WO2016182190A1 - Method for continuously preparing neopentyl glycol - Google Patents
Method for continuously preparing neopentyl glycol Download PDFInfo
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- WO2016182190A1 WO2016182190A1 PCT/KR2016/002992 KR2016002992W WO2016182190A1 WO 2016182190 A1 WO2016182190 A1 WO 2016182190A1 KR 2016002992 W KR2016002992 W KR 2016002992W WO 2016182190 A1 WO2016182190 A1 WO 2016182190A1
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- aldol condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
Definitions
- 2,2-dimethyl-1,3-propanediol is an organic compound used for the synthesis of polyesters, paints, lubricants and plasticizers.
- HPA 3-hydroxy-2,2-dimethylpropanal
- formaldehyde in the raw material for the production of HPA is azeotropic with water contained in the product of the aldol condensation process is difficult to recover, and may act as a catalyst poison to the hydrogenation reaction of HPA. For this reason, the residual of formaldehyde should be minimized in the product of the aldol condensation process.
- Patent Document 1 US Registered Patent No. 3939216 (19 7 6.02.17)
- Patent Document 2 Korean Registered Patent No. 0231644 (1999.08.31)
- the present invention aims to provide a process for the continuous production of NPG with high yields and simplified processes.
- the extraction process is carried out in an extraction column having a plurality of stages partitioned by perforated trays.
- a method of continuously manufacturing NPG according to an embodiment of the present invention will be described.
- the feed of the extraction process is a liquid mixture containing the solute to be extracted, and the solute of the solute that is soluble to the extraction solvent and the other components that do not have the solubility It is a compound.
- an extraction solvent is added to the feed, the solute is dissolved from the feed into the extraction solvent by mass transfer. Extraction solvents in which a significant amount of solute is dissolved form an extract solution, and feeds that lose a significant amount of solute To form a trafficin solution.
- the inventors' continuous studies have shown that when the product of the aldol condensation process is brought into contact with the extraction solvent to improve the efficiency of the extraction process of obtaining the extract containing HPA, the subsequent process can be markedly simplified.
- the low boiling point material included in the product of the aldol condensation process may be separated by only one step after the extraction process, and may be recycled without additional purification facilities for the separated low boiling point material.
- the aldol condensation process for obtaining HPA was sequentially performed in three or more series of continuous stirring reactors connected in series, and isobutylaldehyde in the raw material compound at different ratios in each reactor. Simultaneously with the quarter addition, it was confirmed that HPA can be obtained with a significantly improved yield when the reaction mixture of the aldol condensation reaction product is allowed to react under different residence times in each reaction vessel.
- the aldol condensation process can not only significantly reduce the amount of unreacted formaldehyde, but also effectively suppress the formation of by-products such as neopentyl glycol hydroxy pivalate.
- the aldol condensation process by sequentially reducing the ratio of isobutyl aldehyde branched into each reaction stage, and sequentially increasing the residence time of the reaction product in each reaction stage, a more improved effect can be expressed.
- the extraction process is provided for a continuous production method of NPG, which is carried out in an extraction column having a plurality of stages partitioned by porous plates.
- FIG. 1 schematically illustrates a method of continuously manufacturing NPG according to one embodiment of the present invention
- FIG. 2 schematically illustrates an aldol condensation process in the method of continuously manufacturing NPG.
- the continuous production method of the NPG Aldol condensation reaction system 100, extraction column 200, low boiling point material separation column 300, hydrogenation reaction system 400, distillation column 500, and high boiling It may be carried out in a flow including a point material removal tower 600.
- the aldol condensation step is a step of obtaining a product containing HPA through an aldol condensation reaction of an aqueous formaldehyde solution and isobutylaldehyde in the presence of a catalyst.
- the aldol condensation process may be carried out in three or more, preferably three to five groups, more preferably three or four groups of continuous stirring reaction in series.
- the increase in the efficiency of the aldol condensation reaction may be expected by increasing the number of continuous stirring reactions, but it is preferable to determine the number of reaction reactions in consideration of process efficiency and equipment complexity.
- FIG. 2 schematically illustrates one embodiment of an aldol condensation reaction system 100 comprising three continuous stirred reaction reactors.
- the aldol condensation process is three continuous stirring It may be carried out in the aldol condensation reaction system 100 including the counterunggi (R1, R2 and R3).
- the catalyst (F0-TEA) and the raw material compounds (FO-iBAL and F0-FA) applied to the aldol condensation reaction are introduced into the first reactor (R1) to start reaction.
- the reaction product is sequentially delivered to the other reaction vessels R2 and R3 through the connecting pipes F1 and F2 and the reaction proceeds.
- isobutylaldehyde (FO-iBAL) in the raw material compound is branched (S1, S2 and S3) into each reactor (R1, R2 and R3) at different ratios, The reaction is carried out under different residence times in each reaction.
- the ratio of isobutyl aldehyde branched into each reactor may be sequentially decreased, and the residence time of the reaction product in each reactor may be sequentially increased.
- the deceleration width of the isobutyl aldehyde content and the increase width of the reaction time residence time is not particularly limited.
- the residence time of the reaction product in the three consecutive stirred agitators is, on the premise of increasing sequentially, from 10 to 13 minutes in the first reaction period (R1), the second 13 to 17 minutes in the reactor (R2), and 17 to 19 minutes in the third reaction stage (R3).
- the residence time of the counterungmul in each counterunggi is the space velocity of the counterungung.
- the Reynolds number, the linear velocity at the tip of the impeller, and the linear velocity at the wall surface of the semi-ungwoon for effective agitation of the reactants in each reactor should be considered.
- the Reynolds number of each semi-unggi is 50000 or more, and the difference between the linear velocity at the tip of the impeller and the wall of the reactor may be adjusted to 2 to 5 m / sec.
- the aldol condensation reaction of formaldehyde aqueous solution and isobutyl aldehyde is exothermic reaction. Therefore, it is preferable to remove the semiungung heat while circulating the semiungung of each halfunggi to the outside of the semiungunggi. Particularly, in circulating the reaction product to the outside, by using the injector equipped with a venturi nozzle, the reaction product may be strongly sprayed into the reaction device to ensure more improved reaction efficiency.
- the aldol condensation process is connected in series via a semi-acre water circulation unit including a circulation pip, a heat exchanger and a reactant injector, respectively.
- isobutyl aldehyde as is advantageous in that the amount of isomer used to 0.5 0/0 of less than suppressing the formation of by-products.
- isobutyl aldehyde may be used in a molar ratio of 1.1 to 1.5, preferably in a molar ratio of 1.1 to 1.2 with respect to 1 mol of formaldehyde. That is, in order to induce complete reaction of the formaldehyde used in the aldol condensation reaction, isobutylaldehyde may be used in excess of formaldehyde, preferably in a molar ratio of 1: 1 or more. However, when isobutyl aldehyde is used too much, the production of by-products due to Tishchenko banung may be increased. Therefore, isobutyl aldehyde is preferably used in a molar ratio of less than 1: 1.5 relative to formaldehyde.
- formaldehyde is used as an aqueous solution of formaldehyde having a concentration of formaldehyde having a concentration of 35 to 45 and increasing 0 /. It is advantageous for the improvement of reaction efficiency and the reduction of waste water generation.
- methanol is added to the aqueous formaldehyde solution to prevent the polymerization of formaldehyde, the content of which is relative to the aqueous formaldehyde solution.
- the catalyst is L H, NaOH, KOH,
- Hydroxides such as Ca (OH) 2 ; Alkali metal carbonates such as NaCO 3 , LiCO 3 , KCO 3 , Ca (CO 3 ) 2 , NH 4 CO 3 ; Tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine can be used. Tertiary amine compounds, particularly triethylamine, in the catalyst may be more preferably used in view of improving the efficiency of the aldol condensation reaction.
- the catalyst may be used in a molar ratio of 0.01 to 0.5, preferably 0.15 to 0.25, and more preferably 0.18 to 0.22 with respect to 1 mol of formaldehyde. That is, in order to express the catalytic effect, the catalyst may be used in a molar ratio of 1: 0.01 or more relative to formaldehyde. However, if the catalyst is used too much, recovery of the catalyst may be required and generation of by-products may be caused. Therefore, the catalyst is preferably used in a molar ratio of 1: 0.5 or less relative to formaldehyde.
- the reaction temperature may be maintained at 70 to 100 ° C, preferably 70 to 85 ° C.
- the reaction temperature is preferably 70 ° C or more.
- the reaction temperature is preferably 100 ° C. or less.
- the aldol condensation reaction may be performed under pressure to ensure yield.
- the aldol condensation process performed under the above-described conditions enables the maximization of the mixing efficiency of the raw material compound, thereby improving the efficiency of the aldol condensation reaction, and minimizing the remaining of the non-banung formaldehyde and the generation of by-products.
- the aldol condensation process may ensure a high HPA yield of 99% or more and a low residual formaldehyde concentration of 2000 ppm or less.
- the extraction step is a step of obtaining the extract containing HPA by bringing the product of the aldol condensation step into contact with the extraction solvent.
- the extraction process is performed in an extraction column having a plurality of stages partitioned by the porous plates. Accordingly, the extraction process can ensure a significantly improved HPA extraction efficiency, it is possible to simplify the subsequent low boiling point material separation process.
- the extraction column 200 of the excellent stirring system having a stage partitioned by the perforated plates having the vertically repeating movement as the extraction column according to the liquid-liquid contacting method can be preferably applied.
- the extraction column 200 includes a Kuhni column, a Karr type reciprocating plate column, a rotary-disk contactor, a Scheibel column, and a spray extraction column. ), Packed extraction columns, pulse packed columns, and the like may be used.
- the extraction process may be performed in an extraction column having 20 or more stages, preferably 20 to 30 stages, stages partitioned by the porous plates so that the divided extraction efficiency can be expressed under the extraction column.
- the height of one stage in the extraction column may be advantageous to improve the extraction efficiency of 300 to 500 mm.
- the number of stages and the height of the stage of the extraction column may be an example limited to the pilot column, and may be extended to an appropriate range in the commercialization process.
- the product of the aldol condensation process supplied to the extraction column 200 is brought into contact with the extraction solvent, and extracts containing a significant amount of HPA and a weight loss of a significant amount of HPA are lost. ution).
- the relatively light phase of the extract is obtained through the upper outlet of the extraction column 200
- the relatively heavy phase of the extract is obtained through the lower outlet of the extraction column (200).
- the extraction solvent having solubility in HPA preferably octanol may be used.
- the extraction solvent may be used in a weight ratio of 1: 0.3 to 1: 0.7, preferably 1: 0.4 to 1: 0.6, based on the product of the aldol condensation process supplied to the extraction column 200.
- the extraction solvent is preferably used in a weight ratio of 1: 0.3 or more with respect to the product.
- the weight ratio of the extraction solvent exceeds 1: 0.7, the extraction efficiency may be improved, but the loss amount of HPA may be increased in the subsequent low boiling point material separation process, and the reflux flow of the azeotropic solvent to prevent this is excessive. It can be high, which is undesirable.
- the temperature of the extraction process is preferably maintained at 40 ° C or more. However, if the temperature is too high, the phase separation of the extract may not be made, it is preferable that the temperature of the extraction process is maintained at 90 ° C or less.
- an extraction efficiency of 99% or more may be secured through the extraction process as described above. That is, the extract obtained through the extraction process may contain more than 99% by weight of the HPA contained in the product of the aldol condensation process. In addition, since most of the water contained in the product of the aldol condensation process is discharged to the weight balance, the extract contains less than 3 weight 0 /.
- the loss of HPA in the extraction step may be minimized as a 99 weight 0/0 over the HPA obtained in the aldol condensation step extraction through the extraction process.
- the extraction process may lower the equipment burden and energy consumption of the subsequent low-boiling point material separation process.
- the low boiling point material separation step is a step of distilling the extract to obtain a distillate from which a low boiling point material having a lower boiling point than HPA is removed.
- the extract contains low-boiling substances such as isobutyl aldehyde, aldol condensation reaction catalyst, water contained in aqueous formaldehyde and methane.
- This low boiling point material may be separated from the extract by distillation.
- the low boiling point material can be separated by only one distillation after the extraction process.
- isobutylaldehyde and the catalyst in the separated low boiling point material may be recycled to the aldol condensation process.
- the extract liquid supplied to the low boiling point material separation column 300 is contacted with an azeotropic solvent and heated to an appropriate temperature to be distilled by evaporation and expansion.
- the low boiling point material separation process is preferably carried out by azeotropic distillation.
- azeotropic distillation method As the solvent applied to the azeotropic distillation method, a common one having a lower boiling point and azeotropic boiling point than HPA may be applied. (4) hydrogenation process
- the hydrogenation step is a step of hydrogenating the distillate from which the low boiling point material is removed in the presence of a catalyst to obtain a product containing NPG.
- a conventional nickel catalyst may be used as the catalyst for the hydrogenation reaction.
- the catalyst may be used in an amount of 2 to 10 weight 0 / .about HPA contained in the distillate.
- the hydrogenation reaction is a gas-liquid reaction. Therefore, in order to increase the contact efficiency of the reactants, the hydrogenation reaction system may include a hydrogenation reaction system 400 having a venturi nozzle for spraying the HPA-containing distillate into the reaction system.
- the hydrogenation reaction is preferably performed under a hydrogen pressure of 100 to 1500 psig and a temperature of 100 to 200 ° C. in terms of securing a yield.
- the product of the hydrogenation step is distilled to obtain NPG. It is a process of obtaining.
- HPA dimer high boiling point material may be included. Accordingly, the product of the hydrogenation process may be distilled in the distillation column 500 to obtain high purity NPG.
- the continuous manufacturing method of NPG according to the present invention enables extraction of HPA with improved efficiency, which simplifies subsequent processing and improves NPG yield.
- FIG. 1 schematically shows a method of continuously manufacturing NPG according to an embodiment of the present invention.
- FIG. 2 schematically shows an aldol condensation process in the continuous production method of NPG according to an embodiment of the present invention. [Explanation of code]
- NPG neopentyl glycol HB: high boiling point material
- F0-FA formaldehyde aqueous solution supply line
- the device of the same structure as 1 was prepared.
- an aldol condensation reaction system 100 including three continuous stirring reactors R1, R2 and R3 connected in series is used for the aldol condensation process.
- a Kuhni column 400 mm in height having a total of 24 stages stages partitioned by the perforated plates having vertical and repeating motions was used.
- Triethylamine (TEA) was prepared as a catalyst.
- Formaldehyde isobutylaldehyde: triethylamine was used in a molar ratio of 1: 1.1: 0.2. Formaldehyde aqueous solution and catalyst were added to the first reactor. And, based on the total content of isobutyl aldehyde, 91% by weight of isobutylaldehyde is in the first half foot group (R1), 7.5 weight 0 /. Isobutylaldehyde in the second half foot group (R2), 1. 5 weights 0 /. Of isobutylaldehyde were each branched to the third half-aerator (R3). At the same time, the residence time of the semi-treatment in each reaction period was adjusted as shown in Table 1 below. Table 1
- the aldol condensation process was carried out continuously at a temperature of 72 to 78 ° C and a pressure of 3 atm, through which a product containing HPA was obtained (conversion rate 89.8%, residual formaldehyde concentration in the product 2000 ppm, HPA Yield 99.20%).
- the product of the aldol condensation process was introduced into the extraction column (200).
- the extraction column 200 has been introduced into the octanol in 50 parts by weight 0/0 compared to the product by solvent extraction.
- Extraction of HPA was performed by vigorous stirring in the extraction column, and the composition of the organic layer in the extract obtained therefrom is shown in Table 2 below.
- the extract was distilled in the low boiling point material separation column 300 to separate isobutyl aldehyde, triethylamine, water, methanol, and the like, which were low boiling point materials.
- the separated low boiling point material was discharged to the top of the low boiling point material separation column 300 and recycled to the aldol condensation reaction system 100.
- the composition of the low boiling point material is shown in Table 2 below.
- the distillate from which the low boiling point material was removed was continuously introduced into the hydrogenation reaction system 400, and the hydrogenation process was performed in the presence of a nickel catalyst.
- the product of the hydrogenation process was continuously introduced into the distillation column 500 to purify, finally obtaining NPG.
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Abstract
Description
[명세서 ] [Specification ]
【발명의 명칭】 [Name of invention]
네오펜틸 글리콜의 연속 제조 방법 Continuous production method of neopentyl glycol
【기술분야】 Technical Field
관련 출원과의 상호 인용 Cross Citation with Related Applications
본 출원은 2015년 5월 13일자 한국 특허 출원 제 10-2015-0066894호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. 본 발명은 높은 수율과 단순화된 공정으로 네오펜틸 글리콜을 연속 제조하는 방법에 관한 것이다. This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0066894 dated May 13, 2015, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification. The present invention relates to a process for the continuous production of neopentyl glycol in high yield and simplified processes.
【배경기술】 Background Art
네오펜틸 글리콜 (Neopentyl glycol, synonyms: Neopentyl glycol, synonyms:
2,2-dimethyl-1 ,3-propanediol, 이하 NPG)은 폴리에스터, 페인트, 윤활제, 가소제 등의 합성에 사용돠는 유기 화합물이다. 2,2-dimethyl-1,3-propanediol, or NPG), is an organic compound used for the synthesis of polyesters, paints, lubricants and plasticizers.
NPG는 아이소부틸알데하이드 (isobutyraldehyde, synonyms: NPG isobutyl aldehyde (synonyms:
2- methylpropanal)와 포름알데하이드 수용액의 알돌 축합 반웅에 의해 생성된 하이드록시피브알데하이드. (hydroxypivalaldehyde, synonyms:2-methylpropanal) and hydroxyfibaldehyde produced by the aldol condensation reaction of aqueous formaldehyde solution. (hydroxypivalaldehyde, synonyms:
3- hydroxy-2,2-dimethylpropanal, 이하 HPA)를 수소화 반웅시킴으로써 얻어진 Obtained by hydrogenation of 3-hydroxy-2,2-dimethylpropanal (hereinafter HPA)
Isobutyraldehyde Formaldehyde Hydroxypivalaldehyde Isobutyraldehyde Formaldehyde Hydroxypivalaldehyde
Hydroxypivalaldehyde Neopentyl glycol 그런데, HPA를 얻기 위한 알돌 축합 반웅의 생성물에는 HPA 이외에 미반응 원료 화합물, 촉매, 그리고 2,2,4-트리메틸 -1 ,3-펜탄디올 네오펜틸 글리콜 하이드록시 피발레이트, 네오펜틸 글리콜 아이소부틸레이트와 같은 부산물들이 포함되어 있다. 특히, 상기 부산물들을 분리하기 위해서는 복잡한 분리 공정과 설비가 요구되기 때문에, HPA를 얻기 위한 반웅에서 부산물의 생성을 최소화하는 것이 중요하다. Hydroxypivalaldehyde Neopentyl glycol By the way, the product of aldol condensation reaction to obtain HPA, in addition to HPA Unreacted raw compounds, catalysts, and by-products such as 2,2,4-trimethyl-1,3-pentanediol neopentyl glycol hydroxy pivalate and neopentyl glycol isobutylate are included. In particular, it is important to minimize the production of by-products in the reaction to obtain the HPA, because the complex separation process and equipment is required to separate the by-products.
특히, HPA의 제조를 위한 원료 화합물 중 포름알데하이드는 알돌 축합 공정의 생성물에 포함된 물과 공비되어 회수가 어렵고, HPA의 수소화 반웅에 촉매 독으로써 작용할 수 있다. 이러한 이유로, 상기 알돌 축합 공정의 생성물에는 포름알데하이드의 잔류가 최소화되어야 한다. In particular, formaldehyde in the raw material for the production of HPA is azeotropic with water contained in the product of the aldol condensation process is difficult to recover, and may act as a catalyst poison to the hydrogenation reaction of HPA. For this reason, the residual of formaldehyde should be minimized in the product of the aldol condensation process.
이와 관련하여, 알돌 축합 반응에서 반웅물의 몰비 또는 촉매의 조성을 조절하거나, 복수의 연속 교반 반웅기 (continuous stirred-tank reactor, CSTR)를 적용하는 등의 방법을 통해 HPA의 수율을 향상시키고, 포름알데하이드의 잔존량과 부산물의 생성량을 최소화하려는 시도들이 있었다. 그리고, 알돌 축합 공정의 생성물로부터 고순도의 NPG를 얻기 위한 다양한 정제 공정들이 제안되었다. In this regard, it is possible to improve the yield of HPA by adjusting the molar ratio of the reaction product or the composition of the catalyst in the aldol condensation reaction, or by applying a plurality of continuous stirred-tank reactors (CSTRs), and formingaldehyde. Attempts have been made to minimize the amount of residues and by-products produced. In addition, various purification processes have been proposed to obtain high purity NPG from the product of the aldol condensation process.
하지만, 지금까지 제안된 방법들은 HPA의 수율이 여전히 낮을 뿐만 아니라, 비효율적인 정제로 인해 NPG를 얻기까지 복잡한 공정이 요구되며, 과다한 설비 비용과 운전 비용이 동반되는 한계를 갖는다. 【선행기술문헌】 However, the methods proposed so far are not only low in yield of HPA, but also require complicated processes to obtain NPG due to inefficient purification, and have limitations that are accompanied by excessive facility cost and operation cost. Prior Art Documents
【특허문헌】 [Patent literature]
(특허문헌 1 ) 미국 등록특허 제 3939216 호 (1976.02.17) (Patent Document 1) US Registered Patent No. 3939216 (19 7 6.02.17)
(특허문헌 2) 대한민국 등록특허 제 0231644 호 (1999.08.31 ) 【발명의 내용】 (Patent Document 2) Korean Registered Patent No. 0231644 (1999.08.31)
【해결하려는 과제】 [Problem to solve]
본 발명은 높은 수율과 단순화된 공정으로 NPG를 연속 제조하는 방법을 제공하기 위한 것이다. The present invention aims to provide a process for the continuous production of NPG with high yields and simplified processes.
【과제의 해결 수단】 본 발명에 따르면, [Measures of problem] According to the invention,
촉매의 존재 하에 포름알데하이드 수용액과 아이소부틸알데하이드의 알돌 축합 반웅을 통해 HPA가 함유된 생성물을 얻는 알돌 축합 공정, Aldol condensation process to obtain a product containing HPA through the aldol condensation reaction of aqueous formaldehyde and isobutylaldehyde in the presence of a catalyst,
상기 알돌 축합 공정의 생성물을 추출 용매와 접촉시켜, HPA가 함유된 추출액을 얻는 추출 공정, An extraction step of bringing the product of the aldol condensation step into contact with an extraction solvent to obtain an extract containing HPA;
상기 추출액을 증류하여 HPA보다 낮은 비점을 갖는 저비점 물질이 제거된 증류액을 얻는 저비점 물질 분리 공정, A low boiling point material separation process of distilling the extract to obtain a distillate from which a low boiling point material having a lower boiling point than HPA is removed;
상기 저비점 물질이 제거된 증류액을 촉매의 존재 하에 수소화 반웅시켜 NPG가 함유된 생성물을 얻는 수소화 공정, 및 A hydrogenation process in which the distillate from which the low boiling point material has been removed is hydrogenated in the presence of a catalyst to obtain a product containing NPG; and
상기 수소화 공정의 생성물을 증류하여 NPG을 얻는 정제 공정을 포함하고; A purification step of distilling the product of the hydrogenation step to obtain NPG;
상기 추출 공정은 다공판들 (perforated trays)에 의해 구획된 복수의 스테이지를 갖는 추출 컬럼에서 수행되는, NPG의 연속 제조 방법이 제공된다. 이하, 발명의 구현 예에 따른 NPG의 연속 제조 방법 에 대하여 설명하기로 한다. The extraction process is carried out in an extraction column having a plurality of stages partitioned by perforated trays. Hereinafter, a method of continuously manufacturing NPG according to an embodiment of the present invention will be described.
그에 앞서, 본 명세서 전체에서 명시적인 언급이 없는 한, 전문 용어는 단지 특정 실시예를 언급하기 위한 것이며, 본 발명을 한정하는 것을 의도하지 않는다. 그리고, 여기서 사용되는 단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다. 또한, 명세서에서 사용되는 '포함 '의 의미는 특정 특성, 영역, 정수, 단계, 동작, 요소 또는 성분을 구체화하며, 다른 특정 특성, 영역, 정수, 단계, 동작, 요소, 또는 성분의 부가를 제외시키는 것은 아니다. Prior to that, unless otherwise stated throughout the specification, the terminology is merely for reference to particular embodiments and is not intended to limit the invention. As used herein, the singular forms “a,” “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite. In addition, the meaning of "included" as used in the specification specifies a specific characteristic, region, integer, step, operation, element or component, excluding the addition of other specific characteristics, region, integer, step, operation, element, or component. It is not meant to be.
그리고, 추출 공정의 피드 (feed)는 추출하고자 하는 용질 (solute)을 함유한 액체 흔합물로서, 추출 용매 (extraction solvent)^ 대하여 가용성을 갖는 용질과 가용성을 갖지 않는 기타 성분 (inert material)의 흔합물이다. 상기 피드에 추출 용매를 가하면 물질 전달 현상에 의해 상기 용질이 피드로부터 추출 용매로 용해된다. 상당량의 용질이 용해된 추출 용매는 추출액 (extract solution)을 형성하고, 용질의 상당량을 잃은 피드는 추잔액 (raffinate solution)을 형성한다. 한편, 본 발명자들의 계속적인 연구 결과, 알돌 축합 공정의 생성물을 추출 용매와 접촉시켜 HPA가 함유된 추출액을 얻는 추출 공정의 효율을 향상시킬 경우, 후속 공정의 현저한 단순화가 가능이 확인되었다. In addition, the feed of the extraction process is a liquid mixture containing the solute to be extracted, and the solute of the solute that is soluble to the extraction solvent and the other components that do not have the solubility It is a compound. When an extraction solvent is added to the feed, the solute is dissolved from the feed into the extraction solvent by mass transfer. Extraction solvents in which a significant amount of solute is dissolved form an extract solution, and feeds that lose a significant amount of solute To form a trafficin solution. On the other hand, the inventors' continuous studies have shown that when the product of the aldol condensation process is brought into contact with the extraction solvent to improve the efficiency of the extraction process of obtaining the extract containing HPA, the subsequent process can be markedly simplified.
구체적으로, 상기 추출 공정이 다공판들에 의해 구획된 복수의 스테이지를 갖는 추출 컬럼에서 수행될 경우, 99 % 이상의 HPA 추출 효율이 확보될 수 있고 물의 함량도 현저히 낮출 수 있다. 그에 따라, 상기 추출 공정 이후에 한 차례의 공정만으로 상기 알돌 축합 공정의 생성물에 포함된 저비점 물질을 분리할 수 있고, 분리된 저비점 물질에 대한 추가적인 정제 설비 없이 리사이클이 가능하다. Specifically, when the extraction process is carried out in an extraction column having a plurality of stages partitioned by the porous plates, HPA extraction efficiency of 99% or more can be ensured and the water content can be significantly lowered. Accordingly, the low boiling point material included in the product of the aldol condensation process may be separated by only one step after the extraction process, and may be recycled without additional purification facilities for the separated low boiling point material.
부가하여, 본 발명자들의 계속적인 연구 결과, HPA를 얻기 위한 알돌 축합 공정을 직렬 연결된 3 기 이상의 연속 교반 반웅기에서 순차로 수행하고, 상기 원료 화합물 중 아이소부틸알데하이드를 각 반웅기에 서로 다른 비율로 분기 투입함과 동시에, 상기 알돌 축합 반웅의 반웅물이 각 반웅기에서 서로 다른 체류 시간 하에 반웅하도록 할 경우, 현저히 향상된 수율로 HPA를 얻을 수 있음이 확인되었다. In addition, as a result of the continuous study by the present inventors, the aldol condensation process for obtaining HPA was sequentially performed in three or more series of continuous stirring reactors connected in series, and isobutylaldehyde in the raw material compound at different ratios in each reactor. Simultaneously with the quarter addition, it was confirmed that HPA can be obtained with a significantly improved yield when the reaction mixture of the aldol condensation reaction product is allowed to react under different residence times in each reaction vessel.
그리고, 이러한 알돌 축합 공정을 통해 미반응 포름알데하이드의 잔류량을 현저히 낮출 수 있을 뿐 아니라, 네오펜틸 글리콜 하이드록시 피발레이트와 같은 부산물의 생성도 효과적으로 억제할 수 있음이 확인되었다. 특히, 상기 알돌 축합 공정에서 각 반웅기에 분기 투입되는 아이소부틸알데하이드의 비율을 순차적으로 감소시키고, 각 반웅기에서 반웅물의 체류시간을 순차적으로 증가시킴으로써, 보다 향상된 효과가 발현될 수 있다. 이러한 발명의 일 구현 예에 따르면, In addition, it was confirmed that the aldol condensation process can not only significantly reduce the amount of unreacted formaldehyde, but also effectively suppress the formation of by-products such as neopentyl glycol hydroxy pivalate. In particular, in the aldol condensation process by sequentially reducing the ratio of isobutyl aldehyde branched into each reaction stage, and sequentially increasing the residence time of the reaction product in each reaction stage, a more improved effect can be expressed. According to one embodiment of this invention,
촉매의 존재 하에 포름알데하이드 수용액과 아이소부틸알데하이드의 알돌 축합 반웅을 통해 HPA가 함유된 생성물을 얻는 알돌 축합 공정, Aldol condensation step of obtaining a product containing HPA through the aldol condensation reaction of aqueous formaldehyde and isobutylaldehyde in the presence of a catalyst,
상기 알돌 축합 공정의 생성물을 추출 용매와 접촉시켜, HPA가 함유된 추출액을 얻는 추출 공정, 상기 추출액을 증류하여 HPA보다 낮은 비점을 갖는 저비점 물질이 제거된 증류액을 얻는 저비점 물질 분리 공정, An extraction step of contacting the product of the aldol condensation step with an extraction solvent to obtain an extract containing HPA; A low boiling point material separation process of distilling the extract to obtain a distillate from which a low boiling point material having a lower boiling point than HPA is removed;
상기 저비점 물질이 제거된 증류액을 촉매의 존재 하에 수소화 반웅시켜 NPG가 함유된 생성물을 얻는 수소화 공정, 및 A hydrogenation process in which the distillate from which the low boiling point material has been removed is hydrogenated in the presence of a catalyst to obtain a product containing NPG, and
상기 수소화 공정의 생성물을 증류하여 NPG를 얻는 정제 공정을 포함하고; A purification step of distilling the product of the hydrogenation step to obtain NPG;
상기 추출 공정은 다공판들에 의해 구획된 복수의 스테이지를 갖는 추출 컬럼에서 수행되는, NPG의 연속 제조 방법이 제공된다. The extraction process is provided for a continuous production method of NPG, which is carried out in an extraction column having a plurality of stages partitioned by porous plates.
첨부된 도면에서, 도 1은 발명의 일 구현 예에 따른 NPG의 연속 제조 방법을 모식적으로 나타낸 것이고, 도 2는 상기 NPG의 연속 제조 방법에서 알돌 축합 공정을 모식적으로 나타낸 것이다. In the accompanying drawings, FIG. 1 schematically illustrates a method of continuously manufacturing NPG according to one embodiment of the present invention, and FIG. 2 schematically illustrates an aldol condensation process in the method of continuously manufacturing NPG.
도 1을 참고하면, 상기 NPG의 연속 제조 방법은 알돌 축합 반웅 시스템 (100), 추출 컬럼 (200), 저비점 물질 분리 컬럼 (300), 수소화 반웅 시스템 (400), 증류 컬럼 (500), 및 고비점 물질 제거탑 (600)을 포함한 흐름으로 수행될 수 있다. Referring to Figure 1, the continuous production method of the NPG Aldol condensation reaction system 100, extraction column 200, low boiling point material separation column 300, hydrogenation reaction system 400, distillation column 500, and high boiling It may be carried out in a flow including a point material removal tower 600.
이하, 도 1 및 도 2를 참고하여, 상기 NPG의 연속 제조 방법에 포함될 수 있는 각 공정에 대하여 설명한다. Hereinafter, with reference to FIGS. 1 and 2, each process that may be included in the method for continuously manufacturing the NPG will be described.
(1 ) 알돌축합공정 (1) aldol condensation process
상기 알돌 축합 공정은, 촉매의 존재 하에 포름알데하이드 수용액과 아이소부틸알데하이드의 알돌 축합 반웅을 통해 HPA가 함유된 생성물을 얻는 공정이다. The aldol condensation step is a step of obtaining a product containing HPA through an aldol condensation reaction of an aqueous formaldehyde solution and isobutylaldehyde in the presence of a catalyst.
상기 알돌 축합 공정은 직렬 연결된 3 기 이상, 바람직하게 3 기 내지 5 기, 보다 바람직하게는 3 기 또는 4기의 연속 교반 반웅기에서 수행될 수 있다. 상기 연속 교반 반웅기의 개수를 증가시킴으로써 상기 알돌 축합 반웅의 효율 향상이 기대될 수 있지만, 공정의 효율과 설비의 복잡성 등을 고려하여, 상기 반웅기의 개수를 결정하는 것이 바람직하다. The aldol condensation process may be carried out in three or more, preferably three to five groups, more preferably three or four groups of continuous stirring reaction in series. The increase in the efficiency of the aldol condensation reaction may be expected by increasing the number of continuous stirring reactions, but it is preferable to determine the number of reaction reactions in consideration of process efficiency and equipment complexity.
도 2는 3 기의 연속 교반 반웅기를 포함한 알돌 축합 반웅 시스템 (100)에 대한 일 구현 예를 모식적으로 나타낸 것이다. FIG. 2 schematically illustrates one embodiment of an aldol condensation reaction system 100 comprising three continuous stirred reaction reactors.
도 2를 참고하면, 상기 알돌 축합 공정은 3 기의 연속 교반 반웅기 (R1 , R2 및 R3)를 포함한 알돌 축합 반응 시스템 (100)에서 수행될 수 있다. 상기 알돌 축합 반응 시스템 (100)에서, 알돌 축합 반웅에 적용되는 촉매 (F0-TEA)와 원료 화합물 (FO-iBAL 및 F0-FA)은 첫 번째 반응기 (R1 )에 투입되어 반웅이 시작된다. 그리고, 그 반웅물은 연결관 (F1 및 F2)을 통해 다른 반웅기 (R2 및 R3)에 순차로 전달되어 반응이 진행된다. Referring to Figure 2, the aldol condensation process is three continuous stirring It may be carried out in the aldol condensation reaction system 100 including the counterunggi (R1, R2 and R3). In the aldol condensation reaction system 100, the catalyst (F0-TEA) and the raw material compounds (FO-iBAL and F0-FA) applied to the aldol condensation reaction are introduced into the first reactor (R1) to start reaction. The reaction product is sequentially delivered to the other reaction vessels R2 and R3 through the connecting pipes F1 and F2 and the reaction proceeds.
특히, 상기 알돌 축합 공정에서, 원료 화합물 중 아이소부틸알데하이드 (FO-iBAL)는 각 반응기 (R1 , R2 및 R3)에 서로 다른 비율로 분기 투입 (S1 , S2 및 S3)되고, 상기 알돌 축합 반웅의 반웅물은 각 반웅기에서 서로 다른 체류 시간 하에서 반응이 이루어진다. In particular, in the aldol condensation process, isobutylaldehyde (FO-iBAL) in the raw material compound is branched (S1, S2 and S3) into each reactor (R1, R2 and R3) at different ratios, The reaction is carried out under different residence times in each reaction.
바람직하게는, 상기 알돌 축합 공정에서 각 반응기에 분기 투입되는 아이소부틸알데하이드의 비율은 순차적으로 감소하고, 각 반응기에서 반웅물의 체류 시간은 순차적으로 증가하도록 수행될 수 있다. 여기서, 각 반웅기에 분기 투입되는 아이소부틸알테하이드 함량의 감속 폭과 반웅물 체류 시간의 증가 폭은 특별히 제한되지 않는다. Preferably, in the aldol condensation process, the ratio of isobutyl aldehyde branched into each reactor may be sequentially decreased, and the residence time of the reaction product in each reactor may be sequentially increased. Here, the deceleration width of the isobutyl aldehyde content and the increase width of the reaction time residence time is not particularly limited.
구체적으로, 3 기의 연속 교반 반웅기 (R1 , R2 및 R3)를 포함한 알돌 축합 반웅 시스템 (100)의 경우, 상기 반웅 시스템에 투입되는 아이소부틸알데하이드의 전체 함량을 기준으로, 89 내지 94 중량0 /。의 아이소부틸알데하이드는 첫 번째 반웅기 (R1 )에 투입되고, 5 내지 10 중량 0/。의 아이소부틸알데하이드는 두 번째 반응기 (R2)에 투입되고, 1 내지 3 중량0 /。의 아이소부틸알데하이드는 세 번째 반웅기 (R3)에 투입될 수 있다. 즉, 촉매가 나타내는 활성의 양상과 알돌 축합 반웅의 전체적인 효율을 고려하여, 첫 번째 반웅기 (R1 )에는 89 증량 % 이상의 아이소부틸알데하이드가 투입되도록 하는 것이 바람직하고, 세 번째 반웅기 (R3)에는 3 중량0 /。 이하의 아이소부틸알데하이드가 투입되도록 하는 것이 바람직하다. Specifically, in the case of the aldol condensation reaction system 100 including three continuous stirring reaction groups R1, R2 and R3, 89 to 94 weight 0 based on the total content of isobutylaldehyde added to the reaction system. /. Isobutylaldehyde is charged to the first reaction vessel (R1), 5 to 10 weight 0 /。 isobutylaldehyde is charged to the second reactor (R2), 1 to 3 weight 0 /。 isobutyl Aldehyde may be added to the third reaction stage (R3). That is, in consideration of the activity of the catalyst and the overall efficiency of the aldol condensation reaction, it is preferable to add at least 89% by weight of isobutylaldehyde to the first reaction stage (R1), and to the third reaction stage (R3). 3 parts by weight 0 /. it is preferable that less than isobutyl aldehyde is put in.
특히, 상기 아이소부틸알데하이드의 분기 투입과 함께, 상기 3 기의 연속 교반 반웅기에서 반웅물의 체류 시간은, 순차적으로 증가함을 전제로, 첫 번째 반웅기 (R1 )에서 10 내지 13 분, 두 번째 반응기 (R2)에서 13 내지 17 분, 그리고 세 번째 반웅기 (R3)에서 17 내지 19 분으로 조절될 수 있다. 여기서, 각 반웅기에서의 반웅물의 체류 시간은 반웅물의 공간 속도, 특히 상기 알돌 축합 반웅에서 반웅물의 액체 공간 속도 (liquid hourly space velocity; LHSV = Reactant Liquid Flow Rate I Reactor Volume)의 측정을 통해 상술한 범위 내에서 조절될 수 있다. In particular, with the branched dosing of the isobutylaldehyde, the residence time of the reaction product in the three consecutive stirred agitators is, on the premise of increasing sequentially, from 10 to 13 minutes in the first reaction period (R1), the second 13 to 17 minutes in the reactor (R2), and 17 to 19 minutes in the third reaction stage (R3). Here, the residence time of the counterungmul in each counterunggi is the space velocity of the counterungung, In particular, the aldol condensation reaction can be controlled within the above-described range through measurement of the liquid hourly space velocity (LHSV = Reactant Liquid Flow Rate I Reactor Volume).
그리고, 상기 알돌 축합 공정에 있어서, 각 반응기에서 반웅물의 효과적인 교반을 위해서는 레이놀즈 수 (Reynolds number), 임펠러 (impeller)의 팁 (tip)에서의 선속도 (linear velocity), 반웅기 벽면에서의 선속도 등의 인자가 고려되어야 한다. 바람직하게는, 상기 알돌 축합 반웅기 시스템에서 각 반웅기의 레이놀즈 수는 50000 이상, 임펠러의 팁과 반응기의 벽면에서의 선속도의 차이는 2 내지 5 m/sec로 조절될 수 있다. In the aldol condensation process, the Reynolds number, the linear velocity at the tip of the impeller, and the linear velocity at the wall surface of the semi-ungwoon for effective agitation of the reactants in each reactor. And other factors should be considered. Preferably, in the aldol condensation semi-agitator system, the Reynolds number of each semi-unggi is 50000 or more, and the difference between the linear velocity at the tip of the impeller and the wall of the reactor may be adjusted to 2 to 5 m / sec.
그리고, 포름알데하이드 수용액과 아이소부틸알데하이드의 알돌 축합 반웅은 발열 반웅이다. 따라서, 각 반웅기의 반웅물을 반웅기의 외부로 순환시키면서 반웅열을 제거하는 것이 바람직하다. 특히, 상기 반웅물을 외부로 순환시킴에 있어서, 벤츄리 노즐 (venturi nozzle)이 구비된 분사기를 이용하여 반웅물을 반웅기 내에 강력하게 분사함으로써 보다 향상된 반웅 효율을 확보할 수 있다. 즉, 상기 알돌 축합 공정은 각각 순환 핍프, 열 교환기 및 반응물 분사기를 포함한 반웅물 순환 유닛을 매개로 직렬 연결된 And the aldol condensation reaction of formaldehyde aqueous solution and isobutyl aldehyde is exothermic reaction. Therefore, it is preferable to remove the semiungung heat while circulating the semiungung of each halfunggi to the outside of the semiungunggi. Particularly, in circulating the reaction product to the outside, by using the injector equipped with a venturi nozzle, the reaction product may be strongly sprayed into the reaction device to ensure more improved reaction efficiency. In other words, the aldol condensation process is connected in series via a semi-acre water circulation unit including a circulation pip, a heat exchanger and a reactant injector, respectively.
3 기 이상의 연속 교반 반응기에서 수행될 수 있다. It may be carried out in three or more continuous stirred reactors.
한편, 상기 알돌 축합 공정에 있어서, 아이소부틸알데하이드로는 이성질체의 함량이 0.5 중량0 /0 미만인 것을 사용하는 것이 부산물의 생성을 억제하는데 유리하다. On the other hand, in the aldol condensation step, isobutyl aldehyde as is advantageous in that the amount of isomer used to 0.5 0/0 of less than suppressing the formation of by-products.
그리고, 아이소부틸알데하이드는 포름알데하이드 1몰에 대하여 1 .1 내지 1 .5의 몰비, 바람직하게는 1 .1 내지 1 .2의 몰비로 사용될 수 있다. 즉, 알돌 축합 반웅에 사용된 포름알데하이드의 완전한 반웅을 유도하기 위하여, 아이소부틸알데하이드는 포름알데하이드 대비 과량으로, 바람직하게는 1 : 1 .1 이상의 몰비로 사용될 수 있다. 다만, 아이소부틸알데하이드가 너무 과하게 사용될 경우 티쉬첸코 반웅 등에 의한 부산물의 생성이 증가할 수 있다. 그러므로, 아이소부틸알데하이드는 포름알데하이드 대비 1 : 1 .5 이하의 몰비로 사용되는 것이 바람직하다. In addition, isobutyl aldehyde may be used in a molar ratio of 1.1 to 1.5, preferably in a molar ratio of 1.1 to 1.2 with respect to 1 mol of formaldehyde. That is, in order to induce complete reaction of the formaldehyde used in the aldol condensation reaction, isobutylaldehyde may be used in excess of formaldehyde, preferably in a molar ratio of 1: 1 or more. However, when isobutyl aldehyde is used too much, the production of by-products due to Tishchenko banung may be increased. Therefore, isobutyl aldehyde is preferably used in a molar ratio of less than 1: 1.5 relative to formaldehyde.
상기 알돌 축합 공정에 있어서, 포름알데하이드 수용액으로는 포름알데하이드의 농도 35 내지 45 증량0 /。의 포르말린 (formalin)을 사용하는 것이 반웅 효율의 향상과 폐수 발생의 저감을 위해 유리하다. 그리고, 일반적으로 포름알데하이드 수용액에는 포름알데하이드의 중합을 방지하기 위해 메탄올이 첨가되는데, 그 함량은 포름알데하이드 수용액에 대하여In the above-mentioned aldol condensation step, formaldehyde is used as an aqueous solution of formaldehyde having a concentration of formaldehyde having a concentration of 35 to 45 and increasing 0 /. It is advantageous for the improvement of reaction efficiency and the reduction of waste water generation. In general, methanol is added to the aqueous formaldehyde solution to prevent the polymerization of formaldehyde, the content of which is relative to the aqueous formaldehyde solution.
0.1 -5 중량 0/。인 것이 바람직하다. It is preferable that it is 0.1-5 weight 0 /.
상기 알돌 축합 공정에 있어서, 상기 촉매로는 L H, NaOH, KOH, In the aldol condensation process, the catalyst is L H, NaOH, KOH,
Ca(OH)2 와 같은 수산화물; NaCO3, LiC03, KCO3, Ca(CO3)2, NH4C03와 같은 알칼리금속 카보네이트; 트리메틸아민, 트리에틸아민, 트리프로필아민과 같은 3차 아민 화합물이 사용될 수 있다. 상기 촉매 중 3차 아민 화합물, 특히 트리에틸아민은 알돌 축합 반응의 효율 향상 측면에서 보다 바람직하게 사용될 수 있다. Hydroxides such as Ca (OH) 2 ; Alkali metal carbonates such as NaCO 3 , LiCO 3 , KCO 3 , Ca (CO 3 ) 2 , NH 4 CO 3 ; Tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine can be used. Tertiary amine compounds, particularly triethylamine, in the catalyst may be more preferably used in view of improving the efficiency of the aldol condensation reaction.
그리고, 상기 촉매는 포름알데하이드 1몰에 대하여 0.01 내지 0.5의 몰비, 바람직하게는 0.15 내지 0.25의 몰비, 보다 바람직하게는 0.18 내지 0.22의 몰비로 사용될 수 있다. 즉, 촉매 효과의 발현을 위하여, 상기 촉매는 포름알데하이드 대비 1 : 0.01 이상의 몰비로 사용될 수 있다. 다만, 촉매가 너무 과하게 사용될 경우 촉매의 회수가 요구되고 부산물의 생성이 유발될 수 있다. 그러므로, 상기 촉매는 포름알데하이드 대비 1 : 0.5 이하의 몰비로 사용되는 것이 바람직하다. In addition, the catalyst may be used in a molar ratio of 0.01 to 0.5, preferably 0.15 to 0.25, and more preferably 0.18 to 0.22 with respect to 1 mol of formaldehyde. That is, in order to express the catalytic effect, the catalyst may be used in a molar ratio of 1: 0.01 or more relative to formaldehyde. However, if the catalyst is used too much, recovery of the catalyst may be required and generation of by-products may be caused. Therefore, the catalyst is preferably used in a molar ratio of 1: 0.5 or less relative to formaldehyde.
한편, 상기 알돌 축합 공정에 있어서, 반웅 온도는 70 내지 100 °C , 바람직하게는 70 내지 85 °C로 유지될 수 있다. 상기 반웅의 수율 확보를 위하여, 상기 반웅 온도는 70 °C 이상인 것이 바람직하다. 다만, 반웅 온도가 너무 높을 경우 부산물의 생성이 가속화될 수 있으므로, 상기 반웅 온도는 100 °C 이하인 것이 바람직하다. 그리고, 상기 알돌 축합 반웅은 가압 하에서 수행되는 것이 수율의 확보를 위해 바람직할 수 있다. On the other hand, in the aldol condensation process, the reaction temperature may be maintained at 70 to 100 ° C, preferably 70 to 85 ° C. In order to ensure the yield of the reaction, the reaction temperature is preferably 70 ° C or more. However, when the reaction temperature is too high, the production of by-products may be accelerated, and the reaction temperature is preferably 100 ° C. or less. The aldol condensation reaction may be performed under pressure to ensure yield.
상술한 조건 하에서 수행되는 알돌 축합 공정은 원료 화합물에 대한 흔합 효율의 극대화를 가능케 하여, 상기 알돌 축합 반웅의 효율을 향상시키고, 이와 함께 미반웅 포름알데하이드의 잔존과 부산물의 생성을 최소화할 수 있다. 구체적으로, 상기 알돌 축합 공정을 통해 99 % 이상의 높은 HPA 수율과 2000 ppm 이하의 낮은 잔류 포름알데하이드의 농도가 확보될 수 있다. (2)추출공정 The aldol condensation process performed under the above-described conditions enables the maximization of the mixing efficiency of the raw material compound, thereby improving the efficiency of the aldol condensation reaction, and minimizing the remaining of the non-banung formaldehyde and the generation of by-products. Specifically, the aldol condensation process may ensure a high HPA yield of 99% or more and a low residual formaldehyde concentration of 2000 ppm or less. (2) Extraction process
상기 추출 공정은, 상기 알돌 축합 공정의 생성물을 추출 용매와 접촉시켜 HPA가 함유된 추출액을 얻는 공정이다. The extraction step is a step of obtaining the extract containing HPA by bringing the product of the aldol condensation step into contact with the extraction solvent.
특히, 본 발명에 있어서 상기 추출 공정은 다공판들에 의해 구획된 복수의 스테이지를 갖는 추출 컬럼에서 수행된다. 그에 따라, 상기 추출 공정을 통해 현저히 향상된 HPA 추출 효율이 확보될 수 있고, 후속되는 저비점 물질 분리 공정의 단순화가 가능하다. In particular, in the present invention, the extraction process is performed in an extraction column having a plurality of stages partitioned by the porous plates. Accordingly, the extraction process can ensure a significantly improved HPA extraction efficiency, it is possible to simplify the subsequent low boiling point material separation process.
상기 추출 공정에는, 액-액 접촉 방식에 따른 추출 컬럼으로서 상하 반복 운동을 하는 다공판들에 의해 구획된 스테이지를 갖는 우수한 교반 시스템의 추출 컬럼 (200)이 바람직하게 적용될 수 있다. 구체적으로, 상기 추출 컬럼 (200)으로는 Kuhni 컬럼, Karr type의 왕복 플레이트 컬럼 (Karr type reciprocating plate column), 회전-원판형 컬럼 (rotary-disk contactor), Scheibel 컬럼, 분무 추출 컬럼 (spray extraction column), 충진 추출 컬럼 (packed extraction column), 펄스 충진 컬럼 (pulsed packed column) 등이 이용될 수 있다. In the extraction process, the extraction column 200 of the excellent stirring system having a stage partitioned by the perforated plates having the vertically repeating movement as the extraction column according to the liquid-liquid contacting method can be preferably applied. Specifically, the extraction column 200 includes a Kuhni column, a Karr type reciprocating plate column, a rotary-disk contactor, a Scheibel column, and a spray extraction column. ), Packed extraction columns, pulse packed columns, and the like may be used.
그리고, 추출 컬럼 하에서 층분한 추출 효율이 발현될 수 있도록 하기 위하여, 상기 추출 공정은 다공판들에 의해 구획된 20 단 이상, 바람직하게는 20 내지 30 단의 스테이지를 갖는 추출 컬럼에서 수행될 수 있다. 이때, 상기 추출 컬럼에서 한 단의 높이는 300 내지 500 mm인 것이 추출 효율의 향상에 유리할 수 있다. 다만, 상기 추출 컬럼의 스테이지 수와 단의 높이는 파일럿 컬럼에 한정되는 예일 수 있으며, 상용화 공정에는 적정한 범위로 확장하여 적용될 수 있다. In addition, the extraction process may be performed in an extraction column having 20 or more stages, preferably 20 to 30 stages, stages partitioned by the porous plates so that the divided extraction efficiency can be expressed under the extraction column. . At this time, the height of one stage in the extraction column may be advantageous to improve the extraction efficiency of 300 to 500 mm. However, the number of stages and the height of the stage of the extraction column may be an example limited to the pilot column, and may be extended to an appropriate range in the commercialization process.
상기 추출 공정에서, 추출 컬럼 (200)에 공급된 상기 알돌 축합 공정의 생성물은 추출 용매와 접촉하여, 상당량의 HPA이 용해된 추출액 (extract s ution)과 HPA의 상당량을 잃은 추잔액 (raffinate s이 ution)으로 각각 배출된다. 이때, 상대적으로 가벼운 상인 상기 추출액은 추출 컬럼 (200)의 상부 배출구를 통해 수득되고, 상대적으로 무거운 상인 상기 추잔액은 추출 컬럼 (200)의 하부 배출구를 통해 수득된다. In the extraction process, the product of the aldol condensation process supplied to the extraction column 200 is brought into contact with the extraction solvent, and extracts containing a significant amount of HPA and a weight loss of a significant amount of HPA are lost. ution). At this time, the relatively light phase of the extract is obtained through the upper outlet of the extraction column 200, the relatively heavy phase of the extract is obtained through the lower outlet of the extraction column (200).
상기 추출 공정에서, 추출 용매로는 HPA에 대한 가용성을 갖는 것으로서, 바람직하게는 옥탄올이 사용될 수 있다. 상기 추출 용매는 추출 컬럼 (200)에 공급되는 상기 알돌 축합 공정의 생성물에 대하여 1 :0.3 내지 1 :0.7, 바람직하게는 1 :0.4 내지 1 :0.6의 중량비로 사용될 수 있다. 즉, 층분한 추출 효율의 확보를 위하여, 상기 추출 용매는 상기 생성물에 대하여 1 :0.3 이상의 중량비로 사용되는 것이 바람직하다. 그리고, 상기 추출 용매의 중량비가 1 :0.7을 초과하는 경우에도 추출 효율은 좋아질 수 있지만, 후속되는 저비점 물질 분리 공정에서 HPA의 손실량이 증가할 수 있고, 이를 막기 위한 공비 용매의 환류 흐름이 과도하게 높아질 수 있어 바람직하지 않다. In the extraction process, as the extraction solvent having solubility in HPA, preferably octanol may be used. The extraction solvent may be used in a weight ratio of 1: 0.3 to 1: 0.7, preferably 1: 0.4 to 1: 0.6, based on the product of the aldol condensation process supplied to the extraction column 200. In other words, in order to ensure a good extraction efficiency, the extraction solvent is preferably used in a weight ratio of 1: 0.3 or more with respect to the product. In addition, even when the weight ratio of the extraction solvent exceeds 1: 0.7, the extraction efficiency may be improved, but the loss amount of HPA may be increased in the subsequent low boiling point material separation process, and the reflux flow of the azeotropic solvent to prevent this is excessive. It can be high, which is undesirable.
그리고, 온도가 과하게 낮을 경우 HPA가 경화될 수 있으므로, 상기 추출 공정의 온도는 40 °C 이상으로 유지되는 것이 바람직하다. 다만, 온도가 과하게 높을 경우 추출액의 상 분리가 이루어지지 않을 수 있으므로, 상기 추출 공정의 온도는 90 °C 이하로 유지되는 것이 바람직하다. And, since the HPA can be cured when the temperature is excessively low, the temperature of the extraction process is preferably maintained at 40 ° C or more. However, if the temperature is too high, the phase separation of the extract may not be made, it is preferable that the temperature of the extraction process is maintained at 90 ° C or less.
발명의 구현 예에 따르면, 상술한 바와 같은 추출 공정을 통해 99 % 이상의 HPA 추출 효율이 확보될 수 있다. 즉, 상기 추출 공정을 통해 얻어진 추출액은 상기 알돌 축합 공정의 생성물에 함유된 HPA의 99 중량 % 이상을 함유할 수 있다. 또한, 상기 알돌 축합 공정의 생성물에 함유된 물은 대부분 추잔액으로 배출됨에 따라, 상기 추출액에는 물이 3 중량0 /。 이하로 포함된다. According to an embodiment of the present invention, an extraction efficiency of 99% or more may be secured through the extraction process as described above. That is, the extract obtained through the extraction process may contain more than 99% by weight of the HPA contained in the product of the aldol condensation process. In addition, since most of the water contained in the product of the aldol condensation process is discharged to the weight balance, the extract contains less than 3 weight 0 /.
이처럼 상기 알돌 축합 공정에서 얻은 HPA의 99 중량0 /0 이상이 상기 추출 공정을 통해 추출됨에 따라, 추출 공정에서의 HPA의 손실이 최소화될 수 있다. 그리고, 상기 추출 공정은 후속되는 저비점 물질 분리 공정의 설비 부담 및 에너지 소비량을 낮출 수 있다. As such it, the loss of HPA in the extraction step may be minimized as a 99 weight 0/0 over the HPA obtained in the aldol condensation step extraction through the extraction process. In addition, the extraction process may lower the equipment burden and energy consumption of the subsequent low-boiling point material separation process.
(3) 저비점 물질 분리 공정 (3) low boiling point material separation process
상기 저비점 물질 분리 공정은, 상기 추출액을 증류하여 HPA보다 낮은 비점을 갖는 저비점 물질이 제거된 증류액을 얻는 공정이다. The low boiling point material separation step is a step of distilling the extract to obtain a distillate from which a low boiling point material having a lower boiling point than HPA is removed.
상기 추출액에는 HPA 이외에 미반웅된 아이소부틸알데하이드, 알돌 축합 반웅 촉매, 포름알데하이드 수용액에 포함된 물 및 메탄을 등의 저비점 물질이 포함되어 있다. 이러한 저비점 물질은 증류를 통해 상기 추출액으로부터 분리될 수 있다. 특히, 본 발명에서는 상기 추출 공정에서 99 % 이상의 HPA 추출 효율이 확보됨에 따라, 상기 추출 공정 이후에 한 차례의 증류만으로 상기 저비점 물질의 분리가 가능하다. 그리고, 분리된 저비점 물질 중 아이소부틸알데하이드 및 촉매는 상기 알돌 축합 공정에 리사이클될 수 있다. In addition to HPA, the extract contains low-boiling substances such as isobutyl aldehyde, aldol condensation reaction catalyst, water contained in aqueous formaldehyde and methane. This low boiling point material may be separated from the extract by distillation. In particular, in the present invention, as the extraction efficiency of 99% or more HPA is secured in the extraction process, the low boiling point material can be separated by only one distillation after the extraction process. In addition, isobutylaldehyde and the catalyst in the separated low boiling point material may be recycled to the aldol condensation process.
상기 저비점 물질 분리 공정에서 저비점 물질 분리 컬럼 (300)으로 공급된 추출액은 공비 용매와 접촉하고, 적정 온도로 가열되면서 증발과 웅축에 의한 증류가 이루어진다. In the low boiling point material separation process, the extract liquid supplied to the low boiling point material separation column 300 is contacted with an azeotropic solvent and heated to an appropriate temperature to be distilled by evaporation and expansion.
이때, 상기 추출액에 포함된 HPA를 저비점 물질로부터 효율적으로 분리하기 위하여, 상기 저비점 물질 분리 공정은 공비 증류 방식으로 수행되는 것이 바람직하다. 상기 공비 증류 방식에 적용되는 용매로는 상기 저비점 물질과 공비를 이를 수 있고 HPA보다 낮은 끓는 점을 갖는 통상의 것이 적용될 수 있다. (4) 수소화공정 In this case, in order to efficiently separate the HPA contained in the extract from the low boiling point material, the low boiling point material separation process is preferably carried out by azeotropic distillation. As the solvent applied to the azeotropic distillation method, a common one having a lower boiling point and azeotropic boiling point than HPA may be applied. (4) hydrogenation process
상기 수소화 공정은, 상기 저비점 물질이 제거된 증류액을 촉매의 존재 하에 수소화 반응시켜 NPG가 함유된 생성물을 얻는 공정이다. The hydrogenation step is a step of hydrogenating the distillate from which the low boiling point material is removed in the presence of a catalyst to obtain a product containing NPG.
상기 수소화 반웅의 촉매로는 통상의 니켈 촉매가 이용될 수 있다. 상기 촉매는 상기 증류액에 포함된 HPA에 대하여 2 내지 10 중량0 /。로 사용될 수 있다. As the catalyst for the hydrogenation reaction, a conventional nickel catalyst may be used. The catalyst may be used in an amount of 2 to 10 weight 0 / .about HPA contained in the distillate.
상기 수소화 반웅은 기-액 반웅이다. 따라서, 반응물의 접촉 효율을 증대시키기 위하여, 상기 수소화 반웅에는 상기 HPA 함유 증류액을 반웅계에 분사하는 벤츄리 노즐이 구비된 수소화 반웅 시스템 (400)이 이용될 수 있다. The hydrogenation reaction is a gas-liquid reaction. Therefore, in order to increase the contact efficiency of the reactants, the hydrogenation reaction system may include a hydrogenation reaction system 400 having a venturi nozzle for spraying the HPA-containing distillate into the reaction system.
그리고, 상기 수소화 반웅은 100 내지 1500 psig의 수소 압력 및 100 내지 200 °C의 온도 하에서 수행되는 것이 수율의 확보 측면에서 바람직하다. In addition, the hydrogenation reaction is preferably performed under a hydrogen pressure of 100 to 1500 psig and a temperature of 100 to 200 ° C. in terms of securing a yield.
(5) 정제 공정 (5) purification process
상기 정제 공정은, 상기 수소화 공정의 생성물을 증류하여 NPG를 얻는 공정이다. In the purification step, the product of the hydrogenation step is distilled to obtain NPG. It is a process of obtaining.
상기 수소화 공정의 생성물에는 조 (crude) NPG 이외에 미반웅 HPA, In the product of the hydrogenation process, in addition to crude NPG, Mibanung HPA,
HPA의 이량체 고비점 물질 등이 포함되어 있을 수 있다. 따라서, 상기 수소화 공정의 생성물을 증류 컬럼 (500)에서 증류하여 고순도의 NPG를 얻을 수 있다. HPA dimer high boiling point material may be included. Accordingly, the product of the hydrogenation process may be distilled in the distillation column 500 to obtain high purity NPG.
그리고, 필요에 따라, 상기 증류를 통해 NPG로부터 분리된 물질을 고비점 물질 제거탑 (600)에 공급하여 고비점 물질을 분리하는 공정이 수행될 수 있다. 【발명의 효과】 Then, if necessary, a process of separating the high boiling point material by supplying the material separated from the NPG through the distillation to the high boiling point material removal tower 600 may be performed. 【Effects of the Invention】
본 발명에 따른 NPG의 연속 제조 방법은 향상된 효율로 HPA를 추출함으로써 후속 공정의 단순화와 NPG의 수율 향상을 가능케 한다. The continuous manufacturing method of NPG according to the present invention enables extraction of HPA with improved efficiency, which simplifies subsequent processing and improves NPG yield.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 본 발명의 일 구현 예에 따른 NPG의 연속 제조 방법을 모식적으로 나타낸 것이다. 1 schematically shows a method of continuously manufacturing NPG according to an embodiment of the present invention.
도 2는 본 발명의 일 구현 예에 따른 NPG의 연속 제조 방법에서 알돌 축합 공정을 모식적으로 나타낸 것이다. 【부호의 설명】 Figure 2 schematically shows an aldol condensation process in the continuous production method of NPG according to an embodiment of the present invention. [Explanation of code]
R: 원료 화합물 R: raw material compound
100: 알돌 축합 반응 시스템 100: aldol condensation reaction system
200: 추출 컬럼 200: extraction column
300: 저비점 물질 분리 컬럼 300: low boiling point material separation column
400: 수소화 반응 시스템 400: hydrogenation reaction system
500: 증류 컬럼 500: distillation column
600: 고비점 물질 제거탑 600: high boiling point material removal tower
E: 추출 용매 E: extraction solvent
H: 수소 H: hydrogen
NPG: 네오펜틸 글리콜 HB: 고비점 물질 NPG: neopentyl glycol HB: high boiling point material
FO-iBAL: 아이소부틸알데하이드 공급 라인 FO-iBAL: Isobutylaldehyde Supply Line
F0-FA: 포름알데하이드 수용액 공급 라인 F0-FA: formaldehyde aqueous solution supply line
F0-TEA: 촉매 공급 라인 F0-TEA: catalyst supply line
SO: 분배기 SO: distributor
S1 , S2, S3: 아이소부틸알데하이드 분기 투입 라인 S1, S2, S3: Isobutylaldehyde Branch Input Line
R1 , R2, R3: 연속 교반 반웅기 R1, R2, R3: Continuous Stirring Reactor
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로 한정하는 것은 아니다. 실시예 Hereinafter, preferred embodiments of the present invention are provided to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. Example
도. 1과 같은 구성의 장치를 준비하였다. 그 중 알돌 축합 공정에는 도 2와 같이 직렬 연결된 3 기의 연속 교반 반웅기 (R1 , R2 및 R3)를 포함한 알돌 축합 반웅 시스템 (100)이 이용되었다. 그리고, 추출 공정의 추출 컬럼 (200)으로는 상하 반복 운동을 하는 다공판들에 의해 구획된 총 24 단의 스테이지를 갖는 Kuhni 컬럼 (한 단의 높이 400 mm)이 이용되었다. Degree. The device of the same structure as 1 was prepared. Among them, an aldol condensation reaction system 100 including three continuous stirring reactors R1, R2 and R3 connected in series is used for the aldol condensation process. In addition, as the extraction column 200 of the extraction process, a Kuhni column (400 mm in height) having a total of 24 stages stages partitioned by the perforated plates having vertical and repeating motions was used.
알돌 축합 공정을 위한 원료 화합물로, 아이소부틸알데하이드와 포름알데하이드 수용액 (알데하이드 농도 42 중량0 /0, 메탄올 1 중량0 /。 함유)을 준비하였다. 촉매로 트리에틸아민 (TEA)을 준비하였다. As starting compound for the aldol condensation process, was prepared isobutyl aldehyde and formaldehyde solution (concentration 42 weight aldehydes 0/0, methanol, 1 part by weight 0 /. Content). Triethylamine (TEA) was prepared as a catalyst.
포름알데하이드: 아이소부틸알데하이드: 트리에틸아민은 1 : 1 .1 : 0.2의 몰비로 사용되었다. 포름알데하이드 수용액과 촉매는 첫 번째 반응기에 투입되었다. 그리고, 아이소부틸알데하이드의 전체 함량을 기준으로, 91 중량%의 아이소부틸알데하이드는 첫 번째 반웅기 (R1 )에, 7.5 중량0 /。의 아이소부틸알데하이드는 두 번째 반웅기 (R2)에, 1 .5 중량0 /。의 아이소부틸알데하이드는 세 번째 반웅기 (R3)에 각각 분기 투입되었다. 동시에, 각 반웅기에서 반웅물의 체류 시간은 아래 표 1과 같이 조절되었다. 【표 1】 Formaldehyde: isobutylaldehyde: triethylamine was used in a molar ratio of 1: 1.1: 0.2. Formaldehyde aqueous solution and catalyst were added to the first reactor. And, based on the total content of isobutyl aldehyde, 91% by weight of isobutylaldehyde is in the first half foot group (R1), 7.5 weight 0 /. Isobutylaldehyde in the second half foot group (R2), 1. 5 weights 0 /. Of isobutylaldehyde were each branched to the third half-aerator (R3). At the same time, the residence time of the semi-treatment in each reaction period was adjusted as shown in Table 1 below. Table 1
그리고, 상기 알돌 축합 공정은 72 내지 78 °C의 온도와 3 atm의 압력 하에서 연속적으로 수행되었고, 이를 통해 HPA가 함유된 생성물이 얻어졌다 (전환율 89.8%, 생성물 내 잔류 포름알데하이드 농도 2000 ppm, HPA 수율 99.20%). In addition, the aldol condensation process was carried out continuously at a temperature of 72 to 78 ° C and a pressure of 3 atm, through which a product containing HPA was obtained (conversion rate 89.8%, residual formaldehyde concentration in the product 2000 ppm, HPA Yield 99.20%).
한편, 상기 알돌 축합 공정의 생성물은 추출 컬럼 (200)에 도입되었다. 이때, 추출 컬럼 (200)에는 상기 생성물 대비 50 중량0 /0의 옥탄올이 추출 용매로써 도입되었다. 추출 컬럼에서의 격렬한 교반에 의해 HPA의 추출이 수행되었고, 이를 통해 얻은 추출액 중 유기층의 조성을 아래 표 2에 나타내었다. On the other hand, the product of the aldol condensation process was introduced into the extraction column (200). At this time, the extraction column 200 has been introduced into the octanol in 50 parts by weight 0/0 compared to the product by solvent extraction. Extraction of HPA was performed by vigorous stirring in the extraction column, and the composition of the organic layer in the extract obtained therefrom is shown in Table 2 below.
이어서, 상기 추출액을 저비점 물질 분리 컬럼 (300)에서 증류하여 저비점 물질인 아이소부틸알데하이드, 트리에틸아민, 물, 메탄올 등이 분리되었다. 분리된 저비점 물질은 저비점 물질 분리 컬럼 (300)의 상부로 배출되어 알돌 축합 반응 시스템 (100)으로 재순환되었다. 저비점 물질의 조성을 아래 표 2에 나타내었다. Subsequently, the extract was distilled in the low boiling point material separation column 300 to separate isobutyl aldehyde, triethylamine, water, methanol, and the like, which were low boiling point materials. The separated low boiling point material was discharged to the top of the low boiling point material separation column 300 and recycled to the aldol condensation reaction system 100. The composition of the low boiling point material is shown in Table 2 below.
저비점 물질이 제거된 증류액은 수소화 반웅 시스템 (400)에 연속적으로 도입되어, 니켈 촉매의 존재 하에 수소화 공정이 수행되었다. 상기 수소화 공정의 생성물은 증류 컬럼 (500)에 연속적으로 도입되어 정제되었고, 최종적으로 NPG를 얻었다. The distillate from which the low boiling point material was removed was continuously introduced into the hydrogenation reaction system 400, and the hydrogenation process was performed in the presence of a nickel catalyst. The product of the hydrogenation process was continuously introduced into the distillation column 500 to purify, finally obtaining NPG.
【표 2】 Table 2
알돌 축합 공정의 추출액 중 유기층 저비점 물질 생성물 (중량 %) (중량 %) (중량 %) Organic layer low boiling point product (wt%) (wt%) (wt%) in extract of aldol condensation process
HPA 57.3 45.4 4 HPA 57.3 45.4 4
口 23.8 2.7 5 옥탄올 0.4 37.4 2 아이소부틸알데하이드 4.1 3.2 21 Z 23.8 2.7 5 Octanol 0.4 37.4 2 Isobutylaldehyde 4.1 3.2 21
포름알데하이드 0.3 0.2 2 메탄올 2.0 1.5 7Formaldehyde 0.3 0.2 2 Methanol 2.0 1.5 7
TEA 1 1 .4 9.0 59 네오펜틸 글리콜 0.8 0.6 0 아이소부틸레이트 상기 표 2를 참고하면, 상기 추출 공정을 통해 얻어진 추출액에는 상기 알돌 축합 공정의 생성물에 함유된 HPA의 약 99.7 중량0 /0가 함유된 것으로 확인되었다. 그리고, 상기 추출액에는 물이 3 중량0 /。 이하로 포함되었다. 이처럼 상기 추출 공정은 99% 이상와 우수한 HPA 추출 효율을 나타내었다. TEA 1 1 .4 9.0 59 0.8 0.6 0 neopentyl glycol isobutyl acrylate With reference to Table 2, the extract obtained through the extraction process, containing about 99.7 wt. 0/0 of HPA containing the product of the aldol condensation step Was confirmed. And, the extract contained less than 3 weight 0 /. As such, the extraction process showed more than 99% and excellent HPA extraction efficiency.
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| US4855515A (en) * | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
| US4851592A (en) * | 1987-10-27 | 1989-07-25 | Eastman Kodak Company | Triethylamine catalyzed neopentyl glycol production utilizing a gas sparged reactor |
| KR19980028461A (en) * | 1996-10-22 | 1998-07-15 | 성재갑 | How to prepare neopentyl glycol |
| KR20060073044A (en) * | 2004-12-24 | 2006-06-28 | 주식회사 엘지화학 | Method for preparing neopentyl glycol |
| KR20140126876A (en) * | 2013-04-23 | 2014-11-03 | 주식회사 엘지화학 | Method for preparing Neophentylglycol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232177A (en) * | 2018-10-24 | 2019-01-18 | 江苏开磷瑞阳化工股份有限公司 | A kind of method that catalytic hydrogenation prepares neopentyl glycol |
| CN109232177B (en) * | 2018-10-24 | 2021-05-07 | 江苏开磷瑞阳化工股份有限公司 | Method for preparing neopentyl glycol through catalytic hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160133843A (en) | 2016-11-23 |
| KR101808248B1 (en) | 2017-12-12 |
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