WO2023272948A1 - 一种十二碳醇酯的连续生产系统 - Google Patents

一种十二碳醇酯的连续生产系统 Download PDF

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WO2023272948A1
WO2023272948A1 PCT/CN2021/117983 CN2021117983W WO2023272948A1 WO 2023272948 A1 WO2023272948 A1 WO 2023272948A1 CN 2021117983 W CN2021117983 W CN 2021117983W WO 2023272948 A1 WO2023272948 A1 WO 2023272948A1
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tower
raw material
reaction
material tank
continuous production
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PCT/CN2021/117983
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English (en)
French (fr)
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张世元
宋文国
卢小松
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润泰新材料股份有限公司
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Priority to US17/785,926 priority Critical patent/US20240182402A1/en
Publication of WO2023272948A1 publication Critical patent/WO2023272948A1/zh

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    • 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
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the invention relates to the field of organic synthesis, in particular to a continuous production system of dodecyl alcohol esters.
  • Dodecyl alcohol ester scientific name 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate, commercial name dodecyl alcohol ester, molecular formula: C 12 H 24 O 3 , structural formula:
  • Relative molecular weight 216.31 (according to the international relative atomic mass in 2016).
  • Dodecyl alcohol ester is the most widely used film-forming additive for architectural coatings. Compared with ordinary film-forming aids, dodecyl alcohol ester has many advantages: good resin compatibility, less dosage, low film-forming temperature, It has good film leveling and color development, low freezing point, good hydrolytic stability and low toxicity. polymers, and latexes such as pure acrylic, styrene/acrylic, polystyrene butadiene, and vinyl vinyl acetate. There are many manufacturers of dodecyl alcohol esters in the market, and the quality indicators vary greatly. Different qualities of dodecyl alcohol esters have a great impact on the performance of coatings in coating applications, especially the water resistance of coatings.
  • the step-by-step reaction equation includes:
  • 2,2,4-trimethyl-1,3-pentanediol and isobutyric acid obtained by the stepwise reaction are esterified under the action of a catalyst to generate dodecyl alcohol ester.
  • a catalyst to generate dodecyl alcohol ester.
  • side reactions in addition to the above-mentioned main reaction, there are also a large number of side reactions in the reaction system, and the occurrence of side reactions will bring a large number of by-products, which will affect the purity of the product and other issues.
  • most of the synthesis processes of dodecyl alcohol esters are produced by batch method.
  • the batch method production process has problems such as unstable batches, many by-products, and low yield. Under this technical background, continuous production of dodecyl alcohol
  • the ester process has clear advantages.
  • the purpose of the present invention is to overcome the defective of prior art, a kind of continuous production system of dodecyl alcohol ester is provided, described system adopts continuous method production process to prepare dodecyl alcohol ester, greatly improves the production capacity of dodecyl alcohol ester Productivity, purity and yield.
  • the present invention first provides a continuous production system of dodecyl alcohol ester, and the production system includes: a raw material tank, including a raw material tank inlet end and the outlet port of the raw material tank; the reaction tower, the inlet port of the reaction tower is communicated with the outlet port of the raw material tank, and the reaction tower includes the first outlet port of the reaction tower and the second outlet port of the reaction tower; the atmospheric distillation tower , the inlet port of the atmospheric distillation tower communicates with the outlet port of the reaction tower, the atmospheric distillation tower includes a first outlet port of atmospheric distillation and a second outlet port of atmospheric distillation; condenser, the condensing The device includes a first inlet port of the condenser and a second inlet port of the condenser, and the first inlet port of the condenser and the second inlet port of the condenser are respectively connected with the second outlet port of the reaction column and the second outlet
  • the tower includes a first outlet port of vacuum distillation and a second outlet port of vacuum distillation, the second outlet port of vacuum distillation communicates with the inlet port of the reaction tower; a water washing tower, the inlet port of the water washing tower is connected to the The first outlet port of the vacuum distillation tower is connected; the dehydration tower, the inlet port of the dehydration tower is connected with the outlet port of the water washing tower; the evaporator, the inlet port of the evaporator is connected with the outlet port of the dehydration tower Light removal tower, the inlet port of the light removal tower communicates with the outlet port of the evaporation tower; rectification tower, the inlet port of the rectification tower communicates with the outlet end of the light removal tower.
  • the raw material tank, reaction tower, atmospheric distillation tower, vacuum distillation tower, condenser, water washing tower, dehydration tower, evaporator, light removal tower, and rectification tower are all connected by pipelines , the pipeline is provided with a material transfer pump.
  • the reaction tower has a structure of 4-6 layers of square tank reactors connected in series.
  • the height of the reaction tower is 6-8 meters
  • the diameter of the reaction tower is 700-800 millimeters
  • the vertical distance h between the square grooves in the square groove reactor is 200-300 millimeters
  • the height of the bottommost square tank of the square tank reactor is 0.5 to 0.6 times the overall height of the reaction tower.
  • the vacuum distillation column is further provided with a third outlet port of vacuum distillation.
  • the heating temperature at the bottom of the reaction tower is 75-80°C.
  • the raw material tank includes a first raw material tank and a second raw material tank, the first raw material tank and the second raw material tank are connected in parallel, isobutyraldehyde is contained in the first raw material tank, The catalyst aqueous solution is contained in the second raw material tank, and the isobutyraldehyde and the catalyst aqueous solution enter the reaction tower from top to bottom.
  • the feed mass flow ratio of the isobutyraldehyde to the aqueous catalyst solution is (25-50):1.
  • the continuous production system further includes a hexadecyl diester raw material tank, and the hexadecyl diester raw material tank communicates with the bottom outlet port of the rectification tower.
  • the continuous reaction of the present invention transforms the production route of dodecyl alcohol ester from the traditional intermittent tank type production process into a continuous tower reaction process, which effectively improves the batch stability of dodecyl alcohol ester, making the product With the further improvement of the purity and yield, the unit consumption of the product can be reduced from 1.1 to 1.04.
  • the present invention is designed with multiple reflux recovery systems, and is equipped with a separation and purification unit for layer-by-layer separation of by-products, so that the production process of dodecyl alcohol esters has low unit consumption, high purity, and stable batches.
  • the liquid has a high purity and can be subsequently used as a raw material for the production of cetyl alcohol ester. It is a set of energy-saving, environmentally friendly, and green recycling synthesis process.
  • Figure 1 shows a schematic flow diagram of the continuous production system of the present invention.
  • Fig. 2 shows the structural schematic diagram of the reaction tower of the present invention.
  • the present invention provides a continuous production system of dodecyl alcohol esters.
  • the continuous production system includes various unit operations connected in series by pipelines. Materials can be transported by material delivery pumps in the pipelines.
  • the material delivery pump may include a metering pump 100, a discharge pump 200, and the like.
  • described production system can comprise raw material tank (1,2), and described raw material tank can be used for containing and storing the synthetic raw material of dodecyl alcohol ester, and described synthetic raw material can comprise isobutyl Aldehyde and basic catalyst, described raw material tank (1,2) can comprise the first raw material tank 1 and the second raw material tank 2, can hold isobutyraldehyde in the described first raw material tank 1, described second raw material tank Can hold the aqueous solution of basic catalyst in the tank 2.
  • Metering pumps 100 can be arranged on the outlet pipelines of the raw material tanks (1, 2), and the metering pumps 100 can facilitate the quantitative injection of the raw materials in the raw material tanks (1, 2) into subsequent reaction equipment.
  • Described catalyst can be any one or more combinations in potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, and in some embodiments, described catalyst can be sodium hydroxide, calcium hydroxide, hydrogen
  • the barium oxide is composed of (3-5):(1-2):(1-2) in weight ratio.
  • the aqueous solution of the catalyst may be prepared by mixing the catalyst solid and water according to the weight ratio (1-2):1.
  • described continuous production system can comprise reaction tower 3, can finish the synthesis reaction of described dodecyl alcohol ester inside described reaction tower 3, and the top of described reaction tower 3 can be provided with There is a first inlet port 31 of the reaction tower and a second inlet port 32 of the reaction tower, and the raw material in the raw material tank (1, 2) can enter the inside of the reaction tower 3 through the inlet port (31, 32) of the reaction tower to
  • the isobutyraldehyde can be reacted under the action of a catalyst, and the inside of the reaction tower 3 can have a structure in which multilayer square tank reactors are connected in series, for example, it can be provided with 4 to 6 square tanks 35.
  • the number of the 35 square grooves can be 5
  • the side length of the square grooves 35 can be 400-600 mm
  • the square grooves 35 can be connected through the through holes at the bottom of the square grooves 35, and the reaction
  • the structure of the multi-layer square tank reactor inside the tower 3 can improve the conversion rate and yield of the synthesis reaction.
  • the raw material in the raw material tank (1, 2) can enter the reaction tower 3 from the top inlet port (31, 32) of the reaction tower 3 from top to bottom, and finally flow into the bottom of the reaction tower 3,
  • the heating temperature at the bottom of the reaction tower 3 can be 75-80°C.
  • the isobutyraldehyde can react under the action of a catalyst, and the reaction in the reaction tower 3 is normal pressure reaction.
  • the height of the reaction tower 3 can be 6 to 8 meters
  • the diameter of the reaction tower 3 can be 700 to 800 millimeters
  • the vertical distance between the layers of the multilayer square tank reactor h is 200-300 mm
  • the height of the bottommost square tank 35 of the multi-layer square tank reactor is 0.5-0.6 times the overall height of the reaction tower 3 .
  • the isobutyraldehyde in the first raw material tank 1 enters the reaction tower 3 from top to bottom, and the aqueous solution of the catalyst enters the reaction tower 3 from the second raw material tank 2 from top to bottom.
  • the mass flow rate can be (25-50): 1
  • the present invention uses the reaction tower to carry out the reaction so that the isobutyraldehyde and the catalyst can continuously meet in reverse in the square tank reactor and react layer by layer.
  • the conversion rate of dodecyl alcohol ester can be improved and the occurrence of side reactions can be reduced by designing a multi-layer square tank reaction tower 3 .
  • the reaction tower 3 can include a first outlet port 33 of the reaction tower at the bottom and a second outlet port 34 of the reaction tower at the top, and the first outlet port 33 of the reaction tower can be connected with the continuous production system
  • the follow-up separation equipment is connected and then the reaction liquid at the bottom of the reaction tower 3 is continuously sent to the follow-up separation equipment, and the second outlet port 34 of the reaction tower can return the excess isobutyraldehyde in the reaction tower to the first raw material tank 1 in.
  • described continuous production system also includes atmospheric distillation column 4, and described atmospheric distillation column 4 can be used for removing excessive isobutyraldehyde in the reaction liquid, and the inlet port of described atmospheric distillation column 4 It can communicate with the first outlet port 33 of the reaction tower, the temperature of the bottom of the atmospheric distillation tower 4 can be 150-160 °C, and the atmospheric distillation tower 4 can include two outlet ports, for example, it can include a bottom Atmospheric distillation first outlet port 41 and top atmospheric distillation second outlet port 42.
  • the continuous production system can also include a condenser 5, the first inlet port 51 of the condenser 5 and the second inlet port 52 of the condenser can be connected with the second outlet port 34 of the reaction tower and The second outlet port 42 of the atmospheric distillation is communicated, and the condenser 5 can be a multistage condenser, such as a three-stage condenser, and the condenser 5 can connect the reaction column 3 and the atmospheric distillation column 4 Excessive isobutyraldehyde in the process is condensed and recovered, and the condenser 5 can be used to return the isobutyraldehyde that has been dehydrated to the first raw material tank 1.
  • the continuous production system can also include a vacuum distillation tower 6, the pressure in the vacuum distillation tower 6 can be -0.08 ⁇ -0.1MPa, and the temperature of the tower bottom can be 160 ⁇ 170°C.
  • Described decompression distillation tower 6 can discharge a small amount of isobutyraldehyde and a small amount of by-product isobutanol that distill out system, and described a small amount of isobutyraldehyde can return to continue to participate in reaction in described reaction tower 3 by pipeline, so The small amount of isobutanol can be discharged from the system through other outlets of the vacuum distillation tower 6.
  • the vacuum distillation column 6 can include multiple outlet ports, for example, it can include a first outlet port 61 for vacuum distillation, a second outlet port 62 for vacuum distillation, and a third outlet port 63 for vacuum distillation. end, the first outlet 61 end of the vacuum distillation can be communicated with the subsequent water washing equipment, and the second outlet 62 end of the vacuum distillation can return a small amount of isobutyraldehyde separated to the reaction tower 3 to participate in the reaction, so The third outlet 63 of the vacuum distillation can discharge impurities such as isobutanol, which can be a by-product generated by the following reaction.
  • the continuous production system can also include a water-washing tower 7, and the water-washing tower 7 can wash the dealdehyde reaction liquid through the atmospheric distillation tower 4 and the vacuum distillation tower 6 with water for further Remove the impurity in the esterification reaction liquid, the water-soluble substances such as potassium isobutyrate in the reaction liquid can be removed by the water washing tower 7, and the potassium isobutyrate can be obtained by reacting catalyst potassium hydroxide and isobutyric acid By-products, the reaction equation is as follows.
  • the detergent water in the water washing tower 7, the detergent water can be pumped continuously into the water washing tower 7 together with the dealdehyde-depleted reaction solution for water washing.
  • Described continuous production system can also comprise dehydration tower 8, and described dehydration tower 8 is communicated with described washing tower 7, and described dehydration tower 8 can be vacuum dehydration tower 8, and the tower still temperature of described dehydration tower 8 can be 150-160°C, the pressure of the dehydration tower 8 may be -0.09--0.1 MPa.
  • the continuous production system can also include an evaporator 9, the heating temperature at the bottom of the evaporator 9 can be 250-300°C, and the evaporator 9 can further separate the organic and inorganic phases, purify the The above crude ester reaction liquid, and save energy consumption, the vaporized gas phase material can further enter the follow-up light removal tower 10 to remove light component impurities.
  • the continuous production system can also include a light removal tower 10, and the light removal tower 10 can remove the light component by-products in the reaction system, and the light component can include pentylene glycol etc.
  • the light removal tower 10 can be a negative pressure light removal
  • the temperature of the tower bottom of the light removal tower 10 can be 155 ⁇ 160 ° C
  • the pressure in the light removal tower 10 can be -0.09 ⁇ -0.12MPa, For example -0.1MPa.
  • the light removal tower 10 can further remove light component impurities such as pentanediol in the reaction liquid, and the light components containing pentanediol evaporated from the top of the tower can be used as raw materials for hexadecane production.
  • the continuous production system can also include rectifying the crude esters that have taken off the light components.
  • the production system can also include a rectification tower 11, and the rectification
  • the tower 11 can be negative pressure rectification
  • the tower still temperature of described rectification tower 11 can be 165 ⁇ 170 °C
  • the pressure in described rectification tower 11 can be-0.09 ⁇ -0.12MPa, for example-0.1MPa, so Described rectification can remove heavy component impurity
  • described heavy component can include by-products such as cetyl alcohol isoester
  • side reaction equation can be as follows:
  • the residual liquid in the distillation tower 11 tower kettle can be used as part of the production raw material of cetyl diester, and the residual liquid can be sent to storage in the cetyl diester raw material tank 13, and the rectifying tower
  • the dodecyl alcohol ester evaporated from the top of the 11 tower can be pumped to the storage tank 12 in the finished product area for storage after being condensed, and then packed in the packaging room.
  • the continuous production method of the continuous production of described dodecyl alcohol ester comprises the following steps:
  • reaction tower 3 is a series structure of five-layer square tank reactors. The material overflows from top to bottom and finally flows into the bottom of the reaction tower 3. When the material reaches a liquid level above 40% at the bottom of the reactor, the bottom of the reaction tower 3 Heating, when the temperature at the bottom of the reaction tower 3 reaches 80°C, start the tower kettle discharge pump to pump out the reaction solution and start discharging.
  • the height of the synthesis tower is 7 meters, and the diameter is 800 mm.
  • the height of the groove is 0.6 times of the overall height of the reaction tower 3, and the vertical distance between the square groove reactors is 300 mm.
  • the reaction liquid is continuously pumped into the atmospheric distillation column 4 for dealdehydeization under atmospheric pressure, the temperature of the tower kettle is 160°C, and the excess isobutyraldehyde is continuously released from the top of the tower, and returned to the first raw material tank 1 after three-stage condensation, and the aldehyde is completely removed.
  • the tower still liquid is pumped into the vacuum distillation tower 6 again.
  • the height of the atmospheric distillation tower 4 is 12 meters, the diameter is 600 millimeters, and steel wire mesh packing is built-in, and the reflux ratio is 2.
  • reaction solution after dealdehyde removal is continuously pumped into the vacuum distillation tower 6 for dealdehyde removal under negative pressure (-0.09MPa), the reflux ratio is 2, the temperature of the tower kettle is 160-170°C, a small amount of aldehyde (isobutyraldehyde) and alcohol (isobutyraldehyde) Butanol) is continuously withdrawn from the top of the tower, and isobutyraldehyde returns to reaction tower 3 to participate in the reaction.
  • the lauryl alcohol ester crude product that has taken off aldehyde is continuously pumped into the water washing tower 7 (being 12 meters high and 500 mm in diameter) together with water for washing.
  • the esterified liquid after washing enters the dehydration tower 8 (9 meters in height and 600 mm in diameter) for negative pressure (-0.092 MPa) dehydration, and the temperature of the tower kettle is 150°C.
  • the dehydrated crude ester is continuously pumped into the evaporator 9, and the gas phase material is heated from the top of the evaporator into the light removal tower 10 for negative pressure (-0.1MPa) light removal.
  • Diol light components are used as raw materials for the production of cetyl diester.
  • the crude esters that have completely removed the light components are continuously pumped into the rectification tower 11 (15 meters in height and 600 mm in diameter) for negative pressure (-0.1 MPa) rectification.
  • the distillation raffinate of still is used as the part production raw material of hexadecanyl diester, and tower top steams dodecyl alcohol ester and is pumped to storage tank 12 of finished product area after being condensed and stored, then transfers to packing room packing, adopts the present invention
  • the purity of the dodecyl alcohol ester prepared by the continuous preparation process reaches above 99.0%, the yield reaches above 80%, and the total yield reaches above 95%.
  • the present invention also designs the comparative example of embodiment 1 for different reaction towers, has carried out the comparison of purity and yield for the dodecyl alcohol ester obtained at last, and evaluation result is as table 1 shown.

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Abstract

本发明提供了一种十二碳醇酯的连续生产系统，所述连续生产系统通过将原料罐、反应塔、常压蒸馏塔、减压蒸馏塔、冷凝器、水洗塔、脱水塔、蒸发器、脱轻塔、精馏塔均通过管路连通，所述连续生产系统代替传统的间歇式生产工艺，具有批次稳定性好，副产物少，收率高的优势。

Description

一种十二碳醇酯的连续生产系统 技术领域
本发明涉及有机合成领域，具体涉及一种十二碳醇酯的连续生产系统。
背景技术
十二碳醇酯，学名2,2,2-三甲基-1,3-戊二醇单异丁酸酯，商业名称十二碳醇酯，分子式：C 12H 24O 3，结构式为：
Figure PCTCN2021117983-appb-000001
或者为：
Figure PCTCN2021117983-appb-000002
相对分子量：216.31(按2016年国际相对原子质量)。
十二碳醇酯是应用最为广泛的建筑涂料用成膜助剂，与普通成膜助剂相比，十二碳醇酯有诸多优点：树脂相溶性好，用量少，成膜温度低，膜流平性、展色性好，凝固点低，水解稳定性好，毒性低，是一种极好的乳胶漆成膜助剂，可以有效地用于聚乙酸乙烯均聚物、共聚物和三聚物中，以及纯丙烯酸、苯乙烯/丙烯酸、聚丁苯乙烯和乙烯基乙酸乙烯等乳胶中。市场上十二碳醇酯的生产厂家很多，质量指标差异很大，不同品质的十二碳醇酯在涂料应用中，对涂料的性能有很大的影响，特别是对涂料的耐水性能，储存稳定性，耐擦洗等性能有很大的影响。目前十二碳醇酯的合成工艺主要是以异丁醛为原料在碱性催化剂的作用下经过羟醛缩合以及坎尼扎罗反应后酯化制备，总反应方程式为：
Figure PCTCN2021117983-appb-000003
分步反应方程式包括有：
Figure PCTCN2021117983-appb-000004
分步反应得到的2,2,4-三甲基-1,3-戊二醇和异丁酸在催化剂作用下酯化反应生成十二碳醇酯。此外，除了上述主反应外，反应体系内还存在大量的副反应，副反应的发生会带来大量的副产物，进而影响产品的纯度等问题。目前大部分十二碳醇酯合成工艺均采用间歇法生产，间歇法生产工艺存在批次不稳定，副产物较多，收率偏低等问题，在此技术背景下连续化生产十二碳醇酯工艺具有明显的优势。
发明内容
本发明的目的在于克服现有技术的缺陷，提供了一种十二碳醇酯的连续生产系统，所述系统采用连续法生产工艺制备十二碳醇酯，大大提高了十二碳醇酯的生产效率、纯度以及收率。
为了实现以上目的及其他目的，本发明是通过包括以下技术方案实现的：本发明首先提供了一种十二碳醇酯的连续生产系统，所述生产系统包括：原料罐，包括有原料罐入口端和原料罐出口端；反应塔，所述反应塔的入口端和所述原料罐出口端连通，所述反应塔包括有反应塔第一出口端以及反应塔第二出口端；常压蒸馏塔，所述常压蒸馏塔的入口端和所述反应塔的出口端连通，所述常压蒸馏塔包括有常压蒸馏第一出口端和常压蒸馏第二出口端；冷凝器，所述冷凝器包括有冷凝器第一入口端以及冷凝器第二入口端，所述冷凝器的第一入口端以及冷凝器第二入口端分别和所述反应塔第二出口端以及常压蒸馏第二出口端连通，所述冷凝器的出口端和所述原料罐入口端连通；减压蒸馏塔，所述减压蒸馏塔的入口端和所述常压蒸馏第一出口端连通，所述减压蒸馏塔包括有减压蒸馏第一出口端以及减压蒸馏第二出口端，所述减压蒸馏第二出口端和所述反应塔的入口端连通；水洗塔，所述水洗塔的入口端和所述减压蒸馏塔第一出口端连通；脱水塔，所述脱水塔的入口端和所述水洗塔的出口端连通；蒸发器，所述蒸发器的入口端和所述脱水塔的出口端连通；脱轻塔，所述脱轻塔的入口端和所述蒸发塔的出口端连通；精馏塔，所述精馏塔的入口端和所述脱轻塔的出口端连通。
在一实施例中，所述原料罐、反应塔、常压蒸馏塔、减压蒸馏塔、冷凝器、水洗塔、脱水塔、蒸发器、脱轻塔、精馏塔之间均通过管路连通，所述管路上设置有物料输送泵。
在一实施例中，所述反应塔内具有4～6层方槽反应器串联的结构。
在一实施例中，所述反应塔的高度为6～8米，所述反应塔的直径为700～800毫米，所述方槽反应器中方槽之间的垂直距离h为200～300毫米，所述方槽反应器的最底层方槽的高度为所述反应塔整体高度的0.5～0.6倍。
在一实施例中，所述减压蒸馏塔上还设置有减压蒸馏第三出口端。
在一实施例中，所述反应塔塔底的加热温度为75～80℃。
在一实施例中，所述原料罐包括有第一原料罐以及第二原料罐，所述第一原料罐和所述第二原料罐并联，所述第一原料罐中盛放异丁醛，所述第二原料罐中盛放催化剂水溶液，所述异丁醛和所述催化剂的水溶液自上而下进入所述反应塔内。
在一实施例中，所述异丁醛和催化剂水溶液的进料质量流量比为(25～50)：1。
在一实施例中，所述连续生产系统还包括有十六碳双酯原料罐，所述十六碳双酯原料罐和所述精馏塔的底部出口端连通。
如上所述，本发明连续化反应将十二碳醇酯的生产路线由传统的间歇釜式生产工艺改造成连续塔式反应工艺，有效提升了十二碳醇酯的批次稳定性，使得产品的纯度以及收率的进一步提升，产品单耗可以从1.1降低至1.04。
本发明设计有多个回流回收体系，并且设置层层分离副产物的分离提纯单元，使得十二碳醇酯的生产工艺单耗低，纯度高，批次稳定，本系统最后得到的反应液残液纯度较高，可以后续作为十六碳醇酯的生产原料使用，是一套节能环保、绿色循环的合成工艺。
附图说明
图1显示为本发明连续生产系统的流程示意图。
图2显示为本发明反应塔的结构示意图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所提供的内容较容易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
请参阅图1。本发明提供了一种十二碳醇酯的连续生产系统，所述连续生产系统中包括有利用管路串联起来的各类单元操作，所述管路中可以通过物料输送泵来输送物料，所述物料输送泵可以包括有计量泵100、出料泵200等。
如图1所示，所述生产系统可以包括有原料罐(1，2)，所述原料罐可以用来盛放和储存十二碳醇酯的合成原料，所述合成原料可以包括有异丁醛和碱性催化剂，所述原料罐(1，2)可以包括有第一原料罐1和第二原料罐2，所述第一原料罐1中可以盛放异丁醛，所述第二原料罐2中可以盛放碱性催化剂的水溶液。所述原料罐(1，2)的出口管路上均可以设置有计量泵100，所述计量泵100可以便于将原料罐(1，2)中的原料定量的打入后续反应设备中。所述催化剂可以是氢氧化钾、氢氧化钠、氢氧化钙、氢氧化钡中的任意一种或多种组合，在一些实施例中，所述催化剂可以是氢氧化钠、氢氧化钙、氢氧化钡按照重量比为(3～5)：(1～2)：(1～2)组成。所述催化剂的水溶液可以是将催化剂固体和水按照重量比(1～2)：1配合而成。
如图1和图2所示，所述连续生产系统可以包括有反应塔3，在所述反应塔3内部可以完成所述十二碳醇酯的合成反应，所述反应塔3的顶部可以设置有反应塔第一入口端31以及反应塔第二入口端32，所述原料罐(1，2)中的原料可以通过所述反应塔入口端(31，32)进入所述反应塔3内部以使得所述异丁醛可以在催化剂的作用下进行反应，所述反应塔3内部可以具有多层方槽反应器串联的结构，例如可以是设置有4～6个方槽35，在一实施例中，所述方槽35个数可以是5个，所述方槽35的边长可以是400～600毫米，所述方槽35之间可以通过方槽35底部的通孔连通，所述反应塔3内部具有的多层方槽反应器的结构可以提高合成反应的转化率以及收率。所述原料罐(1，2)中的原料可以是由所述反应塔3的顶部入口端(31，32)自上而下进入所述反应塔3内，最终流入所述反应塔3底部，所述反应塔3底部的加热温度可以是75～80℃，在此反应温度下，所述异丁醛可以在催化剂作用下进行反应，所述反应塔3中的反应为常压反应。在一实施例中，所述反应塔3的高度可以为6～8米，所述反应塔3的直径可以为700～800毫米，所述多层方槽反应器之间层与层的垂直距离h为200～300毫米，所述多层方槽反应器的最底层方槽35的高度为所述反应塔3整体高度的0.5～0.6倍。
在一些实施例中，所述第一原料罐1中的异丁醛自上而下进入所述反应塔3中，催化剂的水溶液自第二原料罐2自上而下打入所述反应塔3中，所述反应塔3塔釜中液位达到30～50％时，塔底开始升温，当所述塔底升温到80℃时，开始出料，所述异丁醛和催化剂水溶液的进料质量流量可以是(25～50)：1，本发明采用所述反应塔进行反应可以使得所述异丁醛和所述催化剂不停的在所述方槽反应器逆向相遇并逐层反应，本发明通过设计多层的方槽反应塔3，可以提高十二碳醇酯的转化率，降低副反应的发生。
如图1所示，所述反应塔3可以包括有底部的反应塔第一出口端33以及顶部的反应塔第二出口端34，所述反应塔第一出口端33可以和所述连续生产系统的后续分离设备相连进而将所述反应塔3底部的反应液连续送入后续分离设备，所述反应塔第二出口端34可以将反应塔中过量的异丁醛送回所述第一原料罐1中。
如图1所示，所述连续生产系统还包括有常压蒸馏塔4，所述常压蒸馏塔4可以用于除去反应液中过量的异丁醛，所述常压蒸馏塔4的入口端可以和所述反应塔第一出口端33连通，所述常压蒸馏塔4塔釜的温度可以是150～160℃，所述常压蒸馏塔4可以包括两个出口端，例如可以包括有底部的常压蒸馏第一出口端41以及顶部的常压蒸馏第二出口端42。
如图1所示，所述连续生产系统还可以包括有冷凝器5，所述冷凝器5的第一入口端51以及冷凝器第二入口端52可以和所述反应塔第二出口端34以及所述常压蒸馏第二出口端42 连通，所述冷凝器5可以是多级冷凝器，例如三级冷凝器，所述冷凝器5可以将所述反应塔3以及所述常压蒸馏塔4中过量的异丁醛冷凝回收，所述冷凝器5可以是将去除掉水分的异丁醛送回所述第一原料罐1中。
如图1所示，所述连续生产系统还可以包括有减压蒸馏塔6，所述减压蒸馏塔6内的压力可以是-0.08～-0.1MPa，塔釜温度可以是160～170℃，所述减压蒸馏塔6可以将蒸馏出的少量异丁醛以及少量的副产物异丁醇排出系统，所述少量的异丁醛可以通过管路返回所述反应塔3中继续参与反应，所述少量的异丁醇可以通过所述减压蒸馏塔6的其他出口排出系统。在一些实施例中，所述减压蒸馏塔6可以包括有多个出口端，例如可以包括有减压蒸馏第一出口端61、减压蒸馏第二出口62端以及减压蒸馏第三出口63端，所述减压蒸馏第一出口61端可以和后续的水洗设备连通，所述减压蒸馏第二出口62端可以将分离出的少量异丁醛送回所述反应塔3参与反应，所述减压蒸馏第三出口63端可以排出异丁醇等杂质，所述异丁醇可以是通过如下反应生成的副产物。
Figure PCTCN2021117983-appb-000005
如图1所示，所述连续生产系统还可以包括有水洗塔7，所述水洗塔7可以将经过所述常压蒸馏塔4和所述减压蒸馏塔6的脱醛反应液进行水洗进一步去掉酯化反应液中的杂质，所述水洗塔7可以将反应液中的例如异丁酸钾等水溶性物质去掉，所述异丁酸钾可以是催化剂氢氧化钾和异丁酸发生反应得到的副产物，反应方程式如下。
Figure PCTCN2021117983-appb-000006
如图1所示，在所述水洗塔7中，洗涤剂水可以和所述脱完醛的反应液一起通过泵连续打入所述水洗塔7中进行水洗。所述连续生产系统还可以包括有脱水塔8，所述脱水塔8和所述水洗塔7连通，所述脱水塔8可以是减压脱水塔8，所述脱水塔8的塔釜温度可以是150～160℃，所述脱水塔8的压力可以是-0.09～-0.1MPa。
如图1所示，所述连续生产系统还可以包括有蒸发器9，所述蒸发器9底部的加热温度可以是250～300℃，所述蒸发器9可以进一步将有机无机相分离，提纯所述粗酯反应液，并 节约能耗，蒸发后的气相物料可以进一步进入后续的脱轻塔10中脱掉轻组分杂质。
如图1所示，所述连续生产系统还可以包括有脱轻塔10，所述脱轻塔10可以将反应体系中的轻组分副产物去除，所述轻组分可以包括有戊二醇等，所述脱轻塔10可以是负压脱轻，所述脱轻塔10的塔釜温度可以是155～160℃，所述脱轻塔10中的压力可以是-0.09～-0.12MPa，例如-0.1MPa。所述脱轻塔10可以进一步去除反应液中的戊二醇等轻组分杂质，所述塔顶蒸出含戊二醇轻组分可以作为十六碳生产的原材料。
如图1所示，所述连续生产系统还可以包括有将脱完轻组分的粗酯进行精馏，在一些实施中，所述生产系统还可以包括有精馏塔11，所述精馏塔11可以是负压精馏，所述精馏塔11的塔釜温度可以是165～170℃，所述精馏塔11中的压力可以是-0.09～-0.12MPa，例如-0.1MPa，所述精馏可以脱除重组分杂质，所述重组分可以包括有十六碳醇异酯等副产物，副反应方程式可以是如下所示：
Figure PCTCN2021117983-appb-000007
如图1所示，所述精馏塔11塔釜中的残留液可以作为十六双酯的部分生产原料，所述残留液可以送至十六碳双酯原料罐13中储存，精馏塔11塔顶蒸出的十二碳醇酯冷凝后可以用泵送至成品区储存罐12中进行储存，再到包装间包装。
实施例1
在一实施例中，所述十二碳醇酯的连续生产的连续生产方法包括以下步骤：
(1)合成酯化
异丁醛从第一原料罐1用泵以1.5吨/小时的流速打进合成塔顶部，催化剂氢氧化钾的水 溶液自第二原料罐2以60kg/小时的流速自上而下打入所述反应塔3中。反应塔3为五层方槽反应器的串联结构，物料溢流自上而下，最终流入反应塔3底部，当物料在所述塔釜底部达到40％以上的液位时，反应塔3底部加热，当所述反应塔3底部的温度达到80℃，开启塔釜出料泵泵出反应液开始出料，合成塔的高度为7米，直径为800毫米，方槽反应器的最底层方槽的高度为所述反应塔3整体高度的0.6倍，方槽反应器之间的垂直距离为300毫米。
(2)常压蒸馏
反应液连续泵入常压蒸馏塔4中常压脱醛，塔釜温度160℃，过量的异丁醛从塔顶连续脱出，经三级冷凝后返回第一原料罐1中，脱完醛的塔釜液再泵入减压蒸馏塔6中，常压蒸馏塔4的高度为12米，直径为600毫米，内置有钢丝网填料，回流比为2。
(3)减压蒸馏
脱完醛的反应液再连续泵入减压蒸馏塔6中负压(-0.09MPa)脱醛，回流比为2，塔釜温度160～170℃，少量醛(异丁醛)及醇(异丁醇)从塔顶连续脱出，异丁醛返回反应塔3参与反应。
(4)水洗分层
脱完醛的十二碳醇酯粗品与水一起连续泵入水洗塔7(高为12米，直径为500毫米)进行水洗。
(5)减压脱水
水洗后的酯化液进入脱水塔8(高为9米，直径为600毫米)进行负压(-0.092MPa)脱水，塔釜温度150℃。
(6)减压脱轻
脱完水的粗酯连续泵入蒸发器9，通过加热气相物料从蒸发器顶部进入脱轻塔10中进行负压(-0.1MPa)脱轻，塔釜温度155℃，塔顶蒸出含戊二醇轻组分作为十六碳双酯生产的原材料。
(7)精制、脱重、包装
脱完轻组分的粗酯连续泵入精馏塔11(高为15米，直径为600毫米)中进行负压(-0.1MPa)精馏，回流比为3，塔釜温度165℃，塔釜的蒸馏残液作为十六碳双酯的部分生产原料，塔顶蒸出十二碳醇酯经冷凝后用泵送至成品区储存罐12储存，再转至包装间包装，采用本发明所述连续制备工艺制备得到的十二碳醇酯的纯度达到99.0％以上，收率达到80％以上，总收率达到95％以上。
评价
采用和实施例1类似的方法，本发明还针对不同的反应塔设计了实施例1的对比例，针对最后得到的十二碳醇酯进行了纯度和收率的比较,，评价结果如表1所示。
表1 不同反应塔设计的纯度和收率数据对照表
Figure PCTCN2021117983-appb-000008
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (9)

  1. 一种十二碳醇酯的连续生产系统，其特征在于，所述系统包括：
    原料罐，包括有原料罐入口端和原料罐出口端；
    反应塔，所述反应塔的入口端和所述原料罐出口端连通，所述反应塔包括有反应塔第一出口端以及反应塔第二出口端；
    常压蒸馏塔，所述常压蒸馏塔的入口端和所述反应塔的出口端连通，所述常压蒸馏塔包括有常压蒸馏第一出口端和常压蒸馏第二出口端；
    冷凝器，所述冷凝器包括有冷凝器第一入口端以及冷凝器第二入口端，所述冷凝器第一入口端以及冷凝器第二入口端分别和所述反应塔第二出口端以及常压蒸馏第二出口端连通，所述冷凝器的出口端和所述原料罐入口端连通；
    减压蒸馏塔，所述减压蒸馏塔的入口端和所述常压蒸馏第一出口端连通，所述减压蒸馏塔包括有减压蒸馏第一出口端以及减压蒸馏第二出口端，所述减压蒸馏第二出口端和所述反应塔的入口端连通；
    水洗塔，所述水洗塔的入口端和所述减压蒸馏塔第一出口端连通；
    脱水塔，所述脱水塔的入口端和所述水洗塔的出口端连通；
    蒸发器，所述蒸发器的入口端和所述脱水塔的出口端连通；
    脱轻塔，所述脱轻塔的入口端和所述蒸发塔的出口端连通；
    精馏塔，所述精馏塔的入口端和所述脱轻塔的出口端连通。
  2. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述原料罐、反应塔、常压蒸馏塔、减压蒸馏塔、冷凝器、水洗塔、脱水塔、蒸发器、脱轻塔、精馏塔之间均通过管路连通，所述管路上设置有物料输送泵。
  3. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述反应塔内具有4～6层方槽反应器串联的结构。
  4. 根据权利要求3所述的十二碳醇酯的连续生产系统，其特征在于：所述反应塔的高度为6～8米，所述反应塔的直径为700～800毫米，所述方槽反应器中方槽之间的垂直距离h为200～300毫米，所述方槽反应器的最底层方槽的高度为所述反应塔整体高度的0.5～0.6倍。
  5. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述减压蒸馏塔 上还设置有减压蒸馏第三出口端。
  6. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述反应塔塔底的加热温度为75～80℃。
  7. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述原料罐包括有第一原料罐以及第二原料罐，所述第一原料罐和所述第二原料罐并联，所述第一原料罐中盛放异丁醛，所述第二原料罐中盛放催化剂水溶液，所述异丁醛和所述催化剂的水溶液自上而下进入所述反应塔内。
  8. 根据权利要求7所述的十二碳醇酯的连续生产系统，其特征在于：所述异丁醛和催化剂水溶液的进料质量流量比为(25～50)：1。
  9. 根据权利要求1所述的十二碳醇酯的连续生产系统，其特征在于：所述连续生产系统还包括有十六碳双酯原料罐，所述十六碳双酯原料罐和所述精馏塔的底部出口端连通。
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