CN117085348A - System and method for separating and purifying 1, 4-butanediol - Google Patents
System and method for separating and purifying 1, 4-butanediol Download PDFInfo
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- CN117085348A CN117085348A CN202311352249.4A CN202311352249A CN117085348A CN 117085348 A CN117085348 A CN 117085348A CN 202311352249 A CN202311352249 A CN 202311352249A CN 117085348 A CN117085348 A CN 117085348A
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000926 separation method Methods 0.000 claims abstract description 37
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims description 128
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 61
- 238000010992 reflux Methods 0.000 claims description 43
- 230000006835 compression Effects 0.000 claims description 34
- 238000007906 compression Methods 0.000 claims description 34
- 230000006837 decompression Effects 0.000 claims description 22
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005265 energy consumption Methods 0.000 abstract description 41
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000000746 purification Methods 0.000 description 23
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 18
- 239000004280 Sodium formate Substances 0.000 description 12
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 12
- 235000019254 sodium formate Nutrition 0.000 description 12
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 11
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 229920006238 degradable plastic Polymers 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 polybutylene terephthalate Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/007—Energy recuperation; Heat pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/146—Multiple effect distillation
-
- 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
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical industry. In the prior art, when butanediol is separated and purified, the energy consumption cannot be effectively reduced on the premise of ensuring the purity and quality of the product. The invention provides a system and a method for separating and purifying 1, 4-butanediol. The system comprises: a pressure concentration column for pressure concentrating the feed; a reduced pressure concentration tower connected to the pressurized concentration tower for concentrating the primary concentrated solution under reduced pressure; the pre-tower is connected to the reduced pressure concentration tower, the secondary concentrated solution is rectified and separated, gas containing water, hydroxybutanal and 1, 4-butanediol is output from the top of the tower, and liquid containing 1, 4-butanediol and tar is output from the bottom of the tower; the product tower comprises gas and liquid inlets at the upper part and the lower part, wherein the gas inlet is connected to a gas outlet of the pre-tower, the liquid inlet is connected to a liquid outlet of the pre-tower, and 1, 4-butanediol products are obtained through separation. The system has simple structure and convenient use, can be used for separating and purifying the 1, 4-butanediol, and greatly reduces the energy consumption in the separating and purifying process.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a system and a method for separating and purifying 1, 4-butanediol.
Background
1, 4-butanediol (hereinafter referred to as butanediol) is an important basic organic chemical raw material, and is mainly used for producing thermoplastic elastic polyurethane (TPU), polytetrahydrofuran (PTMEG), spandex, degradable plastics such as polybutylene terephthalate (PBAT), polybutylene adipate (PBS) and the like. Particularly, with the gradual awareness of social environmental protection, the adoption of degradable plastics instead of non-degradable plastics is a trend. However, the high cost of use is a significant obstacle to the replacement of degradable plastics. Even the current alkynal method with the lowest butanediol production cost has the problem of excessively high energy consumption. Therefore, the new technology and the new process are adopted to reduce the energy consumption and the cost in the butanediol production process, and the problem that the sustainable development of the industry needs to be solved urgently is solved.
In the butanediol mixture synthesized by the alkynal method, the butanediol accounts for about half of the ratio, and the other half is mainly water and other reaction byproducts including low-boiling-point substances such as n-butanol and the like, and high-boiling-point substances such as hydroxybutanal and tar and the like. Rectification is a key step in the butanediol refining process, because it not only relates to the purity and quality of the final product, but also the energy consumption of the rectification unit is about more than half of the whole production process.
CN 114853573A discloses a system and a method for separating and purifying 1, 4-butanediol, which increase the relative volatility of butanediol and 2- (4-hydroxy butoxy) tetrahydrofuran by compounding an extractant to obtain a butanediol product with purity of more than 99.99%, reduce butanediol loss and have higher separation efficiency, but the introduction of the extractant requires newly added equipment, and the regeneration and reuse of the extractant requires a large amount of energy consumption.
CN 107778141A proposes a method for purifying 1, 4-butanediol, which comprises the steps of removing aldehyde compounds or acetal compounds by reaction under the condition of hydrogen by using a supported silver catalyst, and obtaining Gao Chunding diol products with chromaticity less than 10 APHA.
CN 114669073A discloses a 1, 4-butanediol multi-effect rectification apparatus system and a multi-effect rectification process, including dehydration, desalination, residue removal, product purification and heat optimization systems. The system provided by the invention can be used for dehydrating first, recovering n-butanol, recovering residual liquid 1, 4-butanediol again and purifying 1, 4-butanediol, so that the purity and recovery rate of 1, 4-butanediol are improved, but the system is more complex and the equipment investment is higher. The invention optimizes energy to a certain extent, but the dehydration system adopts a compression dehydration tower and a decompression dehydration tower which are arranged in parallel, simultaneously reserves a tower top condenser and a tower kettle reboiler of an atmospheric concentration tower and a decompression concentration tower, ensures that the condensation heat of the atmospheric tower top is not completely matched with the heat required by the decompression tower, and has larger energy-saving range.
The current butanediol refining process adopts conventional rectification technology, including a concentration tower, a salt tower, a high-boiling tower and a low-boiling tower. Firstly separating out water and n-butanol in a concentration tower, and then sequentially removing tar, high-boiling substances and low-boiling substances. Since the butanediol accounts for only about half of the mixture obtained by the reaction, the evaporation amount required by rectification is large. On the other hand, because the butanediol has higher boiling point, the rectification separation needs to consume more high-pressure steam, so that the energy consumption occupies larger proportion of the production cost of the whole product. The development age of the traditional butanediol separation process is early, the reboiler at the tower bottom is heated by medium-pressure steam, and the heat of the condenser at the tower top is completely taken by circulating cooling water and finally is scattered in the environment, so that the butanediol separation process is brought into a high-energy consumption process list, and the development of the butanediol industry is limited.
In conclusion, in the process of separating and purifying the butanediol, on the premise of ensuring the purity and quality of the product, the energy consumption is effectively reduced, the equipment investment cost and the occupied area are reduced, and the method has important practical significance.
Disclosure of Invention
The first aim of the invention is to provide a system for separating and purifying 1, 4-butanediol, which has simple structure and convenient use, can be used for separating and purifying 1, 4-butanediol, simplifies equipment and can greatly reduce energy consumption in the separating and purifying process;
The second object of the invention is to provide a method for separating and purifying 1, 4-butanediol by using the system, which can be used for separating and purifying 1, 4-butanediol, can simplify equipment and greatly reduce energy consumption in the separating and purifying process.
In order to achieve the first object of the present invention, the following technical solutions are adopted:
a system for separating and purifying 1, 4-butanediol, which comprises a pressurizing concentration tower C1, a depressurizing concentration tower C2, a pre-tower C3 and a product tower C4 which are connected in sequence;
the pressurized concentration tower C1 is provided with a feed pipeline for introducing and pressurizing and concentrating a feed containing 1, 4-butanediol, water, n-butanol, hydroxybutanal and tar, removing light components containing water and n-butanol from the top of the pressurized concentration tower C1, and outputting a primary concentrated solution containing hydroxybutanal, tar and 1, 4-butanediol from the bottom of the pressurized concentration tower C1;
the feed inlet of the decompression concentration tower C2 is connected to the bottom outlet of the compression concentration tower C1 and is used for receiving the primary concentrated solution from the compression concentration tower C1, decompressing and concentrating the primary concentrated solution, extracting light components containing water and n-butanol from the top of the compression concentration tower C, and outputting secondary concentrated solution which is 1, 4-butanediol crude product from the bottom of the compression concentration tower C2;
The feed inlet of the pre-tower C3 is connected to the bottom outlet of the vacuum concentration tower C2 and is used for receiving the secondary concentrated solution from the vacuum concentration tower C2, rectifying the secondary concentrated solution to primarily separate, outputting gas containing water, hydroxybutanal and 1, 4-butanediol from the top of the pre-tower C3, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the pre-tower C2;
the product column C4 comprises a gas inlet at the upper part and a liquid inlet at the lower part, the gas inlet of the product column C4 is connected to the gas outlet of the pre-column C3, the liquid inlet of the product column C4 is connected to the liquid outlet of the pre-column C3, and is used for respectively receiving the gas and the liquid from the pre-column C3 at different positions to further rectify and separate the gas and the liquid, removing light components containing water and hydroxybutanal from the top of the column, laterally extracting 1, 4-butanediol product from the side line, and discharging heavy components containing tar from the bottom of the column.
In the system for separating and purifying 1, 4-butanediol, preferably, the bottom of the reduced pressure concentration tower C2 is provided with a second tower bottom reboiler E2, and the tower top is provided with a second tower top condenser E3;
the heat medium inlet of the second tower bottom reboiler E2 is connected to the tower top outlet of the pressurizing and concentrating tower C1, and is used for carrying out heat exchange and temperature rise on the secondary concentrated solution from the depressurizing and concentrating tower C2 by taking the light component from the pressurizing and concentrating tower C1 as a heat medium, cooling and condensing the light component from the pressurizing and concentrating tower C1, and outputting the cooled and condensed light component condensate from the heat medium outlet thereof.
In the system for separating and purifying 1, 4-butanediol of the present invention, preferably, the bottom of the pressurized concentration column C1 is provided with a first bottom reboiler E1, but no overhead condenser is provided;
the reflux inlet of the pressurized concentration column C1 is connected to the heat medium outlet of the second bottom reboiler E2 for refluxing the light component condensate from the second bottom reboiler E2.
In the system for separating and purifying 1, 4-butanediol, preferably, the pre-tower C3 is not provided with a tower top condenser and is provided with a reflux inlet; and/or
The pre-tower C3 is not provided with a tower bottom reboiler and is provided with a reboiling inlet;
the product tower C4 is also provided with a gas return port and a liquid return port; the gas return port is positioned at the lower part of the product tower C4 and above the liquid inlet; the liquid return port is positioned at the upper part of the product tower C4 and below the gas inlet; the liquid return port of the device is connected to the reflux inlet at the top of the pre-tower C3, and the gas return port of the device is connected to the reboiling inlet at the bottom of the pre-tower C3, so that liquid and gas are respectively output to the pre-tower C3 at different positions.
The system for separating and purifying 1, 4-butanediol of the invention is characterized in that the gas inlet of the product tower C4 is positioned at 70-90% of the gas inlet from bottom to top; and/or
The liquid inlet of the product tower C4 is positioned at 10-30% of the liquid inlet from bottom to top; and/or
The gas return port of the product tower C4 is positioned at 15-35% of the gas return port from bottom to top; and/or
The liquid return port of the product tower C4 is positioned at 65-85% of the liquid return port from bottom to top.
The system for separating and purifying 1, 4-butanediol of the present invention preferably has a theoretical plate number of 30 to 70 for the product column C4.
In order to achieve the second object of the present invention, the following technical solutions are adopted:
the invention provides a method for separating and purifying 1, 4-butanediol by using the system, which comprises the following steps:
(1) Feeding the feed into a pressurizing and concentrating tower C1 for pressurizing and concentrating, removing light components containing water and n-butanol from the top of the tower, and obtaining primary concentrated solution containing hydroxybutyraldehyde, tar and 1, 4-butanediol from the bottom of the tower;
(2) Sending the primary concentrated solution obtained in the step (1) to a reduced pressure concentration tower C2 for reduced pressure concentration, removing light components containing water and n-butanol from the top of the tower, and obtaining secondary concentrated solution serving as a crude product of 1, 4-butanediol from the bottom of the tower;
(3) Feeding the secondary concentrated solution obtained in the step (2) to the pre-tower C3 for rectification to perform primary separation, outputting gas containing water, hydroxybutyraldehyde and 1, 4-butanediol from the top of the tower, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the tower;
(4) And (3) inputting the gas and the liquid obtained in the step (3) from a gas inlet and a liquid inlet of the product tower C4 respectively, further rectifying and separating light components containing water and hydroxybutyraldehyde from the top of the product tower C4, laterally extracting a 1, 4-butanediol product, and discharging heavy components containing tar from the bottom of the product tower.
In the method, in the step (2), preferably, the tower bottom liquid of the reduced pressure concentration tower C2 is heated and reboiled by using the light component removed in the step (1) as a thermal medium by using a second tower bottom reboiler E2, and meanwhile, the light component removed in the step (1) is cooled and condensed to obtain a light component condensate;
preferably, the process further comprises refluxing the resulting light component condensate from the reflux inlet of the pressurized concentration column C1 to the pressurized concentration column C1.
The process of the present invention, preferably, further comprises a step (5) of said product column C4 outputting gas and liquid from its gas and liquid return ports, respectively, into said pre-column C3.
The method of the present invention, preferably,
the operating conditions of the pressurized concentration column C1 include: the pressure at the top of the tower is 400-900 kPa absolute pressure, and/or the temperature at the top of the tower is 140-170 ℃, and/or the reflux ratio is 0.2-1, and/or the temperature at the bottom of the tower is 165-180 ℃; and/or
The operating conditions of the reduced pressure concentration column C2 include: the pressure at the top of the tower is 20-105 kPa absolute pressure, and/or the temperature at the top of the tower is 60-110 ℃, and/or the reflux ratio is 0.05-0.3, and/or the temperature at the bottom of the tower is 120-160 ℃; and/or
The operating conditions of the pre-column C3 include: the pressure at the top of the tower is 5-20 kPa absolute pressure, and/or the temperature at the top of the tower is 145-165 ℃, and/or the temperature at the bottom of the tower is 155-175 ℃; and/or
The operating conditions of the product column C4 include: the pressure at the top of the column is 5-20 kPa absolute pressure, and/or the temperature at the top of the column is 145-155 ℃, and/or the reflux ratio at the top of the column is 20-40, and/or the temperature at the bottom of the column is 160-180 ℃.
In the method of the present invention, preferably, in the step (1), the content of 1, 4-butanediol in the feed is 40 to 60 wt%;
preferably, in step (1), the feed is a 1, 4-butanediol mixture obtained in the synthesis of 1, 4-butanediol by the aldolization process.
In the process of the present invention, preferably, in the step (2), the water content of the obtained 1, 4-butanediol crude product is not more than 5. 5 wt%.
The invention has the beneficial effects that:
the system for separating and purifying the 1, 4-butanediol and the method for separating and purifying the 1, 4-butanediol by using the system have the following advantages:
(1) The device has the advantages of simple structure and convenient use, can be used for separating and purifying the 1, 4-butanediol, simplifies equipment, and can greatly reduce energy consumption in the separation and purification process;
(2) The system and the process are a novel system and a novel process for separating and purifying 1, 4-butanediol by combining multi-effect rectification and thermocouple rectification, light components such as n-butanol, water and the like in the feed can be separated by utilizing double-effect rectification consisting of a pressurizing concentration tower C1 and a depressurizing concentration tower C2, and the heat at the top of the pressurizing concentration tower C1 is recovered to be used as the heat of a second tower bottom reboiler E2 (a tower bottom reboiler of the depressurizing concentration tower C2), so that the energy consumption for concentrating 1, 4-butanediol is reduced; the thermal coupling rectification formed by the pre-tower C3 and the product tower C4 is utilized, so that at least two heat exchangers can be saved, separation equipment is simplified, and meanwhile, the energy consumption in the separation and purification process of the 1, 4-butanediol can be greatly reduced; therefore, the system and the method can simultaneously reduce the equipment investment and the operation cost of the separation and purification process of the 1, 4-butanediol, thereby reducing the separation and purification cost of the 1, 4-butanediol;
(3) The tower top gas (light component) of the compression concentration tower C1 and the tower bottom liquid (secondary concentrated liquid) of the decompression concentration tower C2 are subjected to heat exchange through a second tower bottom reboiler E2 (tower bottom reboiler of the decompression concentration tower C2), the tower top gas (light component) of the compression concentration tower C1 is completely condensed into liquid (light component condensate) after heat exchange, meanwhile, the heat requirement of the second tower bottom reboiler E2 is just met, the heat recovery of the tower top of the compression concentration tower C1 is realized, and the heating steam consumption of the second tower bottom reboiler E2 is saved;
(4) Light components such as butanediol and water in the feed are separated through double-effect rectification of the compression concentration tower C1 and the decompression concentration tower C2, a crude butanediol product with low water content can be obtained, and the energy consumption of the downstream butanediol purification process is reduced;
(5) The tower top of the pre-tower C3 is not required to be provided with a condenser, meanwhile, the tower bottom of the pre-tower C3 is not required to be provided with a reboiler, the pre-tower C3 and the product tower C4 form thermocouple rectification, and the secondary concentrated solution from the reduced pressure concentration tower C2 fed in the pre-tower C3, the returned liquid from the product tower C4 and the returned gas are subjected to heat and mass transfer in the pre-tower C3 for rectification, so that the primary separation of the secondary concentrated solution from the reduced pressure concentration tower C2 is realized.
Drawings
FIG. 1 is a schematic diagram of the system for separation and purification of 1, 4-butanediol according to the present invention in one embodiment.
Detailed Description
The technical scheme and effects of the present invention are further described below with reference to the accompanying drawings and the detailed description. The following embodiments are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
As shown in fig. 1, the present invention provides a system for separation and purification of 1, 4-butanediol, which comprises a pressurized concentration column C1, a reduced pressure concentration column C2, a pre-column C3 and a product column C4, which are sequentially connected;
the pressurized concentration tower C1 is provided with a feed pipeline for introducing and pressurizing and concentrating a feed containing 1, 4-butanediol, water, n-butanol, hydroxybutanal and tar, removing light components containing water and n-butanol from the top of the pressurized concentration tower C1, and outputting a primary concentrated solution containing hydroxybutanal, tar and 1, 4-butanediol from the bottom of the pressurized concentration tower C1;
the feed inlet of the decompression concentration tower C2 is connected to the bottom outlet of the compression concentration tower C1 and is used for receiving the primary concentrated solution from the compression concentration tower C1, decompressing and concentrating the primary concentrated solution, extracting light components containing water and n-butanol from the top of the compression concentration tower C, and outputting secondary concentrated solution which is 1, 4-butanediol crude product from the bottom of the compression concentration tower C2;
the feed inlet of the pre-tower C3 is connected to the bottom outlet of the vacuum concentration tower C2 and is used for receiving the secondary concentrated solution from the vacuum concentration tower C2, rectifying the secondary concentrated solution to primarily separate, outputting gas containing water, hydroxybutanal and 1, 4-butanediol from the top of the pre-tower C3, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the pre-tower C2;
The product column C4 comprises a gas inlet at the upper part and a liquid inlet at the lower part, the gas inlet of the product column C4 is connected to the gas outlet of the pre-column C3, the liquid inlet of the product column C4 is connected to the liquid outlet of the pre-column C3, and is used for respectively receiving the gas and the liquid from the pre-column C3 at different positions to further rectify and separate the gas and the liquid, removing light components containing water and hydroxybutanal from the top of the column, laterally extracting 1, 4-butanediol product from the side line, and discharging heavy components containing tar from the bottom of the column.
The system for separating and purifying the 1, 4-butanediol has a simple structure and is convenient to use, the system can be used for separating and purifying the 1, 4-butanediol, light components such as n-butanol, water and the like in the feed are removed sequentially through the pressurizing concentration tower C1 and the depressurizing concentration tower C2, light components such as water, hydroxybutanal and the like in the feed, heavy components such as tar and the like are further removed sequentially through the pre-tower C3 and the product tower C4, the 1, 4-butanediol product is obtained, the equipment is simplified, and the energy consumption in the separating and purifying process can be greatly reduced.
In one embodiment, the 1, 4-butanediol content in the feed of the pressurized concentration column C1 is 40-60 wt%, such as 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt% and 58 wt%.
In one embodiment, the feed of the pressurized concentration column C1 is a 1, 4-butanediol mixture obtained during synthesis of 1, 4-butanediol by an alkynal method.
In one embodiment, the feed of the pressurized concentration column C1 comprises 1, 4-Butanediol (BDO), water, n-butanol, hydroxybutanal and tar, and possibly any one or more of methanol, hydrogen, 2-methyl-1, 4-butanediol (MBDO), 4-hydroxybutoxytetrahydrofuran (TBA), pentanediol and sodium formate.
Those skilled in the art will appreciate that in this case, methanol and/or hydrogen are removed as light components from the top of the pressure concentrating column C1; MBDO and/or TBA and/or pentanediol and/or sodium formate as components of the primary concentrate is output from the bottom of the tower;
in the decompression concentration tower C2, residual methanol is taken out of the top of the decompression concentration tower C as a component of wastewater;
in the pre-column C3, pentanediol and/or 2-methyl-1, 4-butanediol (MBDO) is outputted from the top of the pre-column as the composition of the top gas; 4-hydroxybutoxytetrahydrofuran (TBA) and/or sodium formate as a constituent of its bottom liquid is taken off from its bottom;
In the product column C4, pentanediol and/or 2-methyl-1, 4-butanediol (MBDO) is removed from the top of the product column as light components; 4-hydroxybutoxytetrahydrofuran (TBA) and/or sodium formate are discharged as heavy components from the bottom.
In one embodiment, the bottom of the vacuum concentration tower C2 is provided with a second tower bottom reboiler E2, and the top of the vacuum concentration tower C2 is provided with a second tower top condenser E3;
the heat medium inlet of the second tower bottom reboiler E2 is connected to the tower top outlet of the pressurizing and concentrating tower C1, and is used for carrying out heat exchange and temperature rise on the secondary concentrated solution from the depressurizing and concentrating tower C2 by taking the light component from the pressurizing and concentrating tower C1 as a heat medium so as to reboil, cooling and condensing the light component from the pressurizing and concentrating tower C1, and outputting light component condensate from the heat medium outlet.
By the arrangement, the pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, light components such as n-butanol and water in the feed can be removed, and heat at the top of the pressurizing concentration tower C1 can be recovered to serve as reboiling heat of a second tower bottom reboiler E2 (a tower bottom reboiler of the decompressing concentration tower C2), so that energy consumption for concentrating the 1, 4-butanediol is reduced, the operation cost of a 1, 4-butanediol separation and purification process is reduced, and the separation and purification cost of the 1, 4-butanediol is further reduced.
In a preferred embodiment of the system for separating and purifying 1, 4-butanediol of the present invention, the bottom of the pressurized concentration column C1 is provided with a first bottom reboiler E1, but no overhead condenser is provided;
the reflux inlet of the pressurized concentration column C1 is connected to the heat medium outlet of the second bottom reboiler E2 for refluxing the light component condensate from the second bottom reboiler E2.
According to the invention, through the arrangement, the tower top light component can be refluxed in the form of the light component condensate without arranging the tower top condenser on the pressurizing and concentrating tower C1, so that the energy consumption for concentrating the 1, 4-butanediol is reduced, the equipment investment and the operation cost in the process of separating and purifying the 1, 4-butanediol are also reduced, and the cost for separating and purifying the 1, 4-butanediol is further reduced.
In a preferred embodiment of the system for separating and purifying 1, 4-butanediol, a steam auxiliary reboiler is arranged at the bottom of the vacuum concentration tower C2 in parallel or in series, so that the reboiling of tower bottom liquid of the vacuum concentration tower C2 is assisted by the steam auxiliary reboiler, and the operability of the pressurizing concentration tower C1 and the vacuum concentration tower C2 is improved.
In a preferred embodiment of the system for separation and purification of 1, 4-butanediol of the present invention, an auxiliary condenser is provided in parallel or in series at the top of the pressure concentrating column C1, thereby increasing the operability of the pressure concentrating column C1 and the pressure reducing concentrating column C2 by assisting the condensation of the light components of the pressure concentrating column C1 by the auxiliary condenser.
In one embodiment, the pre-tower C3 is not provided with an overhead condenser and is provided with a reflux inlet; and/or
The pre-tower C3 is not provided with a tower bottom reboiler and is provided with a reboiling inlet;
the product tower C4 is also provided with a gas return port and a liquid return port; the gas return port is positioned at the lower part of the product tower C4 and above the liquid inlet; the liquid return port is positioned at the upper part of the product tower C4 and below the gas inlet; the liquid return port of the device is connected to the reflux inlet at the top of the pre-tower C3, and the gas return port of the device is connected to the reboiling inlet at the bottom of the pre-tower C3, so that liquid and gas are respectively output to the pre-tower C3 at different positions.
According to the invention, through the arrangement, the pre-tower C3 and the product tower C4 form thermocouple rectification, so that a tower top condenser and a tower bottom reboiler are not required to be arranged on the pre-tower C3, at least two heat exchangers can be saved, separation equipment is simplified, and meanwhile, the energy consumption in the separation and purification process of the 1, 4-butanediol can be greatly reduced, thereby simultaneously reducing the equipment investment and the operation cost in the separation and purification process of the 1, 4-butanediol, and further reducing the separation and purification cost of the 1, 4-butanediol.
In one embodiment, the gas inlet of the product column C4 is located at 70-90% of its bottom to top, such as 71%, 72%, 74%, 76%, 78%, 80%, 82%, 85% and 89% of the gas inlet.
In one embodiment, the liquid inlet of the product column C4 is located at 10-30% of it from bottom to top, such as 12%, 15%, 18%, 20%, 22%, 24%, 26% and 28%.
In one embodiment, the gas return to the product column C4 is located 15-35% from bottom to top, such as 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32% and 34%.
In one embodiment, the liquid return to the product column C4 is located 65-85% from bottom to top, such as 66%, 68%, 70%, 72%, 75%, 78%, 80% and 82%.
In one embodiment, the side offtake of product column C4 is located from bottom to top 80-95%, such as 82%, 84%, 88%, 90%, 92% and 94%. In the present invention, 1, 4-Butanediol (BDO) concentration is the highest in the whole column in the position range, and the 1, 4-butanediol product with the highest purity can be obtained.
In one embodiment, the theoretical plate number of the product column C4 is 30-70, such as 35, 40, 50, 60 and 65.
In one embodiment, the theoretical plate number of product column C4 is 50;
in a preferred embodiment, the gas inlet of the product column C4 is located at its bottom-to-top trays 35-45, such as 36, 38, 40, 42 and 44;
in a preferred embodiment, the liquid inlet of the product column C4 is located at its bottom-to-top trays 5-15, such as 6, 8, 10, 12 and 14;
in a preferred embodiment, the gas return to the product column C4 is located at its bottom-to-top trays 8-18, such as 10, 12, 14 and 16;
in a preferred embodiment, the liquid return to product column C4 is located at its bottom-to-top trays 32-43, such as 34, 36, 38, 40 and 42;
in a preferred embodiment, the side offtake of the product column C4 is located at its trays 40-48 from bottom to top, such as 41, 43, 45 and 47.
In one embodiment, the bottom of the product column C4 is provided with a fourth bottom reboiler E5 and the top of the column is provided with a fourth top condenser E4.
The system for separating and purifying the 1, 4-butanediol has the following advantages: (1) The device has the advantages of simple structure and convenient use, can be used for separating and purifying the 1, 4-butanediol, simplifies equipment, and can greatly reduce energy consumption in the separation and purification process; (2) The system and the process are a novel system and a novel process for separating and purifying 1, 4-butanediol by combining multi-effect rectification and thermocouple rectification, light components such as n-butanol, water and the like in the feed can be separated by utilizing double-effect rectification consisting of a pressurizing concentration tower C1 and a depressurizing concentration tower C2, and the heat at the top of the pressurizing concentration tower C1 is recovered to be used as the heat of a second tower bottom reboiler E2 (a tower bottom reboiler of the depressurizing concentration tower C2), so that the energy consumption for concentrating 1, 4-butanediol is reduced; the thermal coupling rectification formed by the pre-tower C3 and the product tower C4 is utilized, so that at least two heat exchangers can be saved, separation equipment is simplified, and meanwhile, the energy consumption in the separation and purification process of the 1, 4-butanediol can be greatly reduced; therefore, the system and the method can simultaneously reduce the equipment investment and the operation cost of the separation and purification process of the 1, 4-butanediol, thereby reducing the separation and purification cost of the 1, 4-butanediol; (3) The tower top gas (light component) of the compression concentration tower C1 and the tower bottom liquid (secondary concentrated liquid) of the decompression concentration tower C2 are subjected to heat exchange through a second tower bottom reboiler E2 (tower bottom reboiler of the decompression concentration tower C2), the tower top gas (light component) of the compression concentration tower C1 is completely condensed into liquid (light component condensate) after heat exchange, meanwhile, the heat requirement of the second tower bottom reboiler E2 is just met, the heat recovery of the tower top of the compression concentration tower C1 is realized, and the heating steam consumption of the second tower bottom reboiler E2 is saved; (4) Light components such as butanediol and water in the feed are separated through double-effect rectification of the compression concentration tower C1 and the decompression concentration tower C2, a crude butanediol product with low water content can be obtained, and the energy consumption of the downstream butanediol purification process is reduced; (5) The tower top of the pre-tower C3 is not required to be provided with a condenser, meanwhile, the tower bottom of the pre-tower C3 is not required to be provided with a reboiler, the pre-tower C3 and the product tower C4 form thermocouple rectification, and the secondary concentrated solution from the reduced pressure concentration tower C2 fed in the pre-tower C3, the returned liquid from the product tower C4 and the returned gas are subjected to heat and mass transfer in the pre-tower C3 for rectification, so that the primary separation of the secondary concentrated solution from the reduced pressure concentration tower C2 is realized.
The invention also provides a method for separating and purifying the 1, 4-butanediol by using the system.
In one embodiment, as shown in fig. 1, the method comprises:
(1) Feeding the feed into a pressurizing and concentrating tower C1 for pressurizing and concentrating, removing light components containing water and n-butanol from the top of the tower, and obtaining primary concentrated solution containing hydroxybutyraldehyde, tar and 1, 4-butanediol from the bottom of the tower;
(2) Sending the primary concentrated solution obtained in the step (1) to a reduced pressure concentration tower C2 for reduced pressure concentration, removing light components containing water and n-butanol from the top of the tower, and obtaining secondary concentrated solution serving as a crude product of 1, 4-butanediol from the bottom of the tower;
(3) Feeding the secondary concentrated solution obtained in the step (2) to the pre-tower C3 for rectification to perform primary separation, outputting gas containing water (in the form of steam), hydroxybutanal and 1, 4-butanediol from the top of the tower, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the tower;
(4) And (3) inputting the gas and the liquid obtained in the step (3) from a gas inlet and a liquid inlet of the product tower C4 respectively, further rectifying and separating in the product tower C4, removing light components containing water and hydroxybutyraldehyde from the top of the tower, discharging heavy components containing tar from the bottom of the tower, and obtaining a 1, 4-butanediol product from a lateral line.
In the invention, after the treatment by the method, the light component and the heavy component are separated and removed, and the purity of the obtained 1, 4-butanediol product is higher.
In one embodiment, the 1, 4-butanediol content of the feed to the pressure concentrating column C1 in step (1) is 40-60 wt%, such as 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt% and 58 wt%.
In one embodiment, the feed to the pressurized concentration column C1 in step (1) may comprise any one or more of methanol, hydrogen, 2-methyl-1, 4-butanediol (abbreviated as MBDO), 4-hydroxybutoxytetrahydrofuran (abbreviated as TBA), pentanediol and sodium formate in addition to 1, 4-butanediol (abbreviated as BDO), water, n-butanol, hydroxybutanal and tar.
In this case, as will be understood by those skilled in the art, in step (1), methanol and/or hydrogen are removed as light components from the top of the pressure concentrating column C1; MBDO and/or TBA and/or pentanediol and/or sodium formate as components of the primary concentrate is output from the bottom of the tower;
in the step (2), in the reduced pressure concentration column C2, residual methanol is taken out from the top of the column as a component of the wastewater;
In step (3), in the pre-column C3, pentanediol and/or 2-methyl-1, 4-butanediol (MBDO) is outputted from the top of the column as the composition of its top gas; 4-hydroxybutoxytetrahydrofuran (TBA) and/or sodium formate as a constituent of its bottom liquid is taken off from its bottom;
in step (4), in said product column C4, pentanediol and/or 2-methyl-1, 4-butanediol (MBDO) is removed as light components from the top of the column; 4-hydroxybutoxytetrahydrofuran (TBA) and/or sodium formate are discharged as heavy components from the bottom.
In one embodiment, the feed to the pressurized concentration column C1 is a 1, 4-butanediol mixture obtained in the synthesis of 1, 4-butanediol by the aldolization process.
Those skilled in the art will recognize that the 1, 4-butanediol mixture obtained in the synthesis of 1, 4-butanediol by the alkynal method comprises 1, 4-butanediol, water, n-butanol, hydroxybutyraldehyde and tar, and possibly methanol, hydrogen, 2-methyl-1, 4-butanediol, 4-hydroxybutoxytetrahydrofuran, pentanediol and sodium formate.
In one embodiment, in the step (2), the tower bottom liquid of the reduced pressure concentration tower C2 is heated and reboiled by using the light component removed in the step (1) as a thermal medium by using a second tower bottom reboiler E2, and meanwhile, the light component removed in the step (1) is cooled and condensed to obtain the light component condensate.
In a preferred embodiment of the process of the present invention, the process further comprises refluxing the light component condensate obtained in step (2) from the reflux inlet of the pressurized concentration column C1 to the pressurized concentration column C1.
In a preferred embodiment of the method of the present invention, the method further comprises providing a steam auxiliary reboiler in parallel or in series at the bottom of the vacuum concentration column C2, thereby increasing the operability of the pressure concentration column C1 and the vacuum concentration column C2 by the steam auxiliary reboiler.
In a preferred embodiment of the method of the present invention, the method further comprises providing an auxiliary condenser in parallel or in series at the top of the pressure concentrating column C1, thereby increasing the operability of the pressure concentrating column C1 and the pressure reducing concentrating column C2.
In one embodiment, the method of the present invention further comprises step (5), wherein the product column C4 outputs gas and liquid from its gas and liquid return ports, respectively, to the pre-column C3, so that the pre-column C3 can recycle the heat of the product column C4, saving reboiler and condenser investment, and improving energy utilization efficiency.
In one embodiment, the operating conditions of the pressurized concentration column C1 comprise:
The overhead pressure is 400 to 900 kPa absolute, such as 500 kPa, 600 kPa, 700 kPa, and 800 kPa; and/or
The temperature of the tower top is 140-170 ℃, such as 145 ℃, 150 ℃, 155 ℃, 160 ℃ and 165 ℃; and/or
Reflux ratios of 0.2 to 1, such as 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9; and/or
The tower kettle temperature is 165-180 ℃, such as 170 ℃ and 175 ℃.
In one embodiment, the operating conditions of the reduced pressure concentration column C2 comprise:
the overhead pressure is 20 to 105 kPa absolute, such as 30 kPa, 40 kPa, 50 kPa, 60 kPa, 70 kPa, 80 kPa, 90 kPa and 100 kPa; and/or
The temperature of the top of the column is 60-110deg.C, such as 70deg.C, 80deg.C, 90deg.C and 100deg.C; and/or
Reflux ratios of 0.05 to 0.3, such as 0.1, 0.15, 0.2 and 0.25; and/or
The tower bottom temperature is 120-160deg.C, such as 125deg.C, 130deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C and 155 deg.C.
The process of the present invention, in one embodiment, the operating conditions of the pre-column C3 comprise:
the overhead pressure is 5 to 20 kPa absolute, such as 6 kPa, 8 kPa, 10 kPa, 12 kPa, 14 kPa, 16 kPa and 18 kPa; and/or
The overhead temperature is 145-165 ℃, such as 146 ℃, 148 ℃, 150 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, 160 ℃, 162 ℃ and 164 ℃; and/or
The tower bottom temperature is 155-175 deg.C, such as 156 deg.C, 158 deg.C, 160 deg.C, 162 deg.C, 164 deg.C, 166 deg.C, 168 deg.C, 170 deg.C, 172 deg.C and 174 deg.C.
The process of the present invention, in one embodiment, the operating conditions of the product column C4 comprise:
the overhead pressure is 5 to 20 kPa absolute, such as 6 kPa, 8 kPa, 10 kPa, 12 kPa, 14 kPa, 16 kPa and 18 kPa; and/or
The overhead temperature is 145-155 ℃, such as 146 ℃, 148 ℃, 150 ℃, 152 ℃ and 154 ℃; and/or
The overhead reflux ratio is 20 to 40, such as 25, 30 and 35; and/or
The tower bottom temperature is 160-180deg.C, such as 165 deg.C, 170 deg.C and 175 deg.C.
In one embodiment, the water content of the 1, 4-butanediol crude product obtained in step (2) is less than or equal to 5 wt%, such as 4.5 wt%, 4 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.5 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, etc.
The invention relates to a method for separating and purifying 1, 4-butanediol, which (1) is a novel process for separating and purifying 1, 4-butanediol by combining multi-effect rectification and thermocouple rectification, and light components such as n-butanol, water and the like in the feed can be separated by utilizing double-effect rectification formed by a pressurizing concentration tower C1 and a depressurizing concentration tower C2, and the heat at the top of the pressurizing concentration tower C1 is recovered as the heat of a second tower bottom reboiler E2 (a tower bottom reboiler of the depressurizing concentration tower C2), so that the energy consumption for concentrating 1, 4-butanediol is reduced; the thermal coupling rectification formed by the pre-tower C3 and the product tower C4 is utilized, so that at least two heat exchangers can be saved, separation equipment is simplified, and meanwhile, the energy consumption in the separation and purification process of the 1, 4-butanediol can be greatly reduced; therefore, the method can simultaneously reduce the equipment investment and the operation cost of the separation and purification process of the 1, 4-butanediol, thereby reducing the separation and purification cost of the 1, 4-butanediol; (2) The tower top gas (light component) of the compression concentration tower C1 and the tower bottom liquid (secondary concentrated liquid) of the decompression concentration tower C2 are subjected to heat exchange through a second tower bottom reboiler E2 (tower bottom reboiler of the decompression concentration tower C2), the tower top gas (light component) of the compression concentration tower C1 is completely condensed into liquid (light component condensate) after heat exchange, meanwhile, the heat requirement of the second tower bottom reboiler E2 is just met, the heat recovery of the tower top of the compression concentration tower C1 is realized, and the heating steam consumption of the second tower bottom reboiler E2 is saved; (3) Light components such as butanediol and water in the feed are separated through double-effect rectification of the compression concentration tower C1 and the decompression concentration tower C2, a crude butanediol product with low water content can be obtained, and the energy consumption of the downstream butanediol purification process is reduced; (4) The tower top of the pre-tower C3 is not required to be provided with a condenser, meanwhile, the tower bottom of the pre-tower C3 is not required to be provided with a reboiler, the pre-tower C3 and the product tower C4 form thermocouple rectification, and the secondary concentrated solution from the reduced pressure concentration tower C2 fed in the pre-tower C3, the returned liquid from the product tower C4 and the returned gas are subjected to heat and mass transfer in the pre-tower C3 for rectification, so that the primary separation of the secondary concentrated solution from the reduced pressure concentration tower C2 is realized.
The invention is further illustrated by the following examples.
Example 1
The method for separating and purifying the 1, 4-butanediol by using the system shown in the figure 1 comprises the following steps:
(1) Feeding the feed into a pressurizing and concentrating tower C1 for pressurizing and concentrating, removing light components containing water and n-butanol from the top of the tower, and obtaining primary concentrated solution containing hydroxybutyraldehyde, tar and 1, 4-butanediol from the bottom of the tower;
wherein the feed is a 1, 4-butanediol mixture obtained when synthesizing 1, 4-butanediol by an alkynal method, and comprises 1, 4-butanediol (BDO for short), water, n-butanol, hydroxybutanal, tar, methanol, hydrogen, 2-methyl-1, 4-butanediol (MBDO for short), 4-hydroxybutoxytetrahydrofuran (TBA for short), pentanediol and sodium formate, wherein the content of the 1, 4-butanediol is 54 wt%, the content of the water is 43.5 wt%, the n-butanol is 0.95%, the TBA is 0.5%, the sodium formate is 0.05%, the hydroxybutanal is 0.05%, and the balance is tar and the like;
the operating conditions of the pressurized concentration column C1 include: the pressure at the top of the tower is 700 kPa absolute pressure, the temperature at the top of the tower is 165 ℃, the reflux ratio is 0.53, and the temperature at the bottom of the tower is 176 ℃;
(2) The primary concentrated solution obtained in the step (1) is sent to a decompression concentration tower C2 for decompression concentration, light components (water exists in the form of water vapor) containing water and n-butyl alcohol are removed from the top of the tower, and secondary concentrated solution serving as a crude product of the 1, 4-butanediol is obtained from the bottom of the tower; part of the light components removed from the tower top is taken as reflux liquid after condensation, and the other part of the light components are taken as waste water to directly enter a waste water treatment system; wherein,
The operating conditions of the reduced pressure concentration column C2 include: the pressure at the top of the tower is 60 kPa absolute pressure, the temperature at the top of the tower is 90 ℃, the reflux ratio is 0.12, and the temperature at the bottom of the tower is 140 ℃;
the second tower bottom reboiler E2 heats and reboils tower bottom liquid of the reduced pressure concentration tower C2 by taking the light components removed in the step (1) as heat medium, and simultaneously cools and condenses the light components removed in the step (1) to obtain light component condensate;
(3) Feeding the secondary concentrated solution obtained in the step (2) to the pre-tower C3 for rectification to perform primary separation, outputting gas from the top of the tower and outputting liquid from the bottom of the tower; wherein,
the operating conditions of the pre-column C3 include: the pressure at the top of the tower is 12 kPa absolute pressure, the temperature at the top of the tower is 155 ℃, and the temperature at the bottom of the tower is 165 ℃; the tower top is not provided with a condenser, and the tower bottom is not provided with a reboiler;
(4) The gas and the liquid obtained in the step (3) are respectively input from a gas inlet and a liquid inlet of the product tower C4 and are further rectified and separated in the product tower C4, light components containing water, hydroxybutanal, pentanediol and MBDO are removed from the top of the tower, heavy components containing TBA, sodium formate and tar are discharged from the bottom of the tower, and a 1, 4-butanediol product is obtained from a side line; the product tower C4 also returns the gas and the liquid output by the product tower C4 to the pre-tower C3 through a gas return port and a liquid return port respectively;
Wherein the operating conditions of the product column C4 include:
the pressure at the top of the tower is 5 kPa absolute, the temperature at the top of the tower is 145 ℃, the reflux ratio at the top of the tower is 30, the temperature at the bottom of the tower is 170 ℃, and 50 theoretical plates are arranged;
the gas inlet of the product tower C4 is positioned at the 40 th tower plate from bottom to top;
the liquid inlet of the product tower C4 is positioned at a 7 th tower plate from bottom to top;
the gas return port of the product tower C4 is positioned at the 10 th tower plate from bottom to top;
the liquid return port of the product tower C4 is positioned at the 39 th tower plate from bottom to top;
the side offtake of the product column C4 (1, 4-butanediol product outlet) is positioned at the 42 th column plate from bottom to top.
The results of example 1 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 165 ℃, steam is completely replaced to be used as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 140 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, so that compared with the traditional single concentration tower process, the energy consumption can be saved by 40%;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, energy consumption can be saved by 40% compared with a single two-tower process, and the purity of 1, 4-butanediol in the product can reach more than 99.75%.
Example 2
Compared with example 1, the only difference is that:
in the step (4), the step of "the product column C4 further returns the gas and the liquid outputted therefrom to the pre-column C3 through the gas return port and the liquid return port, respectively" is not performed.
The results of example 2 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 165 ℃, steam is completely replaced to be used as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 140 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, so that compared with the traditional single concentration tower process, the energy consumption can be saved by 40%;
2) The top and the bottom of the pre-tower C3 are respectively provided with an independent condenser and a reboiler, the gas at the top of the tower is condensed into liquid through the independent condenser, one part of the liquid is refluxed, the other part of the liquid is extracted as light components, and the liquid at the bottom of the C3 tower enters a product tower C4 for further separation, thus the method belongs to the traditional two-tower separation process, and the energy consumption and the equipment investment are not saved.
Example 3
Compared with example 1, the only difference is that:
in the step (2), a steam auxiliary reboiler connected in parallel or in series is arranged at the bottom of the vacuum concentration tower C2 to assist in heating and reboiling tower bottom liquid of the vacuum concentration tower C2.
The results of example 3 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 165 ℃, part of steam is replaced as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 140 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, so that compared with the traditional single-stage concentration tower process, the energy consumption can be saved by 30%, and the operability of the compression concentration tower C1 and the decompression concentration tower C2 is enhanced;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, and compared with the independent two-tower process, the energy consumption can be saved by 40%.
Example 4
Compared with example 1, the only difference is that:
in the step (2), an auxiliary condenser connected in parallel or in series is arranged at the top of the pressurizing and concentrating tower C1 to assist in cooling and condensing the light components removed in the step (1).
The results of example 4 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 165 ℃, part of steam is replaced as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 140 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and a small amount of circulating water is used for cooling the gas, so that compared with the traditional single-stage concentration tower process, the energy consumption can be saved by 30%, but the operability of the compression concentration tower C1 and the decompression concentration tower C2 is enhanced;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, and compared with the independent two-tower process, the energy consumption can be saved by 40%.
Example 5
Compared with example 1, the only difference is that:
in the step (1), in the pressurized concentration tower C1, the tower top pressure is 400 kPa, the temperature is 145 ℃, the reflux ratio is 0.2, and the tower bottom temperature is 165 ℃;
in the reduced pressure concentration tower C2 in the step (2), the tower top pressure is 20 kPa absolute pressure, the tower top temperature is 60 ℃, the reflux ratio is 0.05, and the tower bottom temperature is 120 ℃;
in the step (3), in the pre-tower C3, the tower top pressure is 5 kPa, the tower top temperature is 145 ℃, and the tower bottom temperature is 155 ℃;
in the step (4), in the product column C4, the pressure at the top of the column is 20 kPa, the temperature at the top of the column is 155 ℃, the reflux ratio at the top of the column is 20, and the temperature at the bottom of the column is 160 ℃.
The results of example 5 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 145 ℃, steam is completely replaced to be used as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 120 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, however, as the vacuumizing energy consumption of the decompression concentration tower C2 is increased, compared with the traditional single-stage concentration tower process, the energy consumption can be saved by 35%;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, and compared with the independent two-tower process, the energy consumption can be saved by 38%.
Example 6
Compared with example 1, the only difference is that:
in the step (1), in the pressurized concentration tower C1, the tower top pressure is 900 kPa absolute pressure, the tower top temperature is 170 ℃, the reflux ratio is 1, and the tower bottom temperature is 180 ℃;
in the reduced pressure concentration tower C2 in the step (2), the tower top pressure is 105 kPa, the tower top temperature is 110 ℃, the reflux ratio is 0.3, and the tower bottom temperature is 160 ℃;
in the step (3), in the pre-tower C3, the tower top pressure is 20 kPa, the tower top temperature is 165 ℃, and the tower bottom temperature is 175 ℃;
in the step (4), in the product column C4, the pressure at the top of the column is 5 kPa, the temperature at the top of the column is 145 ℃, the reflux ratio at the top of the column is 40, and the temperature at the bottom of the column is 180 ℃.
The results of example 6 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 145 ℃, steam is completely replaced to be used as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 120 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, so that compared with the traditional single-stage concentration tower process, 42% of energy consumption can be saved, but the 1, 4-butanediol in the product has the risk of decomposition and deterioration due to higher temperature at the bottom of the tower;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, and compared with the independent two-tower process, the energy consumption can be saved by 40%.
Example 7
Compared with example 1, the only difference is that:
in step (4), in the product column C4,
the gas inlet of the product tower C4 is positioned at the 45 th tower plate from bottom to top;
the liquid inlet of the product tower C4 is positioned at the 5 th tower plate from bottom to top;
the gas return port of the product tower C4 is positioned at the 8 th tower plate from bottom to top;
the liquid return port of the product tower C4 is positioned at the 43 th tower plate from bottom to top;
the 1, 4-butanediol product outlet of the product tower C4 is positioned at the 48 th tower plate from bottom to top.
The results of example 7 are as follows:
1) The pressurizing concentration tower C1 and the decompressing concentration tower C2 form double-effect rectification, the tower top temperature of the pressurizing concentration tower C1 is 145 ℃, steam is completely replaced to be used as a heat source of a second tower bottom reboiler E2 of the decompressing concentration tower C2, and heat exchange is carried out on tower bottom liquid (secondary concentrated liquid) of the decompressing concentration tower C2 at 120 ℃; the gas (light component) at the top of the compression concentration tower C1 is totally condensed into liquid (light component condensate) after heat exchange, and circulating water is not needed to be used for cooling the gas, so that compared with the traditional single concentration tower process, the energy consumption can be saved by 25%;
2) The pre-tower C3 and the product tower C4 form thermocouple rectification, reflux liquid required by the tower top of the pre-tower C3 and reboiling steam required by the tower kettle are all provided by the side line of the product tower C4 through the gas return port and the liquid return port, a condenser is not required to be arranged on the tower top of the pre-tower C3, a reboiler is not required to be arranged on the tower kettle of the pre-tower C3, the energy consumption is saved by 39% compared with the independent two-tower process, and the purity of the obtained 1, 4-butanediol product can reach more than 99.5%.
The foregoing has outlined the basic flow, main features and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the scope of the present invention in any way, and all technical solutions obtained by equivalent substitution and the like fall within the scope of the present invention. The invention is not related in part to the same as or can be practiced with the prior art.
Claims (10)
1. A system for separating and purifying 1, 4-butanediol, which is characterized by comprising a pressurizing and concentrating tower C1, a depressurizing and concentrating tower C2, a pre-tower C3 and a product tower C4 which are connected in sequence;
the pressurized concentration tower C1 is provided with a feed pipeline for introducing and pressurizing and concentrating a feed containing 1, 4-butanediol, water, n-butanol, hydroxybutanal and tar, removing light components containing water and n-butanol from the top of the pressurized concentration tower C1, and outputting a primary concentrated solution containing hydroxybutanal, tar and 1, 4-butanediol from the bottom of the pressurized concentration tower C1;
The feed inlet of the decompression concentration tower C2 is connected to the bottom outlet of the compression concentration tower C1 and is used for receiving the primary concentrated solution from the compression concentration tower C1, decompressing and concentrating the primary concentrated solution, extracting light components containing water and n-butanol from the top of the compression concentration tower C, and outputting secondary concentrated solution which is 1, 4-butanediol crude product from the bottom of the compression concentration tower C2;
the feed inlet of the pre-tower C3 is connected to the bottom outlet of the vacuum concentration tower C2 and is used for receiving the secondary concentrated solution from the vacuum concentration tower C2, rectifying the secondary concentrated solution to primarily separate, outputting gas containing water, hydroxybutanal and 1, 4-butanediol from the top of the pre-tower C3, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the pre-tower C2;
the product column C4 comprises a gas inlet at the upper part and a liquid inlet at the lower part, the gas inlet of the product column C4 is connected to the gas outlet of the pre-column C3, the liquid inlet of the product column C4 is connected to the liquid outlet of the pre-column C3, and is used for respectively receiving the gas and the liquid from the pre-column C3 at different positions to further rectify and separate the gas and the liquid, removing light components containing water and hydroxybutanal from the top of the column, laterally extracting 1, 4-butanediol product from the side line, and discharging heavy components containing tar from the bottom of the column.
2. The system according to claim 1, wherein the bottom of the vacuum concentration column C2 is provided with a second bottom reboiler E2 and the top is provided with a second top condenser E3;
the heat medium inlet of the second tower bottom reboiler E2 is connected to the tower top outlet of the pressurizing and concentrating tower C1, and is used for carrying out heat exchange and temperature rise on the secondary concentrated solution from the depressurizing and concentrating tower C2 by taking the light component from the pressurizing and concentrating tower C1 as a heat medium, cooling and condensing the light component from the pressurizing and concentrating tower C1, and outputting cooled and condensed light component condensate from the heat medium outlet thereof;
preferably, the bottom of the pressurized concentration column C1 is provided with a first bottom reboiler E1, but no overhead condenser;
the reflux inlet of the pressurized concentration column C1 is connected to the heat medium outlet of the second bottom reboiler E2 for refluxing the light component condensate from the second bottom reboiler E2.
3. The system according to claim 1 or 2, wherein,
the pre-tower C3 is not provided with a tower top condenser and is provided with a reflux inlet; and/or the number of the groups of groups,
the pre-tower C3 is not provided with a tower bottom reboiler and is provided with a reboiling inlet;
the product tower C4 is also provided with a gas return port and a liquid return port; the gas return port is positioned at the lower part of the product tower C4 and above the liquid inlet; the liquid return port is positioned at the upper part of the product tower C4 and below the gas inlet; the liquid return port of the device is connected to the reflux inlet at the top of the pre-tower C3, and the gas return port of the device is connected to the reboiling inlet at the bottom of the pre-tower C3, so that liquid and gas are respectively output to the pre-tower C3 at different positions.
4. The system of claim 3, wherein the system further comprises a controller configured to control the controller,
the gas inlet of the product tower C4 is positioned at 70-90% of the gas inlet from bottom to top; and/or the number of the groups of groups,
the liquid inlet of the product tower C4 is positioned at 10-30% of the liquid inlet from bottom to top; and/or the number of the groups of groups,
the gas return port of the product tower C4 is positioned at 15-35% of the gas return port from bottom to top; and/or the number of the groups of groups,
the liquid return port of the product tower C4 is positioned at 65-85% of the liquid return port from bottom to top.
5. The system of claim 1, wherein the theoretical plate number of product column C4 is from 30 to 70.
6. A method for separating and purifying 1, 4-butanediol using the system according to any one of claims 1-5, comprising:
(1) Feeding the feed into a pressurizing and concentrating tower C1 for pressurizing and concentrating, removing light components containing water and n-butanol from the top of the tower, and obtaining primary concentrated solution containing hydroxybutyraldehyde, tar and 1, 4-butanediol from the bottom of the tower;
(2) Sending the primary concentrated solution obtained in the step (1) to a reduced pressure concentration tower C2 for reduced pressure concentration, removing light components containing water and n-butanol from the top of the tower, and obtaining secondary concentrated solution serving as a crude product of 1, 4-butanediol from the bottom of the tower;
(3) Feeding the secondary concentrated solution obtained in the step (2) to the pre-tower C3 for rectification to perform primary separation, outputting gas containing water, hydroxybutyraldehyde and 1, 4-butanediol from the top of the tower, and outputting liquid containing 1, 4-butanediol and tar from the bottom of the tower;
(4) And (3) inputting the gas and the liquid obtained in the step (3) from a gas inlet and a liquid inlet of the product tower C4 respectively, further rectifying and separating light components containing water and hydroxybutyraldehyde from the top of the product tower C4, laterally extracting a 1, 4-butanediol product, and discharging heavy components containing tar from the bottom of the product tower.
7. The method according to claim 6, wherein in the step (2), the tower bottom liquid of the reduced pressure concentration tower C2 is heated and reboiled by using the second tower bottom reboiler E2 and the light component removed in the step (1) as a thermal medium, and the light component removed in the step (1) is cooled and condensed to obtain a light component condensate;
preferably, the process further comprises refluxing the resulting light component condensate from the reflux inlet of the pressurized concentration column C1 to the pressurized concentration column C1.
8. The method according to claim 6 or 7, further comprising step (5), wherein the product column C4 outputs gas and liquid from its gas and liquid return ports, respectively, into the pre-column C3.
9. The method of claim 6, wherein the step of providing the first layer comprises,
the operating conditions of the pressurized concentration column C1 include: the pressure at the top of the tower is 400-900 kPa absolute pressure, and/or the temperature at the top of the tower is 140-170 ℃, and/or the reflux ratio is 0.2-1, and/or the temperature at the bottom of the tower is 165-180 ℃; and/or the number of the groups of groups,
The operating conditions of the reduced pressure concentration column C2 include: the pressure at the top of the tower is 20-105kPa absolute pressure, and/or the temperature at the top of the tower is 60-110 ℃, and/or the reflux ratio is 0.05-0.3, and/or the temperature at the bottom of the tower is 120-160 ℃; and/or the number of the groups of groups,
the operating conditions of the pre-column C3 include: the pressure at the top of the tower is 5-20 kPa absolute pressure, and/or the temperature at the top of the tower is 145-165 ℃, and/or the temperature at the bottom of the tower is 155-175 ℃; and/or the number of the groups of groups,
the operating conditions of the product column C4 include: the pressure at the top of the column is 5-20 kPa absolute pressure, and/or the temperature at the top of the column is 145-155 ℃, and/or the reflux ratio at the top of the column is 20-40, and/or the temperature at the bottom of the column is 160-180 ℃.
10. The method of claim 6, wherein the step of providing the first layer comprises,
in the step (1), the content of 1, 4-butanediol in the feed is 40-60 wt%;
preferably, in the step (1), the feed is a 1, 4-butanediol mixture obtained in the synthesis of 1, 4-butanediol by an alkynal method;
preferably, in the step (2), the water content of the obtained 1, 4-butanediol crude product is less than or equal to 5 and wt percent.
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