is preferably kept within the range of 2mmHg to 6 mmHg; if the vacuum drops to 10mmHg for some reason and there is a further trend, the feed valve of the ethylene glycol evaporator is closed, the ethylene glycol feed pump is stopped, the evaporator heating is closed, the cooling water condition of the vacuum system or the main cooling condenser is checked, and if the cooling water condition cannot be recovered, the relevant measures are taken immediately.
Along with the progress of depolymerization reaction, the temperature of the depolymerization kettle gradually rises, when the temperature of the depolymerization kettle reaches 250 ℃, the feeding of entrainer ethylene glycol is stopped, and the depolymerization reaction is finished.
Finally, 1022kg of crude Kunlun musk product with the content of 93.6 percent and the yield of 79.7 percent is obtained.
Example 5
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 160 ℃ within 3 hours, the top temperature is 115 ℃, about 200kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 180mmHg at the speed of 2.8mmHg/min, keeping the kettle temperature at 160 ℃ and the top temperature of about 125 ℃, and distilling out about 350kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 3mmHg at the speed of 0.85mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and finishing the ethylene glycol recovery process for about 3.5 hours in the whole process. The polycondensation product (polyester) was measured to have a degree of polymerization of 32.
3. Preparation and addition of depolymerization catalyst
It was confirmed that at least 2000kg of ethylene glycol was present in the de-polymerization entrainer ethylene glycol feed storage tank.
35kg of new ethylene glycol (anhydrous requirement) is added into the head tank, and then 2.5kg of titanium isopropoxide is added; slowly adding the prepared titanium isopropoxide glycol solution into the reaction kettle through the head tank, wherein the adding time is about 5 minutes, after the solution is added, adding 24kg of glycol (requiring no water) to wash the pipeline, and taking care to avoid air from entering the whole process.
Vacuum-pumping to 5mmHg at 25mmHg/min by automatic control system, heating to 210 deg.C for 3 hr, and collecting ethylene glycol together with ethylene glycol recovered at the end of esterification when the temperature is reached.
4. Depolymerization reaction
Stopping stirring, starting a hot oil valve of the ethylene glycol evaporator, starting an ethylene glycol feeding pump, adjusting the flow rate of ethylene glycol to 120L/h, keeping the speed, feeding 240kg of ethylene glycol (about 2 hours), and if a feeding system and a reaction kettle are normal, adjusting the flow rate to 190L/h;
the valve of the discharging pump of the depolymerization receiver is switched, the material enters the depolymerization receiver, the Kunlun musk is on the upper layer, and the lower layer is entrainer glycol.
During the depolymerization process, the vacuum is preferably kept within the range of 2mmHg to 6 mmHg; if the vacuum drops to 10mmHg for some reason and there is a further trend, the feed valve of the ethylene glycol evaporator is closed, the ethylene glycol feed pump is stopped, the evaporator heating is closed, the cooling water condition of the vacuum system or the main cooling condenser is checked, and if the cooling water condition cannot be recovered, the relevant measures are taken immediately.
Along with the progress of depolymerization reaction, the temperature of the depolymerization kettle gradually rises, when the temperature of the depolymerization kettle reaches 240 ℃, the feeding of entrainer ethylene glycol is stopped, and the depolymerization reaction is finished.
Finally, 942kg of crude Kunlun musk product with the content of 96.3 percent and the yield of 75.6 percent is obtained.
EXAMPLE 6 rectification of crude Kunlun Musk
1. Feeding and vacuumizing
1200kg of the crude Kunlun musk product prepared in example 1 is put into a rectifying still, and the content of the Kunlun musk is 95.8%. Starting a Roots vacuum unit to ensure that the top absolute pressure of the tower is below 150pa in the rectification process.
2. Total reflux and prefractionation
Opening a feed valve of the front rectifier receiver, setting the temperature of the rectifying still to be 190 ℃, starting timing when the temperature of the top of the rectifying still rises to be above 125 ℃, and carrying out total reflux for 1-2 h;
after the total reflux is finished, the extraction rate is 60L/h, the material is discharged to the top temperature of 162 ℃ and 165 ℃, the extraction amount of the front distillation is 90kg, and the content of the Kunlun musk in the front distillation is 55 percent.
3. Discharging the main material
Switching a feed valve of the receiver;
setting the kettle temperature at 200 ℃, setting the reflux ratio at 1:1, and taking out 50% of the total amount of the fed materials;
setting the kettle temperature at 205 ℃, setting the reflux ratio at 1.5:1, and taking out 25% of the total amount of the feed;
the kettle temperature is set to 205 ℃, the reflux ratio is 2:1, and the extraction amount is 10 percent of the total feeding amount.
The above raw materials are 1020kg in total, the concentration of Kunlun Moschus is 99.1%, and the product has pure fragrance and no bad smell such as sour taste and burnt taste.
4. After distillation
And switching a feeding valve of the receiver, setting the kettle temperature to be 210 ℃, and discharging until the materials become turbid in a visual clock. The weight of the post distillation is 55kg, and the content of the Kunlun musk is 90%.
The front distillation and the back distillation are continuously carried out for rectification separation, the front distillation obtains 45kg of the positive material (the purity is 98.5 percent), the back distillation obtains 42kg of the positive material (the purity is 98.7 percent), and the total amount of the positive material is 1107kg (the purity is 99.0 percent, and the yield is 92.2 percent).
Comparative example 1
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 170 ℃ within 3 hours, the top temperature is 120 ℃, about 225kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 200mmHg at the speed of 2mmHg/min, keeping the kettle temperature at 170 ℃ and the top temperature at about 128 ℃ in the process, and distilling about 330kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 5mmHg at the speed of 0.8mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and finishing the ethylene glycol recovery process for about 4 hours in the whole process. The polycondensation product (polyester) was measured to have a degree of polymerization of 75.
Comparative example 2
1. Feeding material
Feeding 360kg of ethylene glycol into a polycondensation reaction kettle; then 1200kg of tridecanedioic acid is added from a manhole of the reaction kettle, and 450kg of ethylene glycol is added after the feeding is finished; vacuumizing to 100mmHg, and recovering the nitrogen to normal pressure.
2. Polycondensation reaction
Starting a condenser to cool water, and raising the temperature to 120 ℃ without stirring; continuously heating until reflux is generated, and then starting stirring, wherein the temperature of the kettle is about 138 ℃; the temperature of the kettle is raised from 138 ℃ to 170 ℃ within 3 hours, the top temperature is 120 ℃, about 225kg of water is evaporated, and the water is collected and enters a collecting tank as waste water; then vacuumizing to 200mmHg at the speed of 4.5mmHg/min, keeping the kettle temperature at 170 ℃ and the top temperature at about 128 ℃ in the process, and distilling about 330kg of water/glycol; the component is collected and ethylene glycol is recovered, the water phase enters a wastewater collection pool, and the ethylene glycol is recycled; and finally, vacuumizing to 5mmHg at the speed of 1.6mmHg/min by an automatic control system, keeping the kettle temperature at 170 ℃ in the process, and finishing the ethylene glycol recovery process for about 2 hours in the whole process. The polycondensation product (polyester) was measured to have a degree of polymerization of 30.
As can be seen from comparative examples 1 and 2, when the evacuation rate was too fast or too slow, a polyester having a desired degree of polymerization could not be obtained.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of Kunlun musk is characterized by comprising the following steps of:
(1) condensation reaction: mixing ethylene glycol and tridecanedioic acid in a sealable container, heating to 110-140 ℃ in the atmosphere of nitrogen or inert gas, and heating for 2-4 hours to 160-180 ℃;
(2) polymerization reaction: keeping the temperature unchanged, and vacuumizing for 2.5-3.5 hours to ensure that the vacuum degree in the container reaches 180-220 mmHg;
(3) and (3) polymerization degree adjustment: then vacuuming for 2.5-3.5 h to make the vacuum degree in the container reach 3-10 mmHg.
2. The method according to claim 1, wherein in the step (1), the material is heated to 120 ℃ and then heated for 3 hours to 170 ℃.
3. The preparation method according to claim 1, wherein in steps (2) and (3), the vacuumizing is carried out at a constant speed;
further, vacuumizing the step (2) to 200mmHg, and vacuumizing the step (3) to 5 mmHg;
further, the rate of evacuation in step (2) was 3mmHg/min, and the rate of evacuation in step (3) was 1 mmHg/min.
4. The production method according to claim 1, wherein the ratio of ethylene glycol: the mass ratio of the tridecanedioic acid is (60-90): 120, further (66-81): 120, and further 81: 120.
5. the method according to claim 1, further comprising a depolymerization step after the polycondensation step: and mixing the polyester obtained in the polycondensation step with a catalyst titanium isopropoxide, vacuumizing, heating to 210-230 ℃, and continuously adding an entrainer ethylene glycol into a depolymerization reaction system until the temperature of the depolymerization reaction system reaches 240-250 ℃.
Further, mixing the polyester obtained in the polycondensation step with a catalyst titanium isopropoxide, vacuumizing, heating to 220 ℃, and continuously adding an entrainer ethylene glycol into a depolymerization reaction system until the temperature of the depolymerization reaction system reaches 240 ℃.
6. The method according to claim 5, wherein the catalyst titanium isopropoxide is used in an amount of: tridecanedioic acid: the mass ratio of titanium isopropoxide is (300-1000): 1, further (450 to 800): 1, further 480: 1.
7. the method according to claim 5 or 6, wherein the entrainer glycol is added at a rate of from 0.05 to 0.2L, preferably from 0.075 to 0.16L, more preferably from 0.1 to 0.16L, ethylene glycol per hour for every 1kg of tridecanedioic acid used.
8. The method according to claim 5 or 6, wherein the evacuation is performed such that the degree of vacuum in the reaction vessel is not more than 10mmHg, preferably 2 to 6 mmHg.
9. The method according to claim 5 or 6, wherein the catalyst titanium isopropoxide is mixed with the polyester in the form of glycol solution, and the glycol is recovered after mixing.
10. The method according to claim 1 or 5, further comprising a rectification step after the polycondensation and depolymerization steps: rectifying crude Kunlun musk obtained by depolymerization; furthermore, the absolute pressure at the top of the rectifying tower is less than or equal to 50pa in the rectifying process.
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| CN113144655A (en) * | 2021-04-28 | 2021-07-23 | 安徽金轩科技有限公司 | Jiale musk rectification unit and rectification process thereof |
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