TWI686377B - Apparatus and method for manufacturing dimethylhexane-1,6-dicarbamate - Google Patents
Apparatus and method for manufacturing dimethylhexane-1,6-dicarbamate Download PDFInfo
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本發明是有關於一種化合物的製造裝置及製造方法,且特別是有關於一種六亞甲基-1,6-二氨基甲酸甲酯(dimethylhexane-1,6-dicarbamate,HDC)的製造裝置及製造方法。The invention relates to a compound manufacturing device and manufacturing method, and in particular to a manufacturing device and manufacturing of hexamethylene-1,6-dicarbamate (HDC) method.
六亞甲基-1,6-二異氰酸酯(hexamethylene-1,6-diisocyanate,HDI)這類脂肪族異氰酸酯是聚氨酯(PU)工業的重要原料,利用HDI生產的PU具有保色、保光、抗粉化、耐曬、耐油、耐磨等特點,此為芳香族異氰酸酯生產的PU所不及。Hexamethylene-1,6-diisocyanate (hexadiethylene-1,6-diisocyanate, HDI) such as aliphatic isocyanate is an important raw material for the polyurethane (PU) industry, PU produced by HDI has color retention, gloss retention, resistance Powdering, light resistance, oil resistance, wear resistance, etc., this is unmatched by PU produced by aromatic isocyanate.
HDI傳統上是由1,6-己二胺(1,6-hexanediamine,HDA)經光氣化合成,但此法有光氣極端毒性和副產物鹽酸嚴重腐蝕的缺點。因此,HDI的有效且環保的合成方法受到高度的注意。最近,以HDA為原料使用兩個步驟合成HDI的非光氣方法引起很多關注,第一步是HDC的合成,第二步是HDC進行熱裂解生成HDI。在這種方法中,HDC是一種中間體,其合成在整個HDI生產過程扮演重要腳色。HDI is traditionally synthesized from 1,6-hexanediamine (HDA) via phosgenation, but this method has the disadvantages of extreme toxicity of phosgene and severe corrosion of by-product hydrochloric acid. Therefore, the effective and environmentally friendly synthesis method of HDI has received high attention. Recently, a non-phosgene method using two steps to synthesize HDI using HDA as a raw material has attracted much attention. The first step is the synthesis of HDC, and the second step is the thermal cracking of HDC to generate HDI. In this method, HDC is an intermediate, and its synthesis plays an important role in the entire HDI production process.
然而,在生產HDC時的能耗與生產成本高。因此,如何有效地降低在生產HDC時的能耗與生產成本為目前持續努力的目標。However, the energy consumption and production cost when producing HDC are high. Therefore, how to effectively reduce the energy consumption and production cost in the production of HDC is the goal of continuous efforts at present.
本發明提供一種HDC的製造裝置與製造方法,其可大幅度降低在生產HDC時的能耗與生產成本。The invention provides an HDC manufacturing device and manufacturing method, which can greatly reduce the energy consumption and production cost when producing HDC.
本發明提出一種HDC的製造裝置,包括反應器、HDA供應裝置、碳酸二甲酯(dimethyl carbonate,DMC)供應裝置與第一蒸餾塔。HDA供應裝置連接至反應器。DMC供應裝置連接至反應器。第一蒸餾塔連接至反應器的出料口。第一蒸餾塔包括上段塔、下段塔與壓縮機。壓縮機連接在下段塔的氣體出口與上段塔的氣體入口之間。The invention provides an HDC manufacturing device, including a reactor, an HDA supply device, a dimethyl carbonate (DMC) supply device, and a first distillation tower. The HDA supply device is connected to the reactor. The DMC supply device is connected to the reactor. The first distillation column is connected to the discharge port of the reactor. The first distillation column includes an upper column, a lower column and a compressor. The compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower.
依照本發明的一實施例所述,在上述HDC的製造裝置中,在反應器中可具有觸媒。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, a catalyst may be provided in the reactor.
依照本發明的一實施例所述,在上述HDC的製造裝置中,上段塔的液體出口可連接至下段塔的液體入口。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the liquid outlet of the upper column can be connected to the liquid inlet of the lower column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,上段塔的塔頂氣體產物溫度高於下段塔的塔底液體產物溫度。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,上段塔的塔頂氣體產物溫度可比下段塔的塔底液體產物溫度高5°C以上。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the temperature of the gas product at the top of the upper column may be higher than the temperature of the liquid product at the bottom of the lower column by more than 5°C.
依照本發明的一實施例所述,在上述HDC的製造裝置中,上段塔中的壓力大於下段塔中的壓力。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the pressure in the upper column is greater than the pressure in the lower column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,更包括第一再沸器。第一再沸器連接至下段塔的塔底。可將上段塔的塔頂氣體產物作為第一再沸器的熱源。According to an embodiment of the invention, the HDC manufacturing device further includes a first reboiler. The first reboiler is connected to the bottom of the lower column. The top gas product of the upper column can be used as the heat source of the first reboiler.
依照本發明的一實施例所述,在上述HDC的製造裝置中,更包括第二再沸器。第二再沸器連接至下段塔的塔底。According to an embodiment of the present invention, the HDC manufacturing apparatus further includes a second reboiler. The second reboiler is connected to the bottom of the lower column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,更包括第二蒸餾塔。第二蒸餾塔連接至下段塔的塔底。According to an embodiment of the present invention, the HDC manufacturing device further includes a second distillation column. The second distillation column is connected to the bottom of the lower column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,更包括萃取蒸餾塔。萃取蒸餾塔連接至上段塔的塔頂。According to an embodiment of the present invention, the HDC manufacturing apparatus further includes an extractive distillation column. The extractive distillation column is connected to the top of the upper column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,更包括萃取劑回收塔。萃取劑回收塔連接至萃取蒸餾塔的塔底。According to an embodiment of the present invention, the HDC manufacturing device further includes an extractant recovery tower. The extractant recovery tower is connected to the bottom of the extractive distillation tower.
依照本發明的一實施例所述,在上述HDC的製造裝置中,可將第二蒸餾塔的塔底液體產物作為連接至萃取蒸餾塔的塔底的再沸器、連接至萃取劑回收塔的塔底的再沸器與連接在上段塔與萃取蒸餾塔之間的熱交換器中的至少一者的熱源。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the liquid product at the bottom of the second distillation column can be used as a reboiler connected to the bottom of the extractive distillation column and connected to the extractant recovery column. The reboiler at the bottom of the column and the heat source of at least one of the heat exchangers connected between the upper column and the extractive distillation column.
依照本發明的一實施例所述,在上述HDC的製造裝置中,可將萃取劑回收塔的塔底液體產物作為連接在上段塔與萃取蒸餾塔之間的熱交換器的熱源。According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the bottom liquid product of the extractant recovery column can be used as the heat source of the heat exchanger connected between the upper column and the extractive distillation column.
本發明提出一種HDC的製造方法,包括以下步驟。在反應器中,使HDA與DMC在存在觸媒的環境下進行反應,而產生反應後之產物。使反應後之產物進入第一蒸餾塔中,而產生第一塔頂氣體產物與第一塔底液體產物。第一蒸餾塔包括上段塔、下段塔與壓縮機。由上段塔產生第一塔頂氣體產物。由下段塔產生第一塔底液體產物。壓縮機連接在下段塔的氣體出口與上段塔的氣體入口之間。The invention provides a method for manufacturing HDC, including the following steps. In the reactor, HDA and DMC are reacted in the presence of a catalyst to produce a product after the reaction. The product after the reaction enters the first distillation column to produce the first gas product at the top of the column and the liquid product at the bottom of the first column. The first distillation column includes an upper column, a lower column and a compressor. The first overhead gas product is produced from the upper column. The first bottom liquid product is produced from the lower column. The compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower.
依照本發明的一實施例所述,在上述HDC的製造方法中,上段塔的液體出口可連接至下段塔的液體入口。According to an embodiment of the present invention, in the above HDC manufacturing method, the liquid outlet of the upper column can be connected to the liquid inlet of the lower column.
依照本發明的一實施例所述,在上述HDC的製造方法中,上段塔的塔頂氣體產物溫度高於下段塔的塔底液體產物溫度。According to an embodiment of the present invention, in the above HDC manufacturing method, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column.
依照本發明的一實施例所述,在上述HDC的製造方法中,上段塔的塔頂氣體產物溫度可比下段塔的塔底液體產物溫度高5°C以上。According to an embodiment of the present invention, in the above HDC manufacturing method, the temperature of the gas product at the top of the upper column may be higher than the temperature of the liquid product at the bottom of the lower column by more than 5°C.
依照本發明的一實施例所述,在上述HDC的製造方法中,上段塔中的壓力大於下段塔中的壓力。According to an embodiment of the present invention, in the above HDC manufacturing method, the pressure in the upper column is greater than the pressure in the lower column.
依照本發明的一實施例所述,在上述HDC的製造方法中,在HDA與DMC的反應中,可使用過量的DMC作為反應物。According to an embodiment of the present invention, in the above HDC manufacturing method, in the reaction of HDA and DMC, excess DMC may be used as a reactant.
依照本發明的一實施例所述,在上述HDC的製造方法中,在HDA與DMC的反應中,DMC與HDA的進料莫耳比值例如是3至9。According to an embodiment of the present invention, in the above HDC manufacturing method, in the reaction of HDA and DMC, the feed molar ratio of DMC to HDA is, for example, 3 to 9.
依照本發明的一實施例所述,在上述HDC的製造方法中,反應後之產物可包括HDC、甲醇(methanol,MeOH)與DMC。第一塔頂氣體產物可包括MeOH與DMC。第一塔底液體產物可包括HDC與DMC。According to an embodiment of the present invention, in the above HDC manufacturing method, the products after the reaction may include HDC, methanol (MeOH), and DMC. The first overhead gas product may include MeOH and DMC. The first bottom liquid product may include HDC and DMC.
依照本發明的一實施例所述,在上述HDC的製造方法中,可將上段塔的第一塔頂氣體產物作為連接至下段塔的塔底的再沸器的熱源。According to an embodiment of the present invention, in the above HDC manufacturing method, the first overhead gas product of the upper column can be used as the heat source of the reboiler connected to the bottom of the lower column.
依照本發明的一實施例所述,在上述HDC的製造方法中,更可包括使第一塔底液體產物進入第二蒸餾塔中,而產生第二塔頂液體產物與第二塔底液體產物。According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, it may further include allowing the first bottom liquid product to enter the second distillation column to produce a second top liquid product and a second bottom liquid product .
依照本發明的一實施例所述,在上述HDC的製造方法中,第二塔頂液體產物可包括DMC。第二塔底液體產物可包括HDC。According to an embodiment of the invention, in the above HDC manufacturing method, the second overhead liquid product may include DMC. The second bottom liquid product may include HDC.
依照本發明的一實施例所述,在上述HDC的製造方法中,更可包括使第一塔頂氣體產物經冷凝後所得的第一塔頂液體產物與萃取劑進入萃取蒸餾塔中,而產生第三塔頂液體產物與第三塔底液體產物。According to an embodiment of the present invention, in the above HDC manufacturing method, it may further include that the first overhead liquid product and the extractant obtained after the condensation of the first overhead gas product are condensed into an extractive distillation column to produce The liquid product at the top of the third column and the liquid product at the bottom of the third column.
依照本發明的一實施例所述,在上述HDC的製造方法中,第三塔頂液體產物可包括MeOH。第三塔底液體產物可包括DMC與萃取劑。According to an embodiment of the invention, in the above HDC manufacturing method, the third overhead liquid product may include MeOH. The third bottom liquid product may include DMC and extractant.
依照本發明的一實施例所述,在上述HDC的製造方法中,更可包括使第三塔底液體產物進入萃取劑回收塔中,而產生第四塔頂液體產物與第四塔底液體產物。According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, it may further include allowing the third bottom liquid product to enter the extractant recovery column to produce a fourth top liquid product and a fourth bottom liquid product .
依照本發明的一實施例所述,在上述HDC的製造方法中,第四塔頂液體產物可包括DMC。第四塔底液體產物可包括萃取劑。According to an embodiment of the present invention, in the above HDC manufacturing method, the fourth overhead liquid product may include DMC. The fourth bottom liquid product may include an extractant.
依照本發明的一實施例所述,在上述HDC的製造方法中,可將第二蒸餾塔的第二塔底液體產物作為連接至萃取蒸餾塔的塔底的再沸器、連接至萃取劑回收塔的塔底的再沸器與連接在上段塔與萃取蒸餾塔之間的熱交換器中的至少一者的熱源。According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, the second bottom liquid product of the second distillation column can be used as a reboiler connected to the bottom of the extractive distillation column and connected to the extractant recovery The reboiler at the bottom of the column and the heat source of at least one of the heat exchangers connected between the upper column and the extractive distillation column.
依照本發明的一實施例所述,在上述HDC的製造方法中,可將萃取劑回收塔的第四塔底液體產物作為連接在上段塔與萃取蒸餾塔之間的熱交換器的熱源。According to an embodiment of the present invention, in the above HDC manufacturing method, the fourth bottom liquid product of the extractant recovery column can be used as the heat source of the heat exchanger connected between the upper column and the extractive distillation column.
基於上述,在上述HDC的製造裝置與製造方法中,由於下段塔操作在低壓,所以可有效地降低下段塔的塔底再沸器能耗(reboiler duty)。另外,由於DMC-MeOH共沸物的DMC組成會隨壓力的增加而減少,因此上段塔的壓力因壓縮機的加入而增加,將趨使更多的DMC可往下段塔的塔底收集,如此可明顯降低下段塔的塔底與上段塔的塔頂間之溫差,大幅減少壓縮機的設備費與操作成本,且上段塔的塔頂氣體產物在高溫高壓下,可成為下段塔的塔底再沸器的熱源。另一方面,由於上段塔的塔頂氣體產物的DMC組成更接近DMC-MeOH共沸物的DMC組成,此將減少萃取蒸餾系統分離DMC與MeOH混合物時所需的設備費與操作成本,因此本發明所提的架構可大幅度降低在生產HDC的整個製程的能耗與生產成本。Based on the above, in the above-mentioned HDC manufacturing apparatus and manufacturing method, since the lower column is operated at a low pressure, the bottom reboiler energy consumption (reboiler duty) of the lower column can be effectively reduced. In addition, since the DMC composition of the DMC-MeOH azeotrope will decrease with increasing pressure, the pressure of the upper column will increase due to the addition of the compressor, which will tend to collect more DMC to the bottom of the lower column. It can significantly reduce the temperature difference between the bottom of the lower tower and the top of the upper tower, greatly reducing the equipment cost and operating cost of the compressor, and the gas product at the top of the upper tower can become the bottom of the lower tower under high temperature and high pressure. The heat source of the boiler. On the other hand, since the DMC composition of the top gas product of the upper column is closer to the DMC composition of the DMC-MeOH azeotrope, this will reduce the equipment cost and operating cost required for the extractive distillation system to separate the DMC and MeOH mixture. The architecture proposed by the invention can greatly reduce the energy consumption and production cost of the entire process of producing HDC.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the embodiments are specifically described below in conjunction with the accompanying drawings for detailed description as follows.
圖1為本發明一實施例的HDC的製造裝置的示意圖。FIG. 1 is a schematic diagram of an HDC manufacturing apparatus according to an embodiment of the invention.
請參照圖1,HDC的製造裝置100包括反應器102、HDA供應裝置104、DMC供應裝置106與蒸餾塔108。HDC的製造裝置100適用於使HDA與DMC在存在觸媒的環境下進行反應,以製造HDC。Referring to FIG. 1, the
反應器102包括連續式反應器或批次反應器。在本實施例中,反應器102的數量是以一個為例來進行說明,但本發明並不以此為限,於此技術領域具有通常知識者可依照製程設計來調整反應器102的數量。舉例來說,在其他實施例中,反應器102的數量亦可為兩個以上。此外,在反應器102中可具有觸媒。觸媒可提高反應物的反應轉化率且可加速反應。觸媒例如是乙酸錳(Mn(OAc)
2)或苯酚鈉(C
6H
5ONa)。
The
HDA供應裝置104連接至反應器102,可用以提供HDA至反應器102中。DMC供應裝置106連接至反應器102,可用以提供DMC至反應器102中。在一實施例中,在HDA供應裝置104與反應器102之間以及DMC供應裝置106與反應器102之間可設置儲存槽(未示出),藉此可將HDA與DMC在儲存槽中進行預混,再將儲存槽中的HDA與DMC的混合物供應至反應器102中,但本發明並不以此為限。在另一實施例中,HDA供應裝置104的輸送管路與DMC供應裝置106的輸送管路可先會合後,再連接至反應器102,藉此可將HDA與DMC在輸送管路中進行預混,再將HDA與DMC的混合物供應至反應器102中。在另一實施例中,HDA供應裝置104與DMC供應裝置106亦可分別將HDA與DMC供應至反應器102中。The
基於上述,在反應器102中,可發生的反應如下。 HDA + DMC → HMC + MeOH HMC + DMC → HDC + MeOH 上述反應的總反應式如下。 HDA + 2DMC → HDC + 2MeOH 其中,HMC為六亞甲基-1,6-單氨基甲酸甲酯(dimethylhexane-1,6-monocarbamate)。HDC為本反應系統的主產物。Based on the above, the reactions that can occur in the
蒸餾塔108連接至反應器102的出料口102a。蒸餾塔108包括上段塔110、下段塔112與壓縮機114,且更可包括洩壓閥115。在本實施例中,是以上段塔110連接至反應器102的出料口102a為例,但本發明並不以此為限。壓縮機114連接在下段塔112的氣體出口112a與上段塔110的氣體入口110a之間。此外,上段塔110的液體出口110b可連接至下段塔112的液體入口112b。洩壓閥115可連接在上段塔110的液體出口110b與下段塔112的液體入口112b之間。舉例來說,上段塔110的氣體入口110a與液體出口110b可位在上段塔110的塔底,且下段塔112的氣體出口112a與液體入口112b可位在下段塔112的塔頂,但本發明並不以此為限。The
藉由壓縮機114的運轉,上段塔110中的壓力大於下段塔112中的壓力。由於下段塔112操作在低壓,因此可有效地降低下段塔112的塔底的再沸器能耗,進而大幅度降低在生產HDC時的能耗與生產成本。By the operation of the
此外,由於壓縮機114可提高上段塔110中的壓力,因此趨使DMC更有利從下段塔112的塔底收集,此將使上段塔110的塔頂的DMC組成較接近DMC-MeOH共沸物的DMC組成,因而降低萃取蒸餾系統的能耗與成本。此外,在降低上段塔110中的DMC的含量時,需同時考慮到上段塔110的塔頂氣體產物中的MeOH與DMC的含量。舉例來說,若上段塔110的塔頂氣體產物中的MeOH與DMC的含量比值接近共沸組成,則會使得下段塔112的塔底的再沸器能耗大幅提升,因此可對上段塔110的塔頂氣體產物中的MeOH與DMC的含量比進行最適化。In addition, since the
另外,在上段塔110中的壓力提高的情況下,可提高上段塔110的塔頂氣體產物溫度,而有利於產物的後續利用(如,可將上段塔110的塔頂氣體產物作為再沸器116的熱源),進而降低在生產HDC時的能耗與生產成本。上段塔110的塔頂氣體產物溫度高於下段塔112的塔底液體產物溫度。舉例來說,上段塔110的塔頂氣體產物溫度可比下段塔112的塔底液體產物溫度高5°C以上。在一實施例中,上段塔110的塔頂氣體產物溫度可比下段塔112的塔底液體產物溫度高10°C以上。In addition, when the pressure in the
HDC的製造裝置100更可選擇性地包括再沸器116、再沸器118、回流槽(reflux drum)120、冷凝器122、蒸餾塔124、再沸器126、回流槽128、冷凝器130、萃取蒸餾塔132、熱交換器134、再沸器136、再沸器138、回流槽140、冷凝器142、萃取劑回收塔144、再沸器146、再沸器148、回流槽150、冷凝器152、熱交換器154與冷凝器156中的至少一者。The
再沸器116連接至下段塔112的塔底,以提供熱量給下段塔112。由於上段塔110的塔頂氣體產物溫度高於下段塔112的塔底液體產物溫度,因此可將上段塔110的塔頂氣體產物作為再沸器116的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。詳細來說,上段塔110的塔頂氣體產物可將潛熱釋放給下段塔110的再沸器116,而降低塔頂氣體產物的溫度或者使塔頂氣體產物成為塔頂液體產物。The
再沸器118連接至下段塔112的塔底,可作為下段塔112的輔助熱源(auxiliary heat source)。在再沸器116可提供足夠的熱量給下段塔112的情況下,亦可省略再沸器118。The
回流槽120連接至上段塔110的塔頂,可用以儲存上段塔110的塔頂氣體產物經再沸器116進行熱交換或再經冷凝器122冷凝後的塔頂液體產物,且回流槽120中的部分塔頂液體產物可回流至上段塔110中。The
冷凝器122連接在再沸器116與回流槽120之間。在再沸器116中進行熱交換後的塔頂氣體產物或塔頂液體產物可經冷凝器122冷凝後再進入回流槽120中。在另一實施例中,在再沸器116中進行熱交換後的上段塔110的塔頂氣體產物已成為達預定溫度的塔頂液體產物的情況下,亦可省略冷凝器122。The
蒸餾塔124連接至下段塔112的塔底。再沸器126連接至蒸餾塔124的塔底,以提供熱量給蒸餾塔124。回流槽128連接至蒸餾塔124的塔頂,可用以儲存蒸餾塔124的塔頂液體產物,且回流槽128中的部分塔頂液體產物可回流至蒸餾塔124中。冷凝器130連接在蒸餾塔124的塔頂與回流槽128之間。蒸餾塔124的塔頂氣體產物可經冷凝器130冷凝後再進入回流槽128中。The
萃取蒸餾塔132連接至上段塔110的塔頂。在本實施例中,回流槽120可連接在上段塔110的塔頂與萃取蒸餾塔132之間。熱交換器134連接在回流槽120與萃取蒸餾塔132之間,以對來自回流槽120的進料進行加熱,藉此可降低萃取蒸餾塔132的塔底的再沸器能耗。在萃取蒸餾塔132中所添加的萃取劑例如是苯胺(aniline)或酚(phenol)。萃取劑可用於萃取蒸餾塔132中的DMC。再沸器136連接至萃取蒸餾塔132的塔底,以提供熱量給萃取蒸餾塔132。再沸器138連接至萃取蒸餾塔132的塔底,可作為萃取蒸餾塔132的輔助熱源。此外,在再沸器136可提供足夠的熱量給萃取蒸餾塔132的情況下,亦可省略再沸器138。回流槽140連接至萃取蒸餾塔132的塔頂,可用以儲存萃取蒸餾塔132的塔頂液體產物,且回流槽140中的部分塔頂液體產物可回流至萃取蒸餾塔132中。冷凝器142連接在萃取蒸餾塔132的塔頂與回流槽140之間。萃取蒸餾塔132的塔頂氣體產物可經冷凝器142冷凝後再進入回流槽140中。The
萃取劑回收塔144連接至萃取蒸餾塔132的塔底。再沸器146連接至萃取劑回收塔144的塔底,以提供熱量給萃取劑回收塔144。再沸器148連接至萃取劑回收塔144的塔底,可作為萃取劑回收塔144的輔助熱源。在再沸器146可提供足夠的熱量給萃取劑回收塔144的情況下,亦可省略再沸器148。回流槽150連接至萃取劑回收塔144的塔頂,可用以儲存萃取劑回收塔144的塔頂液體產物,且回流槽150中的部分塔頂液體產物可回流至萃取劑回收塔144中。冷凝器152連接在萃取劑回收塔144的塔頂與回流槽150之間。萃取劑回收塔144的塔頂氣體產物可經冷凝器152冷凝後再進入回流槽150中。萃取劑回收塔144的塔底液體產物中的萃取劑可回流至萃取蒸餾塔132中。The
此外,由於蒸餾塔124的塔底液體產物溫度可高於萃取蒸餾塔132的塔底液體產物溫度、萃取劑回收塔144的塔底液體產物溫度與萃取蒸餾塔132的進料溫度,因此可將蒸餾塔124的塔底液體產物作為連接至萃取蒸餾塔132的塔底的再沸器136、連接至萃取劑回收塔144的塔底的再沸器146與連接在上段塔110與萃取蒸餾塔132之間的熱交換器134中的至少一者的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。In addition, since the temperature of the bottom liquid product of the
熱交換器154連接在回流槽120與萃取蒸餾塔132之間,以對來自回流槽120的進料進行加熱,藉此可降低萃取蒸餾塔132的塔底的再沸器能耗。由於萃取劑回收塔144的塔底液體產物溫度可高於萃取蒸餾塔132的進料溫度,因此可將萃取劑回收塔144的塔底液體產物作為連接在上段塔110與萃取蒸餾塔132之間的熱交換器154的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。The
冷凝器156連接在萃取劑回收塔144的塔底與萃取蒸餾塔132之間。在熱交換器154中進行熱交換後的萃取劑回收塔144的塔底液體產物可經冷凝器156冷凝後再進入萃取蒸餾塔132中。The
圖2為本發明一實施例的HDC的製造流程圖。以下,藉由圖2來說明本發明一實施例的HDC的製造方法。圖2的製造方法所使用的裝置是以圖1的HDC的製造裝置100為例,但本發明並不以此為限。此外,關於圖1的HDC的製造裝置100中的各構件的詳細內容可參考上述實施例,不再重複說明。FIG. 2 is a manufacturing flowchart of an HDC according to an embodiment of the invention. Hereinafter, a method of manufacturing an HDC according to an embodiment of the present invention will be described with reference to FIG. 2. The device used in the manufacturing method of FIG. 2 is an example of the
請參照圖2,進行步驟S100,在反應器102中,使HDA與DMC在存在觸媒的環境下進行反應,而產生反應後之產物。反應後之產物可包括HDC、MeOH與DMC,且更可包括微量的HDA、微量的高沸點中間產物(HMC)與微量的高沸點不純物。舉例來說,可藉由HDA供應裝置104與DMC供應裝置106分別提供HDA與DMC至反應器102中,以進行反應。在HDA與DMC的反應中,可使用過量的DMC作為反應物。在HDA與DMC的反應中,DMC與HDA的進料莫耳比值例如是3至9。在一實施例中,在HDA與DMC的反應中,DMC與HDA的進料莫耳比值例如是4至8。觸媒例如是乙酸錳(Mn(OAc)
2)或苯酚鈉(C
6H
5ONa)。
Referring to FIG. 2, step S100 is performed. In the
進行步驟S102,使反應後之產物進入蒸餾塔108中,而產生第一塔頂氣體產物與第一塔底液體產物。第一塔頂氣體產物可包括MeOH與DMC。第一塔底液體產物可包括HDC與DMC,且更可包括微量的HDA、微量的MeOH、微量的高沸點中間產物(HMC)與微量的高沸點不純物。Step S102 is carried out, so that the products after the reaction enter the
蒸餾塔108包括上段塔110、下段塔112與壓縮機114,且更可包括洩壓閥115。由上段塔110產生第一塔頂氣體產物。由下段塔112產生第一塔底液體產物。壓縮機114連接在下段塔112的氣體出口112a與上段塔110的氣體入口110a之間。上段塔110的液體出口110b可連接至下段塔112的液體入口112b。洩壓閥115可連接在上段塔110的液體出口110b與下段塔112的液體入口112b之間。舉例來說,上段塔110的氣體入口110a與液體出口110b可位在上段塔110的塔底,且下段塔112的氣體出口112a與液體入口112b可位在下段塔112的塔頂,但本發明並不以此為限。The
藉由壓縮機114的運轉,上段塔110中的壓力大於下段塔112中的壓力。上段塔110的塔頂氣體產物溫度高於下段塔112的塔底液體產物溫度,因此可將上段塔110的第一塔頂氣體產物作為連接至下段塔112的塔底的再沸器116的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。舉例來說,上段塔110的塔頂氣體產物溫度可比下段塔112的塔底液體產物溫度高5°C以上。在一實施例中,上段塔110的塔頂氣體產物溫度可比下段塔112的塔底液體產物溫度高10°C以上。By the operation of the
基於上述可知,由於下段塔112操作在低壓,所以可有效地降低下段塔112的塔底再沸器能耗(reboiler duty)。另外,由於DMC-MeOH共沸物的DMC組成會隨壓力的增加而減少,因此上段塔110的壓力因壓縮機114的加入而增加,將趨使更多的DMC可往下段塔112的塔底收集,如此可明顯降低下段塔112的塔底與上段塔110的塔頂間之溫差,大幅減少壓縮機的設備費與操作成本,且上段塔110的塔頂氣體產物在高溫高壓下,可成為下段塔112的塔底再沸器的熱源。另一方面,由於上段塔110的塔頂氣體產物的DMC組成更接近DMC-MeOH共沸物的DMC組成,此將減少萃取蒸餾系統分離DMC與MeOH混合物時所需的設備費與操作成本,因此本發明所提的架構可大幅度降低在生產HDC的整個製程的能耗與生產成本。Based on the above, since the
此外,可進行步驟S104,使第一塔底液體產物進入蒸餾塔124中,而產生第二塔頂液體產物與第二塔底液體產物。第二塔頂液體產物可包括DMC,且更可包括微量的MeOH。第二塔底液體產物可包括HDC,且更可包括微量的HDA、微量的高沸點中間產物(HMC)與微量的高沸點不純物。In addition, step S104 may be performed to make the first bottom liquid product enter the
另外,可進行步驟S106,使第一塔頂氣體產物經冷凝後所得的第一塔頂液體產物與萃取劑進入萃取蒸餾塔132中,而產生第三塔頂液體產物與第三塔底液體產物。舉例來說,第一塔頂氣體產物可將潛熱釋放給下段塔110的再沸器116而成為塔頂液體產物後或者經冷凝器122冷凝成塔頂液體產物後進入回流槽120,回流槽120內一部份塔頂液體產物可回流至上段塔110,一部份塔頂液體產物收集在回流槽120中,再使塔頂液體產物與萃取劑進入萃取蒸餾塔中。萃取劑可用於萃取蒸餾塔132中的DMC。在萃取蒸餾塔132中所添加的萃取劑例如是苯胺或酚。第三塔頂液體產物可包括MeOH,且更可包括微量的DMC。第三塔底液體產物可包括DMC與萃取劑,且更可包括微量的MeOH。In addition, step S106 may be performed, so that the first overhead liquid product and the extractant obtained after the condensation of the first overhead gas product enter the
接著,可進行步驟S108,使第三塔底液體產物進入萃取劑回收塔144中,而產生第四塔頂液體產物與第四塔底液體產物。第四塔頂液體產物可包括DMC,且更可包括微量的MeOH。第四塔底液體產物可包括萃取劑,且更可包括微量的DMC。Next, step S108 may be performed to make the third bottom liquid product enter the
另一方面,可將蒸餾塔124的第二塔底液體產物作為連接至萃取蒸餾塔132的塔底的再沸器136、連接至萃取劑回收塔144的塔底的再沸器146與連接在上段塔110與萃取蒸餾塔132之間的熱交換器134中的至少一者的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。此外,可將萃取劑回收塔144的第四塔底液體產物作為連接在上段塔110與萃取蒸餾塔132之間的熱交換器154的熱源,且藉由進行上述熱整合可更進一步地降低能耗與生產成本。另外,在圖1中所示出的熱整合的路徑(以虛線表示)僅為舉例說明,本發明並不以此為限。所屬技術領域中具有通常知識者可參考上述實施例的教示並根據需求對熱整合的路徑進行調整。On the other hand, the second bottom liquid product of the
基於上述實施例可知,在上述HDC的製造裝置與製造方法中,由於下段塔112是操作在低壓,所以可有效地降低下段塔112的塔底的再沸器能耗,進而大幅度降低在生產HDC時的能耗與生產成本。此外,壓縮機114可提高上段塔110中的壓力,藉此可降低上段塔110中的DMC的含量,並可同時提高下段塔112中的DMC的含量,且可提高上段塔110的塔頂氣體產物溫度,而作為再沸器的熱源,進而降低在生產HDC時的能耗與生產成本。Based on the above embodiment, it can be seen that in the above HDC manufacturing apparatus and manufacturing method, since the
綜上所述,在上述實施例的HDC的製造裝置與製造方法中,由於壓縮機連接在下段塔的氣體出口與上段塔的氣體入口之間,因此可藉由壓縮機的作用來大幅度降低在生產HDC時的能耗與生產成本。In summary, in the HDC manufacturing apparatus and manufacturing method of the above embodiment, since the compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower, it can be greatly reduced by the action of the compressor Energy consumption and production costs when producing HDC.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.
100:HDC的製造裝置
102:反應器
102a:出料口
104:HDA供應裝置
106:DMC供應裝置
108、124:蒸餾塔
110:上段塔
110a:氣體入口
110b:液體出口
112:下段塔
112a:氣體出口
112b:液體入口
114:壓縮機
115:洩壓閥
116、118、126、136、138、146、148:再沸器
120、128、140、150:回流槽
122、130、142、152、156:冷凝器
132:萃取蒸餾塔
134、154:熱交換器
144:萃取劑回收塔
S100、S102、S104、S106、S108:步驟100: HDC manufacturing device
102:
圖1為本發明一實施例的HDC的製造裝置的示意圖。 圖2為本發明一實施例的HDC的製造流程圖。FIG. 1 is a schematic diagram of an HDC manufacturing apparatus according to an embodiment of the invention. FIG. 2 is a manufacturing flowchart of an HDC according to an embodiment of the invention.
100:HDC的製造裝置 100: HDC manufacturing device
102:反應器 102: Reactor
102a:出料口 102a: Outlet
104:HDA供應裝置 104: HDA supply device
106:DMC供應裝置 106: DMC supply device
108、124:蒸餾塔 108, 124: distillation tower
110:上段塔 110: Upper tower
110a:氣體入口 110a: gas inlet
110b:液體出口 110b: Liquid outlet
112:下段塔 112: Lower tower
112a:氣體出口 112a: gas outlet
112b:液體入口 112b: Liquid inlet
114:壓縮機 114: Compressor
115:洩壓閥 115: Pressure relief valve
116、118、126、136、138、146、148:再沸器 116, 118, 126, 136, 138, 146, 148: reboiler
120、128、140、150:回流槽 120, 128, 140, 150: reflux tank
122、130、142、152、156:冷凝器 122, 130, 142, 152, 156: condenser
132:萃取蒸餾塔 132: Extractive distillation tower
134、154:熱交換器 134, 154: heat exchanger
144:萃取劑回收塔 144: Extractant recovery tower
Claims (30)
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Citations (3)
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CN102971287A (en) * | 2010-06-16 | 2013-03-13 | 三井化学株式会社 | Carbamate production method, isocyanate production method, carbamate production device and isocyanate production device |
CN103936625A (en) * | 2014-05-08 | 2014-07-23 | 南京工业大学 | Method for synthesizing hexamethylene-1, 6-diamino methyl formate |
CN107417573A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化学工业开发股份有限公司 | Method for preparing carbamate |
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CN102971287A (en) * | 2010-06-16 | 2013-03-13 | 三井化学株式会社 | Carbamate production method, isocyanate production method, carbamate production device and isocyanate production device |
CN103936625A (en) * | 2014-05-08 | 2014-07-23 | 南京工业大学 | Method for synthesizing hexamethylene-1, 6-diamino methyl formate |
CN107417573A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化学工业开发股份有限公司 | Method for preparing carbamate |
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