CN114436779B - Purification device for trans-isomer of 1,4-cyclohexanedimethanol and application method - Google Patents
Purification device for trans-isomer of 1,4-cyclohexanedimethanol and application method Download PDFInfo
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- CN114436779B CN114436779B CN202011187723.9A CN202011187723A CN114436779B CN 114436779 B CN114436779 B CN 114436779B CN 202011187723 A CN202011187723 A CN 202011187723A CN 114436779 B CN114436779 B CN 114436779B
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- cyclohexanedimethanol
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 39
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 58
- 239000013078 crystal Substances 0.000 claims abstract description 46
- 238000007599 discharging Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000010413 mother solution Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 20
- 229920000728 polyester Polymers 0.000 abstract description 9
- 238000000053 physical method Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 66
- 238000002425 crystallisation Methods 0.000 description 41
- 230000008025 crystallization Effects 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 17
- 239000012467 final product Substances 0.000 description 14
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000035900 sweating Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UEHLZRCCIWVHBH-UHFFFAOYSA-N 2-cyclopropyl-2-methylcyclopropane-1-carboxylic acid Chemical compound C1CC1C1(C)CC1C(O)=O UEHLZRCCIWVHBH-UHFFFAOYSA-N 0.000 description 1
- -1 PETG Chemical compound 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a device for purifying trans-isomer of 1,4-cyclohexanedimethanol, which comprises a crystallizer, a heat exchanger, a feeding pipeline, a filter, a first discharging pipeline and a second discharging pipeline; wherein the crystallizer is connected with the heat exchanger through a feeding pipeline; one end of the first discharging pipeline is connected with a second outlet of the heat exchanger, and the other end of the first discharging pipeline is connected with the crystallizer through a filter, so that mother liquor is circulated and enters the crystallizer again; the second discharging pipeline is connected with a second outlet of the heat exchanger and discharges trans-isomer of 1, 4-cyclohexanedimethanol. By designing the heat exchanger and the temperature regulation of the internal and external circulation thereof, the process of efficiently purifying trans-CHDM from the cis-trans mixture of CHDM by using a physical method is simplified; the trans-cis ratio of the purified CHDM crystal is more than 92 percent; the first discharging pipeline and the filter connected with the heat exchanger improve the utilization rate of mother liquor and directly improve the yield of the high-trans-cis ratio CHDM; the influence of solvent residue on polyester modification is effectively avoided.
Description
Technical Field
The invention relates to a purification device and a use method thereof, in particular to a purification device and a use method of trans-isomer of 1, 4-cyclohexanedimethanol.
Background
The molecular formula of 1,4-Cyclohexanedimethanol (CHDM) is C8H12O2, and the preparation method is mainly applied to the fields of paint, polyester modification, medicine and the like. CHDM has both sequential and trans structures, with polyesters modified with high levels of trans CHDM such as PETG, PCTG, etc. having the advantage of high glass transition temperatures, and the higher the trans content, the higher the glass transition temperature.
The CHDM reverse-to-forward ratio sold in the market at the present stage is mainly 7/3, and the method for improving the CHDM reverse-to-forward ratio is a chemical and physical separation method. US4999090, US2917549 respectively describe a method for purifying trans CHDM by chemical methods, which have more severe reaction conditions and high energy consumption. The physical method comprises the following steps: JP2002275108 discloses a method for purifying CHDM trans-isomer, which uses ethyl acetate as solvent, recrystallizes CHDM trans-isomer at room temperature, washes and purifies the product, and then crystallizes and separates under the condition of 20 ℃ below zero to obtain high-purity CHDM trans-isomer; the patent uses ethyl acetate as a solvent, and a washing method cannot completely remove part of ethyl acetate residues in the crystallization process, wherein the residues of the ethyl acetate residues have an influence on the polyester performance and require a temperature of minus 20 ℃ and have high energy consumption.
CN107200677a discloses a method for purifying CHDM trans isomer, which uses ethyl acetate or acetone as solvent, adopts a mode of combining solution cooling crystallization and melt crystallization phase, and obtains high purity CHDM trans isomer at 0-20 ℃, the cooled and crystallized CHDM contains partial solvent, and the residual solvent adopts a process of sweating to purify CHDM.
Whether cooling crystallization or melting crystallization is adopted, the crystallization process is that a supersaturated component in the solution starts to nucleate and gradually grows into crystals in the process that the temperature gradually decreases along with the temperature, and impurities in the mother solution are inevitably occluded into the crude crystals in the growth process of the crystals, so that the crude crystals need to be purified by washing or sweating. The above physical methods for purification of trans CHDM involve the removal of acetone or ethyl acetate.
The impurities in the polyester PET or PBT raw material often affect the performance of the polyester fiber, such as glass transition temperature and color equality, and if the polyester raw material has low-boiling-point micromolecule residues such as acetone or ethyl acetate, the influence in the spinning stage is more obvious, so that the problems of yarn breakage, yarn flying and the like are caused, and the problems are also caused when the high-purity trans-CHDM modified PET or PBT polyester is adopted.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a purification device for reducing purification procedures and effectively improving the trans-cis ratio of 1,4-cyclohexanedimethanol to a trans-isomer of 1, 4-cyclohexanedimethanol;
a second object of the present invention is to provide a method of using the above device.
The technical scheme is as follows: the invention provides a device for purifying trans-isomer of 1,4-cyclohexanedimethanol, which comprises a crystallizer, a heat exchanger, a feeding pipeline, a filter, a first discharging pipeline and a second discharging pipeline; wherein the crystallizer is connected with the heat exchanger through a feeding pipeline; one end of the first discharging pipeline is connected with a second outlet of the heat exchanger, and the other end of the first discharging pipeline is connected with the crystallizer through a filter, so that mother liquor is circulated and enters the crystallizer again; the second discharging pipeline is connected with a second outlet of the heat exchanger and discharges trans-isomer of 1, 4-cyclohexanedimethanol.
Preferably, the heat exchanger comprises heat exchange areas and mother liquor treatment areas which are alternately arranged, and contact boundaries of the heat exchange areas and the mother liquor treatment areas are all wave curves.
Further, the mother solution treatment is divided into a plurality of mother solution solidification and melting units by the wavy curves on two sides, and each unit is of a spherical structure.
The invention also provides a use method of the purification device of the trans isomer of the 1,4-cyclohexanedimethanol, which comprises the following steps:
(1) Storing a mixed solution containing a solvent, a trans-isomer of 1,4-cyclohexanedimethanol and a cis-isomer of 1,4-cyclohexanedimethanol as a mother solution in a crystallizer, cooling to 0-20 ℃ through a heat exchanger, and filtering through a first discharge pipeline and a filter to obtain a crystal A and a filtrate A;
(2) The filtrate A enters a crystallizer to be cooled to below 0 ℃, is solidified and then is heated, and crystals B and filtrate B are obtained through a feeding pipeline;
(3) Heating the crystal B in a heat exchanger until the solid is completely dissolved, and flowing out through a second discharging pipeline to obtain the 1,4-cyclohexanedimethanol trans-isomer solution.
Preferably, the solvent is butanediol or ethylene glycol
Preferably, the cooling rate of the cooling in step (1) is 0.1-1 ℃/min.
Further, the temperature rising rate of the temperature rising after solidification in the step (2) is 0.1-1 ℃/min.
Preferably, the temperature of the step (2) is raised to 15-20 ℃.
Further, the heating rate of heating in the heat exchanger in the step (3) is more than 5 ℃/min.
Further, the temperature in the heat exchanger in the step (3) is raised to be more than 50 ℃.
Preferably, the initial ratio of trans 1,4-cyclohexanedimethanol trans isomer to cis 1,4-cyclohexanedimethanol trans isomer is from 6:4 to 8:2.
The beneficial effects are that: compared with the prior art, the invention has the following advantages: by designing the heat exchanger and the temperature regulation of the internal and external circulation thereof, the process of efficiently purifying trans-CHDM from the cis-trans mixture of CHDM by using a physical method is simplified; the trans-cis ratio of the purified CHDM crystal is more than 92 percent; the first discharging pipeline and the filter connected with the heat exchanger improve the utilization rate of mother liquor and directly improve the yield of the high-trans-cis ratio CHDM; the influence of solvent residue on polyester modification is effectively avoided.
Drawings
FIG. 1 is a schematic diagram of a purification apparatus connection;
fig. 2 is a schematic view of the internal structure of the heat exchanger.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
As shown in fig. 1, the invention provides a device for purifying trans-isomer of 1,4-cyclohexanedimethanol, which comprises a crystallizer, a heat exchanger, a feed pipeline, a filter, a first discharge pipeline and a second discharge pipeline; wherein the crystallizer is connected with the heat exchanger through a feeding pipeline; one end of the first discharging pipeline is connected with a second outlet of the heat exchanger, and the other end of the first discharging pipeline is connected with the crystallizer through a filter, so that mother liquor is circulated and enters the crystallizer again; the second discharging pipeline is connected with a second outlet of the heat exchanger and discharges trans-isomer of 1, 4-cyclohexanedimethanol.
As shown in fig. 2, the heat exchanger comprises heat exchange areas and mother liquor treatment areas which are alternately arranged, and the contact boundaries of the heat exchange areas and the mother liquor treatment areas are all wave curves. The mother liquid treatment is divided into a plurality of mother liquid solidification and melting units by wave curves on two sides, and each unit is of a spherical structure.
The method for utilizing the purification device of the trans isomer of the 1,4-cyclohexanedimethanol comprises the following steps:
(1) Mixing ethylene glycol, a trans isomer of 1,4-cyclohexanedimethanol and a cis isomer of 1,4-cyclohexanedimethanol with a trans-cis ratio of 7/3, wherein the weight ratio of CHDM to ethylene glycol is 8:2, weighing 100g of the total amount of the mixture, heating the mixture in a crystallizer 1 to enable the mixture to be at a temperature of 75 ℃ to prepare a mixed solution, storing the mixed solution in the crystallizer 1 as mother liquor, setting the outer circulation of the crystallizer 1 to be at 25 ℃, setting the inner circulation to be at 15 ℃, cooling at a speed of 0.5 ℃/min, crystallizing and growing the crystal for 5h to obtain 5g of CHDM crystals, wherein the trans-cis ratio is 93:7, filtering the mother liquor, cooling the mother liquor to 0 ℃ by a mother liquor treatment device 8 of a heat exchanger 2, and filtering the mother liquor through a first discharging pipeline 4 and a filter 3 to obtain crystals A and filtrate A;
(2) The filtrate A enters a crystallizer 1 through a first discharging pipeline 4 to be cooled to below 0 ℃, mother liquor treatment equipment 8 is gradually heated to 17 ℃ at the speed of 0.5 ℃/min, and crystals B and filtrate B are obtained through a feeding pipeline 6;
(3) The mother liquor treatment device 8 of the crystal B in the heat exchanger 2 is then quickly heated to 65 ℃ until the solid is completely dissolved, and flows out through the second discharge pipeline 5, so as to obtain the trans-isomer solution of the 1, 4-cyclohexanedimethanol.
The solids were completely dissolved to a crystallization apparatus for recrystallization, and the content of the crystals was varied as shown in Table 1, with a 5% ratio of ethylene glycol in the final product.
TABLE 1
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 5 | 93 |
| Secondary time | 9 | 92.6 |
| Three times | 11 | 92.4 |
| Four times | 12 | 92 |
Example 2
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to butanediol was 8:2, the total amount of the mixture was weighed 100g, and the mixture was heated in a crystallizer at 75℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 1 ℃/min, crystallizing, growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 20 ℃ at the speed of 0.1 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 75 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the example 1, wherein the content change of the crystallization process is shown in the table 2, and the butanediol content in the final product is 5%.
TABLE 2
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 5 | 93 |
| Secondary time | 9 | 92.7 |
| Three times | 11 | 92.5 |
| Four times | 12 | 92.3 |
Example 3
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 9:1, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer at 75℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 0.1 ℃/min, crystallizing, growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 20 ℃ at the speed of 1 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 60 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the example 1, wherein the content change of the crystallization process is shown in the table 3, and the content of ethylene glycol in the final product is 6%.
TABLE 3 Table 3
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 5 | 93 |
| Secondary time | 8 | 93 |
| Three times | 11 | 92.5 |
Example 4
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to butanediol was 9:1, the total amount of the mixture was weighed 100g, and the mixture was heated in a crystallizer to a temperature of 80℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 10 ℃ at the speed of 0.1 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 50 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the embodiment 1, wherein the content of the crystallization process is changed as shown in the table 4, and the butanediol content in the final product is 6%.
TABLE 4 Table 4
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 5 | 93 |
| Secondary time | 8 | 93 |
| Three times | 11 | 92.7 |
Example 5
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 8:2, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer to a temperature of 65℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer to 25 ℃, setting the inner circulation to 5 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 6g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 10 ℃ at the speed of 0.5 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 50 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the embodiment 1, wherein the content of the crystallization process is changed as shown in the table 5, and the content of ethylene glycol in the final product is 5%.
TABLE 5
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.7 |
| Three times | 14 | 92.3 |
| Four times | 15 | 92 |
Example 6
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to butanediol was 8:2, the total amount of the mixture was weighed 100g, and the mixture was heated in a crystallizer at 55℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer to 25 ℃, setting the inner circulation to 5 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 6g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 10 ℃ at the speed of 0.5 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 50 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the embodiment 1, wherein the content change of the crystallization process is shown in the table 6, and the butanediol content in the final product is 5%.
TABLE 6
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.7 |
| Three times | 14 | 92.5 |
| Four times | 15 | 92 |
Example 7
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 9:1, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer at 75℃to completely dissolve the mixture. Setting the outer circulation of the crystallizer at 25 ℃, setting the inner circulation at 5 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 6g of CHDM crystal, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 10 ℃ at the speed of 0.5 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 50 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the embodiment 1, wherein the content of the crystallization process is changed as shown in the table 7, and the proportion of ethylene glycol in the final product is 6%.
TABLE 7
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.7 |
| Three times | 14 | 92.1 |
Example 8
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to butanediol was 9:1, the total amount of the mixture was weighed 100g, and the mixture was heated in a crystallizer to a temperature of 65℃to completely dissolve the mixture. Setting the outer circulation at 25 ℃, setting the inner circulation at 5 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, growing crystals for 5 hours to obtain 6g of CHDM crystals, wherein the trans-cis ratio is 93:7, filtering the mother liquor, then sending the mother liquor to mother liquor treatment equipment to cool to 0 ℃, gradually heating the mother liquor treatment equipment to 10 ℃ at the speed of 0.5 ℃/min, discharging melted liquid, then quickly heating the mother liquor treatment equipment to 50 ℃, completely dissolving the solid to the crystallization equipment for recrystallization, and carrying out the rest steps in the same way as in the example 1, wherein the content change of the crystallization process is shown in the table 8, and the butanediol content in the final product is 5%.
TABLE 8
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.6 |
| Three times | 14 | 92.3 |
Comparative example 1
The CHDM was 3/2 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 8:2, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer at 60℃to completely dissolve the mixture. Setting the outer circulation at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, and the ethylene glycol content in the CHDM crystal is 6%. The remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 9, and the ratio of ethylene glycol in the final product was 5%.
TABLE 9
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 92 |
| Secondary time | 11 | 91.8 |
| Three times | 14 | 91.1 |
Comparative example 2
The CHDM was in a trans/cis ratio of 4/1 and the weight ratio of CHDM to ethylene glycol was 8:2, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer to a temperature of 55℃to completely dissolve the mixture. Setting the outer circulation at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 0.5 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, and the butanediol content in the CHDM crystal is 5%. The remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 10, and the ratio of ethylene glycol in the final product was 5%.
Table 10
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 95 |
| Secondary time | 11 | 94.6 |
| Three times | 14 | 94.2 |
Comparative example 3
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 8:2, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer at 60℃to completely dissolve the mixture. Setting the outer circulation at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 0.1 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, and the ethylene glycol content in the CHDM crystal is 6%. The remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 11, and the ratio of ethylene glycol in the final product was 5%.
TABLE 11
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.8 |
| Three times | 14 | 92.1 |
Comparative example 4
The CHDM was 7/3 in terms of the trans-cis ratio and the weight ratio of CHDM to ethylene glycol was 8:2, the total amount of the mixture was weighed to 100g, and the mixture was heated in a crystallizer to a temperature of 70℃to completely dissolve the mixture. Setting the outer circulation at 25 ℃, setting the inner circulation at 15 ℃, cooling at the speed of 1 ℃/min, crystallizing, and growing the crystal for 5 hours to obtain 5g of CHDM crystal, wherein the trans-cis ratio is 93:7, and the butanediol content in the CHDM crystal is 5%. The remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 12, and the ratio of ethylene glycol in the final product was 5%.
Table 12
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.6 |
| Three times | 14 | 92.2 |
Comparative example 5
The filtrate A enters a crystallizer through a first discharging pipeline to be cooled to below 0 ℃, mother liquor treatment equipment is gradually heated to 17 ℃ at the speed of 0.1 ℃/min, and crystals B and filtrate B are obtained through a feeding pipeline; the remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 13, and the ratio of ethylene glycol in the final product was 5%.
TABLE 13
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.8 |
| Three times | 14 | 92.1 |
Comparative example 6
The filtrate A enters a crystallizer through a first discharging pipeline to be cooled to below 0 ℃, mother liquor treatment equipment is gradually heated to 17 ℃ at a speed of 1 ℃/min, and crystals B and filtrate B are obtained through a feeding pipeline 6; the remaining steps were the same as in example 1, and the content of the crystallization process was varied as shown in Table 14, and the ratio of ethylene glycol in the final product was 5%.
TABLE 14
| Number of crystallization | Total crystalline amount/g | Trans-cis/% |
| Once-through | 6 | 93 |
| Secondary time | 11 | 92.5 |
| Three times | 14 | 92.1 |
Claims (5)
1. A method for purifying trans isomer of 1,4-cyclohexanedimethanol is characterized in that:
(I) Storing a mixed solution containing a solvent, a trans-isomer of 1,4-cyclohexanedimethanol and a cis-isomer of 1,4-cyclohexanedimethanol as a mother solution in a crystallizer, cooling to 0-20 ℃ through a heat exchanger, and filtering through a first discharge pipeline and a filter to obtain a crystal A and a filtrate A; the cooling rate of the cooling is 0.1-1 ℃/min;
(II) the filtrate A enters a crystallizer through a first discharging pipeline to be cooled to below 0 ℃, is solidified and then is heated, and crystals B and filtrate B are obtained through a feeding pipeline; the heating rate of heating after solidification is 0.1-1 ℃/min; raising the temperature to 15-20 ℃;
(III) heating the crystal B in a heat exchanger until the solid is completely dissolved, and flowing out through a second discharging pipeline to obtain the 1,4-cyclohexanedimethanol trans-isomer solution; heating to above 50 ℃ in the heat exchanger;
the device used in the method for purifying the trans isomer of the 1,4-cyclohexanedimethanol comprises a crystallizer (1), a heat exchanger (2), a feeding pipeline (6), a filter (3), a first discharging pipeline (4) and a second discharging pipeline (5); wherein the crystallizer (1) is connected with the heat exchanger (2) through a feeding pipeline (6); one end of the first discharging pipeline (4) is connected with a second outlet of the heat exchanger (2), and the other end of the first discharging pipeline is connected with the crystallizer (1) through the filter (3), so that mother liquor is circulated and enters the crystallizer (1) again; the second discharging pipeline (5) is connected with a second outlet of the heat exchanger (2) to discharge the trans isomer of the 1, 4-cyclohexanedimethanol.
2. The method for purifying trans isomer of 1,4-cyclohexanedimethanol according to claim 1, characterized in that: and (3) heating in the heat exchanger at a heating rate of more than 5 ℃/min.
3. The method for purifying trans isomer of 1,4-cyclohexanedimethanol according to claim 1, characterized in that: the initial ratio of the trans isomer of the 1,4-cyclohexanedimethanol to the cis isomer of the 1,4-cyclohexanedimethanol is 6:4-8:2.
4. The method for purifying trans isomer of 1,4-cyclohexanedimethanol according to claim 1, characterized in that: the heat exchanger comprises heat exchange areas (7) and mother liquor treatment equipment (8) which are alternately arranged, and the contact boundaries of the heat exchange areas (7) and the mother liquor treatment equipment (8) are all wave curves.
5. The method for purifying trans isomer of 1,4-cyclohexanedimethanol according to claim 4, characterized in that: the mother liquor treatment equipment (8) is divided into a plurality of mother liquor solidification and melting units by wavy curves on two sides, and each unit is of a spherical structure.
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