TWI535711B - Method of producing tetrahydrofuran - Google Patents
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Description
本發明係關於四氫呋喃之製造方法,尤其是關於使用酸觸媒,藉由1,4-丁二醇之脫水環化反應而安定且有效率地製造四氫呋喃的方法。 The present invention relates to a process for producing tetrahydrofuran, and more particularly to a process for stably and efficiently producing tetrahydrofuran by a dehydration cyclization reaction of 1,4-butanediol using an acid catalyst.
四氫呋喃(以下有時簡稱為「THF」)係可用於作為包括高分子化合物之各種有機化合物的溶劑、聚丁二醇之原料等。 Tetrahydrofuran (hereinafter sometimes abbreviated as "THF") can be used as a solvent for various organic compounds including a polymer compound, a raw material of polytetramethylene glycol, and the like.
四氫呋喃於工業上大多藉由1,4-丁二醇(以下有時簡稱為「1,4BG」)之脫水環化反應所製造。作為其反應之觸媒,已知不論於均勻系統或不均勻系統中酸觸媒均屬有效。 Tetrahydrofuran is industrially produced by a dehydration cyclization reaction of 1,4-butanediol (hereinafter sometimes abbreviated as "1,4BG"). As a catalyst for the reaction, it is known that an acid catalyst is effective regardless of a uniform system or a heterogeneous system.
例如,已知有使用二氧化矽氧化鋁觸媒(專利文獻1)、或陽離子交換樹脂(專利文獻2)等之固體觸媒的方法,但此等方法存在有於高溫條件下觸媒劣化頗大等問題。近年來,亦提案有以即使在高溫條件下觸媒劣化仍較少的異聚酸(專利文獻3)作為觸媒的四氫呋喃製法。 For example, a method using a solid catalyst such as a cerium oxide alumina catalyst (Patent Document 1) or a cation exchange resin (Patent Document 2) is known, but these methods have a deterioration in the catalyst under high temperature conditions. Great question. In recent years, a tetrahydrofuran method in which a heteropoly acid (Patent Document 3) which is less deteriorated by a catalyst even under high temperature conditions is used as a catalyst has been proposed.
在使用此等觸媒藉由1,4BG之脫水環化反應製造THF時,係使用利用了固定床反應器之液相反應器、或將生成物經由氣相部由反應器予以餾除的反應蒸餾形式等。 When THF is produced by the dehydration cyclization reaction of 1,4 BG using these catalysts, a liquid phase reactor using a fixed bed reactor or a reaction in which a product is distilled off from a reactor via a gas phase portion is used. Distillation form, etc.
此等製程中,雖依使反應中副產生之高沸點成分蓄積於反應器液相部的狀態進行運轉,但副產生固形物之生成亦同時進行。 In these processes, the high-boiling component generated in the reaction is accumulated in the liquid phase of the reactor, and the generation of the secondary solid matter is simultaneously performed.
具體而言,專利文獻3中記載了聚合物等之副產生固形物的析出將使運轉變得困難,並記載有關屬於1,4BG合成時之反應副產生物、於原料1,4BG中以雜質形式含有的2-(4-羥基丁氧基)-四氫呋喃(以下有時簡稱為「BGTF」)由來之固形物的生成。為了避免此種THF製造時之副產生固形物的析出,專利文獻3中記載有規定觸媒之前處理法、或將含氮量保持為較低等。 Specifically, in Patent Document 3, it is described that the precipitation of a solid matter such as a polymer causes difficulty in operation, and the reaction by-products belonging to the synthesis of 1,4BG and impurities in the raw material 1,4BG are described. The formation of a solid matter derived from 2-(4-hydroxybutoxy)-tetrahydrofuran (hereinafter sometimes abbreviated as "BGTF"). In order to avoid precipitation of solid matter in the production of such THF, Patent Document 3 describes a method of pre-catalyst treatment or a low nitrogen content.
(專利文獻1)日本專利特公昭48-1075號公報 (Patent Document 1) Japanese Patent Publication No. Sho 48-1075
(專利文獻2)日本專利特開平7-118253號公報 (Patent Document 2) Japanese Patent Laid-Open No. Hei 7-118253
(專利文獻3)日本專利特表2006-503050號公報 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2006-503050
然而,在由原料1,4BG連續地製造THF時,即使使用將可成為原料1,4BG中之副產生固形物之要因的化合物、例如BGTF之濃度減低至某程度之物,在反應器內蓄積反應液而進行運轉的製程中,仍有固形物之副產生物析出而妨礙連續之THF製造、使生產性降低的問題。 However, when THF is continuously produced from the raw materials 1, 4BG, even if a concentration of a compound which can be a solid substance in the raw material 1, 4BG, for example, a concentration of BGTF is reduced to a certain extent, it is accumulated in the reactor. In the process of operating the reaction liquid, there is still a problem that the by-product of the solid matter is precipitated to hinder continuous THF production and to reduce productivity.
本發明係有鑑於上述課題而形成者,目的在於提供一種在酸觸媒存在下藉由以1,4-丁二醇作為原料之脫水環化反應製造四氫呋喃時,防止副產生固形物之析出,可得到安定之高生產性而工業上有利的四氫呋喃之製造方法。 The present invention has been made in view of the above problems, and it is an object of the invention to provide a method for preventing the precipitation of a solid matter by a dehydration cyclization reaction using 1,4-butanediol as a raw material in the presence of an acid catalyst. A process for producing a stable and highly industrially advantageous tetrahydrofuran can be obtained.
本發明者等人為了解決上述課題而經深入研討,結果發現,藉由在供於四氫呋喃製造之1,4BG中,使特定量之胺及醯胺中之至少一者存在,則於副產生之水的存在下,可於反應器內使2-(4-羥基丁氧基)-四氫呋喃量減低,有效抑制副產生固形物的生成,藉此,即使使用某程度地含有屬於副產生固形物要因之2-(4-羥基丁氧基)-四氫呋喃的原料1,4-丁二醇,仍可防止反應器內之副產生固形物析出,安定維持高生產性。 The inventors of the present invention have intensively studied in order to solve the above problems, and as a result, it has been found that at least one of a certain amount of amine and guanamine is present in 1,4-BB produced in tetrahydrofuran. In the presence of water, the amount of 2-(4-hydroxybutoxy)-tetrahydrofuran can be reduced in the reactor, and the formation of solids in the by-products can be effectively suppressed, thereby, even if the use contains a certain amount of solids belonging to the secondary generation. The raw material of 2-(4-hydroxybutoxy)-tetrahydrofuran, 1,4-butanediol, can prevent the precipitation of solids in the reactor, and maintain high productivity.
本發明即根據此種見解而達成者,以下述[1]~[7]為要旨。 The present invention has been achieved based on such findings, and the following [1] to [7] are the gist of the following.
[1]一種四氫呋喃之製造方法,係於反應器內,在pKa值為4以下之酸觸媒存在下,藉由進行1,4-丁二醇之脫水環化反應而製造四氫呋喃者,其中,含有供於反應之1,4-丁二醇的原料液係含有:2-(4-羥基丁氧基)-四氫呋喃0.01~0.35重量%;與依氮原子換算濃度計為1重量ppm以上、且1000重量ppm以下之胺及醯胺中之至少一者。 [1] A method for producing tetrahydrofuran, wherein a tetrahydrofuran is produced by performing a dehydration cyclization reaction of 1,4-butanediol in the presence of an acid catalyst having a pKa value of 4 or less, wherein The raw material liquid containing the 1,4-butanediol to be reacted contains: 2-(4-hydroxybutoxy)-tetrahydrofuran, 0.01 to 0.35 wt%; and the concentration in terms of nitrogen atom is 1 ppm by weight or more, and At least one of an amine and a guanamine of 1000 ppm by weight or less.
[2]一種四氫呋喃之製造方法,係於反應器內,在pKa值為4以下之酸觸媒存在下,藉由進行1,4-丁二醇之脫水環化反應而製造四氫呋喃者,其中,反應器內之反應液係含有依氮原子換算濃度計為1重量ppm以上、且10000重量ppm以下的胺及醯胺中之至少一者。 [2] A method for producing tetrahydrofuran, which is produced by a dehydrocyclization reaction of 1,4-butanediol in the presence of an acid catalyst having a pKa value of 4 or less in a reactor, wherein The reaction liquid in the reactor contains at least one of an amine and a guanamine in an amount of 1 ppm by weight or more and 10,000 ppm by weight or less in terms of a nitrogen atom-converted concentration.
[3]如[1]之四氫呋喃之製造方法,其中,上述反應器內之反應液係含有依氮原子換算濃度計為1重量ppm以上、且 10000重量ppm以下的胺及醯胺中之至少一者。 [3] The method for producing a tetrahydrofuran according to [1], wherein the reaction liquid in the reactor contains 1 ppm by weight or more in terms of a concentration in terms of a nitrogen atom, and At least one of an amine and a guanamine of 10,000 ppm by weight or less.
[4]如[1]至[3]中任一項之四氫呋喃之製造方法,其中,上述反應器內之反應液係含有水分0.1重量%以上、且10重量%以下。 [4] The method for producing tetrahydrofuran according to any one of [1] to [3] wherein the reaction liquid in the reactor contains 0.1% by weight or more and 10% by weight or less of water.
[5]如[1]至[4]中任一項之四氫呋喃之製造方法,其中,具有將存在於上述反應器內之氣相部的含有四氫呋喃及水之氣體抽出至反應器外的步驟。 [5] The method for producing tetrahydrofuran according to any one of [1] to [4] wherein the gas containing tetrahydrofuran and water present in the gas phase portion in the reactor is taken out of the reactor.
[6]如[1]至[5]中任一項之四氫呋喃之製造方法,其中,上述反應器內之反應液的溫度為80℃以上、且250℃以下的範圍。 [6] The method for producing tetrahydrofuran according to any one of [1] to [5] wherein the temperature of the reaction liquid in the reactor is in a range of 80 ° C or more and 250 ° C or less.
[7]如[1]至[6]中任一項之四氫呋喃之製造方法,其中,具有藉由將粗製1,4-丁二醇於胺及醯胺中之至少一者存在下加熱至80℃以上,而將2-(4-羥基丁氧基)-四氫呋喃含量減低後,供給至上述反應器的步驟。 [7] The method for producing tetrahydrofuran according to any one of [1] to [6] wherein the crude 1,4-butanediol is heated to 80 by the presence of at least one of an amine and a guanamine. After the content of 2-(4-hydroxybutoxy)-tetrahydrofuran is lowered at °C or higher, it is supplied to the above reactor.
根據本發明,於以1,4-丁二醇為原料並藉由酸觸媒存在下之脫水環化反應製造四氫呋喃的方法中,可於反應器內減低2-(4-羥基丁氧基)-四氫呋喃量,故可防止副產生固形物之析出,而可依安定運轉、高生產性製造四氫呋喃。 According to the present invention, in the process for producing tetrahydrofuran by using 1,4-butanediol as a raw material and by dehydration cyclization in the presence of an acid catalyst, 2-(4-hydroxybutoxy) can be reduced in the reactor. - The amount of tetrahydrofuran prevents the precipitation of solids by the secondary, and the tetrahydrofuran can be produced in a stable operation and high productivity.
本發明中,由於可在脫水環化反應中減低2-(4-羥基丁氧基)-四氫呋喃量,故即使使用某程度地含有屬於副產生固形物析出要因之2-(4-羥基丁氧基)-四氫呋喃的原料1,4-丁二 醇,仍可避免副產生固形物析出問題,因此可減低原料1,4-丁二醇之精製所需的成本或時間。 In the present invention, since the amount of 2-(4-hydroxybutoxy)-tetrahydrofuran can be reduced in the dehydration cyclization reaction, even if a certain amount of 2-(4-hydroxybutoxy) which is a cause of precipitation of solids is produced is used to some extent. Base)-tetrahydrofuran raw material 1,4-butane The alcohol can still avoid the problem of secondary solid precipitation, thereby reducing the cost or time required for the purification of the raw material 1,4-butanediol.
另外,由於在反應步驟中防止副產生固形物析出,故在設有精製步驟作為反應步驟的後步驟的情況,亦可獲得在該精製步驟之精製設備(例如蒸餾塔之塔底等)中防止固形物固黏等之髒污的效果,而可達到四氫呋喃之製造設備整體的安定運轉。 Further, since the solid matter is prevented from being precipitated in the reaction step, in the case where the purification step is provided as the subsequent step of the reaction step, it is also possible to prevent the purification equipment (for example, the bottom of the distillation column, etc.) in the purification step from being obtained. The solid effect of the solid matter is fixed, and the stability of the manufacturing equipment of the tetrahydrofuran can be achieved.
本發明之四氫呋喃的製造方法,係於反應器內,在pKa值為4以下之酸觸媒存在下,藉由進行1,4-丁二醇之脫水環化反應而製造四氫呋喃者,其特徵為,該脫水環化反應開始時之該反應器內之含有1,4-丁二醇的原料液中的2-(4-羥基丁氧基)-四氫呋喃含量為0.01~0.35重量%,胺及醯胺中之至少一者的含量係依氮原子換算濃度計為1重量ppm以上、且1000重量ppm以下,或於反應器內之反應液中存在依氮原子換算濃度計為1重量ppm以上、且10000重量ppm以下的胺及醯胺中之至少一者。 The method for producing tetrahydrofuran according to the present invention is a method for producing tetrahydrofuran by performing a dehydration cyclization reaction of 1,4-butanediol in the presence of an acid catalyst having a pKa value of 4 or less in a reactor. The content of 2-(4-hydroxybutoxy)-tetrahydrofuran in the raw material liquid containing 1,4-butanediol in the reactor at the start of the dehydration cyclization reaction is 0.01 to 0.35% by weight, amine and hydrazine The content of at least one of the amines is 1 ppm by weight or more and 1000 ppm by weight or less in terms of a nitrogen atom-converted concentration, or 1 ppm by weight or more in terms of a nitrogen atom-converted concentration in the reaction liquid in the reactor, and At least one of an amine and a guanamine of 10,000 ppm by weight or less.
本發明所使用之1,4BG可藉公知方法獲得。 The 1,4BG used in the present invention can be obtained by a known method.
例如,可在將藉由丁二烯之二乙醯氧基化所獲得的1,4-二乙醯氧基-2-丁烯進行氫化後,予以水解而製造1,4BG。或者亦可使用藉由順丁醯二酸酐之氫化所得的1,4BG、藉雷 佩(Reppe)法由乙炔所衍生的1,4BG、經由丙烯之氧化而獲得之1,4BG、藉發酵法所得之1,4BG等。 For example, 1,4-diethoxycarbonyl-2-butene obtained by methoxylation of butadiene may be hydrogenated and then hydrolyzed to produce 1,4BG. Alternatively, 1,4BG obtained by hydrogenation of cis-succinic anhydride may be used. The Reppe method is 1,4BG derived from acetylene, 1,4BG obtained by oxidation of propylene, 1,4BG obtained by fermentation, and the like.
由此種方法所製造之1,4BG通常係依雜質形式含有屬於反應副產物的BGTF、或1-乙醯氧基-4-羥基丁烷、1,4-丁二醇之脫水二聚物、脫水三聚物、γ-丁內酯等,尤其是BGTF含量通常為0.01~0.5重量%。 The 1,4BG produced by such a method usually contains BGTF which is a by-product of the reaction, or a dehydrated dimer of 1-ethoxycarbonyl-4-hydroxybutane and 1,4-butanediol, depending on the impurity. The dehydrated trimer, γ-butyrolactone and the like, in particular, the BGTF content is usually from 0.01 to 0.5% by weight.
本發明中,只要供給至用於藉脫水環化反應而製造THF之反應器中的原料1,4BG係原料液中之BGTF濃度為後述範圍內即可,並無特別限制,供給至反應器之含有1,4BG的原料液中之BGTF含量為0.01~0.35重量%、較佳0.10重量%~0.33重量%、更佳0.15重量%~0.30重量%。 In the present invention, the BGTF concentration in the raw material 1 and 4BG-based raw material liquid to be used in the reactor for producing THF by the dehydration cyclization reaction is not particularly limited, and is supplied to the reactor. The BGTF content in the raw material liquid containing 1,4 BG is 0.01 to 0.35 wt%, preferably 0.10 wt% to 0.33 wt%, more preferably 0.15 wt% to 0.30 wt%.
因此,本發明中,視需要較佳係在實施了用於將依上述公知方法所製造之粗製1,4BG中之BGTF濃度減低的處理後,再供給至反應器。 Therefore, in the present invention, it is preferred to carry out a treatment for reducing the concentration of BGTF in the crude 1,4BG produced by the above-described known method, and then supply it to the reactor.
作為用於減低該粗製1,4BG中之BGTF濃度的處理並無特別限制,可採用蒸餾等之通常的分離操作,但較佳為於胺與水之存在下將粗製1,4BG加熱至80℃以上的方法。亦即,若於胺與水之存在下加熱粗製1,4BG,則BGTF轉換成2-羥基四氫呋喃或屬於其開環生成物的4-羥基丁醛或其衍生物。其中,2-羥基四氫呋喃不致妨礙脫水環化反應或引起副產生固形物之生成,而且於脫水環化反應後,可藉由蒸餾等輕易地與1,4BG或THF分離。另外,2-羥基四氫呋喃可藉 由氫化而轉換成1,4-丁二醇。 The treatment for reducing the concentration of the BGTF in the crude 1,4BG is not particularly limited, and a usual separation operation such as distillation may be employed, but it is preferred to heat the crude 1,4 BG to 80 ° C in the presence of an amine and water. The above method. That is, if the crude 1,4BG is heated in the presence of an amine and water, the BGTF is converted into 2-hydroxytetrahydrofuran or 4-hydroxybutanal or a derivative thereof which is a ring-opening product thereof. Among them, 2-hydroxytetrahydrofuran does not interfere with the dehydration cyclization reaction or causes the formation of a by-produced solid matter, and can be easily separated from 1,4BG or THF by distillation or the like after the dehydration cyclization reaction. In addition, 2-hydroxytetrahydrofuran can be borrowed It is converted to 1,4-butanediol by hydrogenation.
於該加熱處理中,作為於粗製1,4BG中使胺及醯胺中之至少一者存在的方法,並無特別限定,較佳有如:將粗製1,4BG與從下式(1)所示之胺系化合物及其分解物、或下式(2)所示之醯胺及其分解物所選擇之1種或2種以上混合的方法;或使粗製1,4BG與具有多胺骨架之陰離子交換樹脂接觸,使陰離子交換樹脂所含之胺成分溶出至粗製1,4BG的方法等。 In the heat treatment, the method of allowing at least one of the amine and the decylamine to be present in the crude 1,4BG is not particularly limited, and it is preferred to use the crude 1,4BG as shown in the following formula (1). a method of mixing one or more selected from the amine compound and its decomposition product, or the guanamine represented by the following formula (2) and a decomposition product thereof; or the crude 1,4BG and an anion having a polyamine skeleton The method of contacting the exchange resin to elute the amine component contained in the anion exchange resin to the crude 1,4BG.
尚且,式(1)中,R1~R3分別獨立表示氫原子、烷基、烯基、芳基、烷氧基、羥基、胺基、烷硫基或芳硫基,此等基亦可進一步具有取代基,於該取代基中亦可含有雜原子。又,R1~R3可為相同或相異。 Further, in the formula (1), R 1 to R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxyl group, an amine group, an alkylthio group or an arylthio group, and these groups may also be used. Further, it has a substituent, and a hetero atom may also be contained in the substituent. Also, R 1 to R 3 may be the same or different.
另外,式(2)所示之羧酸醯胺,可使用1級醯胺、2級醯胺、3級醯胺,N取代之取代基數為0~2之範圍,可使用N-烷基 取代醯胺、N-烯基取代醯胺、N-芳基取代醯胺等,亦即可使用取代基Ra、Rb之一者或雙方為烷基、烯基及芳基之任一者的羧酸醯胺等。另外,該取代基Ra、Rb中亦可含有雜原子,取代基Ra、Rb可為相同或相異。另一方面,作為羰基側之取代基Rc,可舉例如氫原子、烷基、烯基、芳基等。 Further, the carboxylic acid oxime represented by the formula (2) may be a guanamine, a guanamine or a guanamine, and the number of substituents substituted by N may be in the range of 0 to 2, and an N-alkyl group may be used. The indoleamine, the N-alkenyl-substituted decylamine, the N-aryl-substituted decylamine, or the like may be any one of the substituents R a and R b or both of the alkyl group, the alkenyl group and the aryl group. Carboxylic acid amide and the like. Further, the substituents R a and R b may further contain a hetero atom, and the substituents R a and R b may be the same or different. On the other hand, examples of the substituent R c on the carbonyl group include a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group.
另外,上述取代基Ra~Rc亦可分別彼此連結形成環。由可抑制副反應或分解等的觀點而言,作為羰基側之取代基Rc較佳為烷基。 Further, the substituents R a to R c may be bonded to each other to form a ring. From the viewpoint of suppressing side reactions, decomposition, and the like, the substituent R c on the carbonyl side is preferably an alkyl group.
供於加熱處理的粗製1,4BG中之胺及醯胺量若過少,則無法充分得到BGTF濃度減低效果,若過多,則成為其後脫水環化反應之阻礙要因,故較佳係依氮原子換算濃度(以下有時簡稱為「氮濃度」)計為1~10000重量ppm、特佳1~1000重量ppm。 If the amount of the amine and the guanamine in the crude 1,4BG supplied to the heat treatment is too small, the effect of reducing the concentration of BGTF cannot be sufficiently obtained. If the amount is too large, the effect of the dehydration cyclization reaction is hindered, so that the nitrogen atom is preferred. The converted concentration (hereinafter sometimes abbreviated as "nitrogen concentration") is 1 to 10000 ppm by weight, particularly preferably 1 to 1000 ppm by weight.
另外,若加熱處理時之加熱溫度過低,則無法充分獲得BGTF濃度減低效果,若過高,則因加熱成本增加及副反應增加而使雜質增加,故其加熱溫度通常為80℃以上、較佳100~250℃、更佳120~200℃。加熱時間係視加熱溫度而異,可任意設定,通常為1分鐘以上、且100小時以下,更佳為5分鐘以上、且10小時以下。 Further, if the heating temperature during the heat treatment is too low, the BGTF concentration reduction effect cannot be sufficiently obtained. If the heating temperature is too high, the increase in the heating cost and the increase in the side reaction increase the impurities. Therefore, the heating temperature is usually 80 ° C or higher. Good 100~250°C, better 120~200°C. The heating time varies depending on the heating temperature, and can be arbitrarily set, and is usually 1 minute or longer and 100 hours or shorter, more preferably 5 minutes or longer and 10 hours or shorter.
此加熱處理之方法並無特別限定,可藉由蒸餾塔或萃取槽、配管或熱交換器等進行加熱。 The heat treatment method is not particularly limited, and heating can be carried out by a distillation column, an extraction tank, a pipe, a heat exchanger or the like.
尚且,供於此加熱處理之粗製1,4BG,較佳係BGTF含量 為0.04~0.5重量%、水分濃度為1.0~25重量%。 Moreover, the crude 1,4BG, preferably BGTF content, for this heat treatment It is 0.04 to 0.5% by weight and the water concentration is 1.0 to 25% by weight.
供於加熱處理之粗製1,4BG中之BGTF含量若過高,則用於減低BGTF濃度之處理的負荷增大而處理成本變高。在BGTF含量夠低的情況,則不需要由此加熱處理所進行的BGTF濃度減低處理。供於加熱處理之粗製1,4BG的BGTF含量,更佳係0.05~0.45重量%、再更佳0.06~0.4重量%。 If the BGTF content in the crude 1,4BG for heat treatment is too high, the load for the treatment for reducing the BGTF concentration is increased and the treatment cost is increased. In the case where the BGTF content is sufficiently low, the BGTF concentration reduction treatment performed by the heat treatment is not required. The BGTF content of the crude 1,4BG for heat treatment is more preferably 0.05 to 0.45 wt%, still more preferably 0.06 to 0.4 wt%.
另外,若供於加熱處理之粗製1,4BG的水分濃度過高,則加熱成本變得過大,若過低,則無法充分獲得在胺存在下使BGTF轉換而減低BGTF濃度的效果。供於加熱處理之粗製1,4BG的水分濃度更佳為2~20重量%、再更佳5~16重量%。 Further, when the water concentration of the crude 1,4BG supplied to the heat treatment is too high, the heating cost becomes too large, and if it is too low, the effect of lowering the BGTF concentration in the presence of an amine cannot be sufficiently obtained. The water concentration of the crude 1,4BG for heat treatment is more preferably 2 to 20% by weight, still more preferably 5 to 16% by weight.
因此,在供於加熱處理之粗製1,4BG的BGTF含量或水分濃度脫離上述適合範圍時,最好進行氫化、蒸餾等之成分調整。 Therefore, when the BGTF content or the water concentration of the crude 1,4BG supplied to the heat treatment is out of the above-mentioned suitable range, it is preferable to adjust the components such as hydrogenation or distillation.
另外,供於加熱處理之粗製1,4BG較佳係pH7以上。亦即,藉由依含有水分的狀態將含既定量胺之pH7以上粗製1,4BG進行加熱,則可更有效地減低BGTF。 Further, the crude 1,4BG to be subjected to heat treatment is preferably pH 7 or higher. That is, by heating the crude 1,4BG having a pH of 7 or more containing a predetermined amount of amine in a state containing water, the BGTF can be more effectively reduced.
在pH未滿7之粗製1,4BG中,藉由加熱處理,於導入至反應器前將生成THF,引起例如蒸餾塔之差壓上昇、或造成1,4BG損失。另一方面,若為pH7以上之粗製1,4BG,則可抑制加熱處理時之THF生成。pH7以上之粗製1,4BG,係在藉上述公知技術所製造之粗製1,4BG之pH為7以上時 可予以直接使用。又,即使在該粗製1,4BG之pH未滿7的情況,亦可藉由上述胺添加或與具有胺骨架之陰離子交換樹脂接觸等而使pH成為7以上。 In the crude 1,4BG having a pH of less than 7, by heat treatment, THF is formed before introduction into the reactor, causing, for example, a rise in the differential pressure of the distillation column or a loss of 1,4 BG. On the other hand, in the case of the crude 1,4BG having a pH of 7 or more, the formation of THF during the heat treatment can be suppressed. The crude 1,4BG having a pH of 7 or higher is when the pH of the crude 1,4BG produced by the above-mentioned known technique is 7 or more. Can be used directly. Further, even when the pH of the crude 1,4BG is less than 7, the pH may be 7 or more by addition of the above amine or contact with an anion exchange resin having an amine skeleton.
供於加熱處理之粗製1,4BG的pH只要為7以上即可,過高時則成為THF製造時之觸媒劣化要因,故pH較佳為12以下、例如7.0~12.0。 The pH of the crude 1,4BG to be subjected to the heat treatment may be 7 or more. When the pH is too high, the catalyst is deteriorated during the production of THF. Therefore, the pH is preferably 12 or less, for example, 7.0 to 12.0.
本發明中,在此種加熱所進行之BGTF濃度的減低處理時,較佳係獲得含有0.01~0.35重量%BGTF、並含有依氮濃度計為1~1000重量ppm的胺及醯胺中之至少一者的1,4BG含有液作為後述的原料液。 In the present invention, in the treatment for reducing the concentration of BGTF by heating, it is preferred to obtain at least 0.01 to 0.35% by weight of BGTF and at least 1 to 1000 ppm by weight of amine and guanamine in terms of nitrogen concentration. One of the 1,4BG-containing liquids is used as a raw material liquid to be described later.
尚且,在上述加熱處理後,亦可藉由蒸餾精製等將1,4BG濃縮。 Further, after the above heat treatment, 1,4BG may be concentrated by distillation or the like.
本發明所使用之酸觸媒只要為pKa(酸解離常數)值為4以下且可使1,4BG進行脫水環化反應成THF者即可,可使用任意之酸觸媒,較佳係磺酸、陽離子交換樹脂、異聚酸、磷酸等,更佳係不含金屬之有機酸或磷酸,特佳係有機磺酸。具體可舉例如對甲苯磺酸、苯磺酸、鄰甲苯磺酸、間甲苯磺酸等之芳香族磺酸衍生物,丁烷磺酸、己烷磺酸、辛烷磺酸、壬烷磺酸等之鏈狀之脂肪族磺酸衍生物等,此等亦可於碳骨架內具有磺酸以外之官能基。此等酸觸媒可單獨使用1種,亦可混合使用2種以上。作為酸觸媒,特佳係使用對甲苯磺 酸。 The acid catalyst used in the present invention may have a pKa (acid dissociation constant) value of 4 or less and may be subjected to a dehydration cyclization reaction to THF, and any acid catalyst may be used, preferably a sulfonic acid. A cation exchange resin, a heteropolymer acid, a phosphoric acid or the like is more preferably a metal-free organic acid or phosphoric acid, and particularly preferably an organic sulfonic acid. Specific examples thereof include aromatic sulfonic acid derivatives such as p-toluenesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, and m-toluenesulfonic acid, butanesulfonic acid, hexanesulfonic acid, octanesulfonic acid, and decanesulfonic acid. A chain-like aliphatic sulfonic acid derivative or the like may have a functional group other than a sulfonic acid in the carbon skeleton. These acid catalysts may be used alone or in combination of two or more. As an acid catalyst, the best use of p-toluene acid.
尚且,酸觸媒中,有機磺酸等通常可溶解於1,4BG。 Further, in the acid catalyst, an organic sulfonic acid or the like is usually soluble in 1,4 BG.
酸觸媒之使用量係於反應器內之反應液中濃度計,通常為0.01~20重量%,較佳0.05~10重量%,特佳0.2~5重量%。 The amount of the acid catalyst used is usually from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.2 to 5% by weight, based on the concentration of the reaction liquid in the reactor.
尚且,酸觸媒可於反應開始時或開始前一次地添加,但為了彌補因經時所造成的觸媒劣化,較佳係逐次地投入,可更有效地使反應安定持續進行。此時,相對於朝反應器之含1,4BG原料液的經時投入量,酸觸媒添加量係以酸觸媒相對於原料液所含之1,4BG之經時投入量的濃度計,較佳為0.0001~0.1重量%,特佳0.0005~0.005重量%的濃度範圍。因此,例如可依成為此種濃度範圍之方式將添加了酸觸媒的原料液導入至反應器中。 Further, the acid catalyst may be added once at the start of the reaction or before the start of the reaction. However, in order to compensate for the deterioration of the catalyst due to the passage of time, it is preferred to carry out the reaction successively, and the reaction stability can be more effectively continued. At this time, the amount of the acid catalyst added is based on the concentration of the acid catalyst to the time-dependent input amount of 1,4 BG contained in the raw material liquid, with respect to the time-dependent input amount of the 1,4 BG raw material liquid contained in the reactor. It is preferably from 0.0001 to 0.1% by weight, particularly preferably from 0.0005 to 0.005% by weight. Therefore, for example, a raw material liquid to which an acid catalyst is added can be introduced into the reactor in such a concentration range.
本發明中,特徵在於將供於反應之含1,4BG原料液的BGTF含量設為0.01~0.35重量%,並使其含有依氮濃度計為1~1000重量ppm的胺及醯胺中之至少一者。又,本發明中,所謂原料液係指供於脫水環化反應之反應器的成分中酸觸媒以外的成分。 In the present invention, the BGTF content of the 1,4BG-containing raw material liquid to be reacted is set to 0.01 to 0.35% by weight, and at least 1 to 1000 ppm by weight of the amine and the guanamine are contained in terms of nitrogen concentration. One. In the present invention, the raw material liquid means a component other than the acid catalyst in the component of the reactor for the dehydration cyclization reaction.
若此原料液中之BGTF含量超過0.35重量%,則有於脫水環化反應中副產生固形物之生成量增大的傾向,損及THF之安定生產。另一方面,雖然原料液中之BGTF含量越少、越可減低副產生固形物之生成量,但為了使BGTF含量過度 減少,則用於粗製1,4BG之精製的負荷變得過大,並不符合本發明之即使不使用過度去除BGTF之原料1,4BG仍可避免脫水環化反應中之副產生固形物析出問題的目的。原料液之BGTF含量較佳為0.01~0.33重量%、更佳0.02~0.30重量%、特佳0.03~0.16重量%。 When the BGTF content in the raw material liquid exceeds 0.35% by weight, the amount of formation of solids in the dehydration cyclization reaction tends to increase, which impairs the stable production of THF. On the other hand, although the BGTF content in the raw material liquid is smaller, the amount of solid matter generated by the secondary material can be reduced, but the BGTF content is excessive. If the reduction is small, the load for the purification of the crude 1,4BG becomes too large, and the raw material which does not use the excessive removal of BGTF is not in accordance with the present invention, and the 4BG can avoid the problem of the solid matter precipitation in the dehydration and cyclization reaction. purpose. The BGTF content of the raw material liquid is preferably from 0.01 to 0.33% by weight, more preferably from 0.02 to 0.30% by weight, particularly preferably from 0.03 to 0.16% by weight.
另外,若原料液中之胺及醯胺中之至少一者的量過少,則無法充分獲得於脫水環化反應中減低來自1,4BG的BGTF而防止副產生固形物生成的本發明效果。雖然胺及醯胺中之至少一者之量越多、上述效果越大,但若胺及醯胺中之至少一者之量過多,則除了胺及醯胺中之至少一者的添加成本增大以外,胺及醯胺中之至少一者亦成為使THF生產性降低的原因。 Further, when the amount of at least one of the amine and the guanamine in the raw material liquid is too small, the effect of the present invention in which the BGTF derived from 1,4BG is reduced in the dehydration cyclization reaction to prevent the formation of solids in the secondary state cannot be sufficiently obtained. Although the amount of at least one of the amine and the guanamine is greater, the effect is greater, but if the amount of at least one of the amine and the guanamine is too large, the addition cost of at least one of the amine and the guanamine increases. In addition to at least one of the amine and the guanamine, the THF productivity is also lowered.
因此,原料液中之胺及醯胺中之至少一者,係以氮濃度計設為1~1000重量ppm、較佳2~200重量ppm、更佳20~80重量ppm。 Therefore, at least one of the amine and the guanamine in the raw material liquid is 1 to 1000 ppm by weight, preferably 2 to 200 ppm by weight, more preferably 20 to 80 ppm by weight, based on the nitrogen concentration.
尚且,在本發明之原料液中僅含有胺、而不含醯胺的情況,原料液中之胺量係以氮濃度計為1~1000重量ppm、較佳2~200重量ppm、更佳20~80重量ppm。另外,在本發明之原料液中僅含有醯胺、不含胺的情況,原料液中之胺量係以氮濃度計為1~1000重量ppm、較佳2~200重量ppm、更佳5~60重量ppm。 Further, in the case where the raw material liquid of the present invention contains only an amine and does not contain guanamine, the amount of the amine in the raw material liquid is 1 to 1000 ppm by weight, preferably 2 to 200 ppm by weight, more preferably 20% by weight. ~80 ppm by weight. Further, in the case where the raw material liquid of the present invention contains only guanamine and no amine, the amount of the amine in the raw material liquid is 1 to 1000 ppm by weight, preferably 2 to 200 ppm by weight, more preferably 5 to 5 parts by weight. 60 ppm by weight.
另外,在原料液中均含有胺與醯胺的情況,原料液中之胺 與醯胺的合計量係以氮濃度計為1~1000重量ppm、較佳2~200重量ppm、更佳20~80重量ppm。 In addition, in the case where the raw material liquid contains amine and decylamine, the amine in the raw material liquid The total amount to be combined with the guanamine is 1 to 1000 ppm by weight, preferably 2 to 200 ppm by weight, more preferably 20 to 80 ppm by weight, based on the nitrogen concentration.
胺及醯胺中之至少一者的濃度範圍若超過下限,則更加表現本發明效果,若小於上限,則有後步驟之處理減輕的傾向。 When the concentration range of at least one of the amine and the guanamine exceeds the lower limit, the effect of the present invention is further exhibited. If the concentration is less than the upper limit, the treatment of the subsequent step tends to be alleviated.
作為於此原料液中使胺及醯胺中之至少一者存在的方法,較佳係於原料液中添加胺及醯胺中之至少一者的方法,或使原料液與具有胺骨架之陰離子交換樹脂接觸,而使陰離子交換樹脂所含之胺成分溶出至原料液中的方法等。來自此陰離子交換樹脂的溶出份為多胺,所謂多胺係指結合了2個以上1級胺基的直鏈脂肪族烴的總稱,本發明中,係指含有2個以上、較佳3~20個來自式(1)所示之含氮化合物中R1~R3任一個以上為烷基之化合物的構成單位的聚合物。 As a method of allowing at least one of an amine and a guanamine to be present in the raw material liquid, it is preferred to add at least one of an amine and a guanamine to the raw material liquid, or to make the raw material liquid and an anion having an amine skeleton A method in which the exchange resin is contacted to elute the amine component contained in the anion exchange resin into the raw material liquid. The eluted component derived from the anion exchange resin is a polyamine, and the polyamine refers to a general term of a linear aliphatic hydrocarbon in which two or more primary amino groups are bonded. In the present invention, it means two or more, preferably 3~. 20 polymers derived from a constituent unit of a compound in which one or more of R 1 to R 3 are an alkyl group in the nitrogen-containing compound represented by the formula (1).
亦可對添加了胺及醯胺中之至少一者後或與具有胺骨架之陰離子交換樹脂等接觸後的原料液進行蒸餾等之分離操作。 It is also possible to carry out a separation operation such as distillation after adding at least one of an amine and a guanamine or a contact with an anion exchange resin having an amine skeleton.
於此所使用之胺,可舉例如辛基胺、壬基胺、1-胺基癸烷、苯胺、苯乙胺等之1級胺,二戊基胺、二己基胺、二庚基胺、二環己基胺、N-甲基苯胺等之2級胺,三丁基胺、三戊基胺、N,N-二甲基苯胺等之3級胺,1,3-丙二胺、N,N-二甲基-1,6-己二胺等之二胺,N-丁基吡咯、N-丁基-2,3-二氫吡咯、N-丁基吡咯啶、2,3-二氫-1H-吲哚等之5員環胺,4-胺基甲基哌啶、4-二甲基胺基吡啶、1,2,3,4-四氫喹啉、4-胺基-5,6- 二氫-2-甲基嘧啶、2,3,5,6-四甲基吡、3,6-二甲基嗒等之6員環胺等;作為進一步含氧原子者,由沸點接近1,4BG之觀點而言,可舉例如4-胺基丁醇、2-胺基丁醇等之鏈狀胺基醇,2-乙基啉、N-甲氧基羰基啉、脯胺醇、3-羥基哌啶、4-羥基哌啶、四氫糠基胺、3-胺基四氫哌喃等之環狀胺。此等胺中,較佳係具有至少1個N-H鍵結的1級或2級胺、或含有具N-H鍵結之1級多胺類的陰離子交換樹脂的溶出份,作為較佳之胺,由促進BGTF分解的觀點而言,較佳可舉例如辛基胺、壬基胺、1-胺基癸烷、苯胺、苯乙胺等之1級胺,二戊基胺、二己基胺、二庚基胺、二環己基胺、N-甲基苯胺等之2級胺,1,3-丙二胺、N,N-二甲基-1,6-己二胺等之二胺,2,3-二氫-1H-吲哚等之5員環胺,4-胺基甲基哌啶、1,2,3,4-四氫喹啉等之6員環胺,含有來自由具有聚乙二胺骨架之陰離子交換樹脂溶出之乙烯胺的構成單位2~20個的聚合體等;作為進一步含氧原子者,由在大氣壓下之沸點溫度接近1,4BG的觀點而言,較佳為4-胺基丁醇、2-胺基丁醇等之鏈狀胺基醇,2-乙基啉、脯胺醇、3-羥基哌啶、4-羥基哌啶、四氫糠基胺、3-胺基四氫哌喃等之環狀胺。再者,由適合使用大氣壓下之沸點溫度為160~260℃之化合物的觀點而言,較佳可舉例如1-胺基癸烷、二己基胺、脯胺醇、3-羥基哌啶、4-羥基哌啶、4-胺基丁醇、四氫糠基胺等。 The amine to be used herein may, for example, be a first-grade amine such as octylamine, mercaptoamine, 1-aminodecane, aniline or phenethylamine, dipentylamine, dihexylamine or diheptylamine. a secondary amine such as dicyclohexylamine or N-methylaniline; a tertiary amine such as tributylamine, tripentylamine or N,N-dimethylaniline; 1,3-propanediamine, N, Diamines such as N-dimethyl-1,6-hexanediamine, N-butylpyrrole, N-butyl-2,3-dihydropyrrole, N-butylpyrrolidine, 2,3-dihydrogen a 5-membered cyclic amine of -1H-indole, 4-aminomethylpiperidine, 4-dimethylaminopyridine, 1,2,3,4-tetrahydroquinoline, 4-amino-5, 6-Dihydro-2-methylpyrimidine, 2,3,5,6-tetramethylpyridyl ,3,6-dimethylhydrazine 6-membered cyclic amine or the like; as a further oxygen-containing atom, a chain amino alcohol such as 4-aminobutanol or 2-aminobutanol may be mentioned from the viewpoint of a boiling point close to 1,4BG. 2-ethyl Porphyrin, N-methoxycarbonyl A cyclic amine such as a porphyrin, a guanamine, a 3-hydroxypiperidine, a 4-hydroxypiperidine, a tetrahydrofurfurylamine or a 3-aminotetrahydropyran. Among these amines, preferred are those having at least one NH-bonded first- or second-order amine or an anion exchange resin containing an NH-bonded first-grade polyamine, which is promoted as a preferred amine. From the viewpoint of decomposition of BGTF, preferred are amines such as octylamine, mercaptoamine, 1-aminodecane, aniline, and phenethylamine, dipentylamine, dihexylamine, and diheptyl. a second amine such as an amine, a dicyclohexylamine or an N-methylaniline; a diamine such as 1,3-propanediamine or N,N-dimethyl-1,6-hexanediamine, 2,3- a 5-membered cyclic amine such as dihydro-1H-indole, a 4-membered cyclic amine, 4-aminomethylpiperidine or 1,2,3,4-tetrahydroquinoline, containing a polyethylenediamine The constituent unit of the vinylamine eluted from the anion exchange resin of the skeleton is 2 to 20 polymers, etc., and the further oxygen-containing atom is preferably a 4-amine from the viewpoint that the boiling point temperature at atmospheric pressure is close to 1,4 BG. Chain-shaped amino alcohol such as butanol, 2-aminobutanol, etc., 2-ethyl A cyclic amine such as a porphyrin, a guanamine, a 3-hydroxypiperidine, a 4-hydroxypiperidine, a tetrahydrofurfurylamine or a 3-aminotetrahydropyran. Further, from the viewpoint of suitably using a compound having a boiling point temperature of 160 to 260 ° C at atmospheric pressure, for example, 1-aminodecane, dihexylamine, decylamine, 3-hydroxypiperidine, 4 is preferable. - hydroxy piperidine, 4-aminobutanol, tetrahydrofurfurylamine, and the like.
另外,作為本發明所使用之較佳醯胺,由大氣壓下之沸點 不過低於1,4BG、及化合物之安定性的觀點而言,可舉例如乙醯胺、N-甲基乙醯胺、N-乙基乙醯胺、N,N-二甲基乙醯胺等之鏈狀骨架的醯胺類,苯甲醯胺等之芳香族醯胺類,2-吡咯啶酮、N-甲基吡咯啶酮、N-乙基吡咯啶酮、N-乙烯基吡咯啶酮、2-哌啶酮、N-甲基哌啶酮等之環狀醯胺類;由與原料之1,4BG沸點接近的觀點而言,更佳可舉例如乙醯胺、N-甲基乙醯胺、2-吡咯啶酮、N-甲基吡咯啶酮。由與原料之1,4BG的沸點接近、安定性高的觀點而言,特佳為2-吡咯啶酮、N-甲基吡咯啶酮。 Further, as the preferred guanamine used in the present invention, the boiling point at atmospheric pressure However, from the viewpoint of lower than 1,4 BG and the stability of the compound, for example, acetamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide Alkaloids such as chain amines, aromatic amides such as benzamide, 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidine a cyclic guanamine such as a ketone, a 2-piperidone or an N-methylpiperidone; more preferably, for example, acetamide or N-methyl from the viewpoint of a boiling point of 1,4 BG of a raw material. Acetamide, 2-pyrrolidone, N-methylpyrrolidone. From the viewpoint of the boiling point of the raw material 1,4BG and the high stability, it is particularly preferably 2-pyrrolidone or N-methylpyrrolidone.
本發明所使用之原料液中,可僅含有上述胺之1種,亦可含有2種以上。本發明所使用之原料液中,可僅含有上述醯胺之1種,亦可含有2種以上。 The raw material liquid used in the present invention may contain only one type of the above amines, or may contain two or more types. The raw material liquid used in the present invention may contain only one type of the above-described guanamine, or may contain two or more types.
另外,本發明所使用之原料液中,可含有上述胺之1種或2種以上與醯胺之1種或2種以上。 In addition, one or two or more kinds of the above-mentioned amines and one or more kinds of the guanamines may be contained in the raw material liquid to be used in the present invention.
尚且,在於原料液中添加胺及醯胺中之至少一者的情況,可添加至導入於反應器前之原料液中,亦可添加至反應器內之原料液中,亦可為其兩者。 Further, in a case where at least one of an amine and a guanamine is added to the raw material liquid, it may be added to the raw material liquid introduced before the reactor, or may be added to the raw material liquid in the reactor, or both of them may be used. .
本發明中,原料液中之水分濃度並無特別限制。亦即,在胺及醯胺中之至少一者存在下的BGTF減低效果,雖亦藉由存在水分所達成,但本發明中,由於在1,4BG之脫水環化反應中生成水,故脫水環化反應開始時之原料液中可含有水或不含有水。 In the present invention, the concentration of water in the raw material liquid is not particularly limited. That is, the BGTF reducing effect in the presence of at least one of an amine and a guanamine is achieved by the presence of moisture, but in the present invention, dehydration occurs due to the formation of water in the dehydration cyclization reaction of 1,4 BG. The raw material liquid at the start of the cyclization reaction may or may not contain water.
然而,若於原料液中過度地含有大量水,則相對於THF之生產能力,反應器容量變得過大,進而亦阻礙脫水環化反應,故水分濃度較佳為25重量%以下。 However, if a large amount of water is excessively contained in the raw material liquid, the reactor capacity becomes too large with respect to the productivity of THF, and the dehydration cyclization reaction is also inhibited. Therefore, the water concentration is preferably 25% by weight or less.
另外,如上述,在由各種公知製造方法所製造之1,4BG中,除了BGTF之外,亦含有1-乙醯氧基-4-羥基丁烷、1,4-丁二醇之脫水二聚物、脫水三聚物、γ-丁內酯等之副產物。 Further, as described above, in 1,4BG produced by various known production methods, in addition to BGTF, dehydration dimerization of 1-ethoxycarbonyl-4-hydroxybutane and 1,4-butanediol is also contained. A by-product of a substance, a dehydrated trimer, γ-butyrolactone or the like.
關於此等BGTF以外之副產物的含量,並無特別限制,但此等BGTF以外之副產物最好為較少,原料液中之此等BGTF及水以外之副產物含量較佳為0.3重量%以下、特佳0.05重量%以下。 The content of the by-products other than the BGTF is not particularly limited, but it is preferable that the by-products other than the BGTF are less, and the content of the by-products other than the BGTF and water in the raw material liquid is preferably 0.3% by weight. The following is particularly preferably 0.05% by weight or less.
本發明中,只要供於反應之原料液中之BGTF含量與胺及醯胺中之至少一者含量為上述範圍即可,如上述,可將胺及醯胺中之至少一者添加至導入於反應器前之原料液中,亦可添加至反應器內的原料液中,或可為其兩者,但關於BGTF含量,係藉由上述加熱處理等而事先減低,較佳係將BGTF含量為0.01~0.35重量%、更佳0.01~0.33重量%、再更佳0.02~0.30重量%、特佳0.03~0.16重量%的原料液導入至反應器中。 In the present invention, the content of the BGTF in the raw material liquid to be reacted and the content of at least one of the amine and the guanamine may be within the above range, and as described above, at least one of an amine and a guanamine may be added to the introduction. The raw material liquid before the reactor may be added to the raw material liquid in the reactor, or both of them may be used. However, the BGTF content is previously reduced by the above heat treatment, etc., and the BGTF content is preferably 0.01 to 0.35 wt%, more preferably 0.01 to 0.33 wt%, still more preferably 0.02 to 0.30 wt%, and particularly preferably 0.03 to 0.16 wt% of the raw material liquid is introduced into the reactor.
尚且,在於上述胺及醯胺中之至少一者與進而水的存在下進行加熱處理的情況,由於加熱處理液中含有胺及醯胺中之至少一者,故藉由將加熱處理時所存在之胺及醯胺中之至少一者的量設為適合供於反應之原料液的量,則可以上述加熱 處理液直接作為原料液並導入至反應器中而開始脫水環化反應。 Further, in the case where at least one of the above amine and guanamine is subjected to heat treatment in the presence of water, since the heat treatment liquid contains at least one of an amine and a guanamine, it is present by heat treatment. The amount of at least one of the amine and the guanamine is set to an amount suitable for the raw material liquid to be reacted, and the above heating may be employed. The treatment liquid is directly used as a raw material liquid and introduced into the reactor to start a dehydration cyclization reaction.
然而,在加熱處理液中之胺及醯胺中之至少一者不足的情況,亦可另外添加胺及醯胺中之至少一者。 However, when at least one of the amine and the guanamine in the heat treatment liquid is insufficient, at least one of an amine and a guanamine may be additionally added.
本發明中,進行環化脫水反應的反應器並無特別限定,可使用填充了陽離子交換樹脂等固體觸媒的固定床反應器、使用了固體觸媒的懸浮床反應器、或使用了可溶解於原料之均勻系統酸觸媒的槽型或管型反應器。又,雖然將反應器內之液相部之含有THF及副產生水的溶液由反應器排出,並於蒸餾塔等之後步驟進行精製亦可得到THF,但亦可由反應器之氣相將含有生成之THF及副產生水的氣體的一部分或全量抽出。此時,由反應器抽出之氣體可藉由熱交換器進行凝縮而得到凝縮液。此熱交換器係使由反應器產生之餾出物凝縮液化的裝置,該凝縮液化係藉由使屬於冷卻液之外部流體與氣體進行熱交換而進行。 In the present invention, the reactor for carrying out the cyclization dehydration reaction is not particularly limited, and a fixed bed reactor filled with a solid catalyst such as a cation exchange resin, a suspended bed reactor using a solid catalyst, or a soluble one can be used. A tank or tubular reactor for the homogeneous system acid catalyst of the feedstock. Further, the THF and the by-product water-containing solution in the liquid phase in the reactor are discharged from the reactor, and after the distillation step or the like, the THF is obtained by the purification step, but the THF may be formed in the gas phase of the reactor. A part or the whole amount of the THF and the by-product water are extracted. At this time, the gas extracted from the reactor can be condensed by a heat exchanger to obtain a condensate. This heat exchanger is a device for condensing and liquefying a distillate generated by a reactor, which is carried out by exchanging heat between an external fluid belonging to a cooling liquid and a gas.
另外,亦可於反應器之氣相部設置填充塔或層板塔,使生成之THF及副產生水餾出,同時將未反應原料分離而保持於反應器液相。藉由將從蒸餾塔所生成之THF及副產生水與未反應原料分離,使未反應原料及二聚物等之高沸點成分循環至反應器,或經由氣相將生成之THF及副產生水由反應器內之氣相部以氣體形式排出,則可使高沸點副產物蓄積 於反應器內之液相部。高沸點副產物中,屬於1,4BG之脫水二聚物的二丁二醇等可轉換成THF,藉由將此等高沸點副產物之一部分或全量蓄積於反應器之液相,則可削減原料使用量而改善經濟性。基於此種理由,較佳係將存在於反應器內之氣相部的含有THF及水之氣體的一部分或全量抽出至反應器外。又,亦可將以氣體形式排出之THF及副產生水冷卻凝縮,將其一部分迴流而循環至反應器內。 Further, a packed column or a layered column may be provided in the gas phase portion of the reactor to distill off the produced THF and the by-produced water, and the unreacted raw material may be separated and held in the reactor liquid phase. By separating the THF and the by-produced water generated in the distillation column from the unreacted raw materials, the high-boiling components such as unreacted raw materials and dimers are recycled to the reactor, or the THF and the secondary produced water are generated via the gas phase. The gas phase in the reactor is discharged as a gas, so that high-boiling by-products can be accumulated. The liquid phase in the reactor. Among the high-boiling by-products, dibutylene glycol or the like belonging to the dehydrated dimer of 1,4BG can be converted into THF, and by partially or completely accumulating one or a whole amount of such high-boiling by-products in the liquid phase of the reactor, the reduction can be reduced. Improve the economy by using raw materials. For this reason, it is preferred to extract a part or the entire amount of the gas containing THF and water present in the gas phase portion in the reactor to the outside of the reactor. Further, the THF and the secondary produced water discharged as a gas may be cooled and condensed, and a part thereof may be refluxed and recycled to the reactor.
在使用此種反應形式,亦即將存在於反應器內之氣相部的含有THF及水之氣體的一部分或全量抽出至反應器外,使該氣體藉由熱交換器凝縮成為凝縮液,而獲得含有THF及副產生水之混合液的形式的情況,亦可在將上述氣體導入至熱交換器前的階段具有填充塔、層板塔等之蒸餾塔。此時,填充塔、層板塔等之段數可為任意,通常之理論段較佳為1段以上、且100段以下,特佳為3段以上、且20段以下。若為此以上的段數,則塔變得過大,為了設備建設而經濟性惡化。又,於該塔上部具有用於上述生成氣體之液化凝縮的熱交換器。 In the case of using such a reaction form, a part or the whole amount of the gas containing THF and water present in the gas phase portion in the reactor is taken out to the outside of the reactor, and the gas is condensed into a condensation liquid by a heat exchanger. In the case of a form containing a mixed liquid of THF and by-product water, a distillation column such as a packed column or a layered column may be provided at a stage before the introduction of the gas into the heat exchanger. In this case, the number of stages of the packed column, the layered column, and the like may be arbitrary, and the normal theoretical section is preferably one stage or more and 100 stages or less, and particularly preferably three stages or more and 20 or less stages. If the number of the above is the number of the above, the tower becomes too large, and the economy deteriorates for the construction of the equipment. Further, a heat exchanger for liquefying and condensing the generated gas is provided in the upper portion of the tower.
屬於反應器內之液相部之內溫的反應溫度,較佳為80~250℃、更佳100~200℃、特佳120~180℃的範圍。在較此低的溫度下則THF生產性顯著降低,在較此高的溫度下則因微量副產物增加或因使用酸觸媒而必須使用高價材料作為反應器材料,故不佳。 The reaction temperature of the internal temperature of the liquid phase portion in the reactor is preferably in the range of 80 to 250 ° C, more preferably 100 to 200 ° C, and particularly preferably 120 to 180 ° C. At a lower temperature, the THF productivity is remarkably lowered, and at such a high temperature, it is not preferable because an increase in a trace amount of by-products or a use of a high-priced material as a reactor material due to the use of an acid catalyst.
反應壓力可採用任意壓力,作為絕對壓為10~1000kPa,特佳為100~500kPa。 The reaction pressure may be any pressure, and the absolute pressure is 10 to 1000 kPa, and particularly preferably 100 to 500 kPa.
本發明中,反應器內之溶液中主要除了原料1,4BG及酸觸媒以外,尚含有於脫水環化反應所生成之THF或副產生之水等,但此等以外,亦可含有來自原料1,4BG中之雜質的高沸點化合物、或由THF與1,4BG所生成的副產物、1,4BG之醋酸酯等。 In the present invention, the solution in the reactor contains, in addition to the raw material 1, 4BG and the acid catalyst, THF or by-product water generated by the dehydration cyclization reaction, but may also contain the raw material. A high boiling point compound of 1,4BG, or a by-product formed from THF and 1,4BG, an acetate of 1,4BG, or the like.
如上述,可藉由將含有所生成之THF及副產生水的氣體由氣相部排出並藉熱交換器予以凝縮而得到凝縮液,將其一部分作為迴流而回到反應器內之氣相部。經凝縮之液的組成可依任意濃度含有THF、副產生水,但較佳係THF濃度為30~95重量%、特佳50~85重量%的範圍。又,本反應係計量性地生成副產生水。因此,該凝縮液中之水濃度通常為1~50重量%、較佳5~30重量%、特佳15~25重量%的範圍。 As described above, the gas containing the produced THF and the by-product water can be discharged from the gas phase portion and condensed by a heat exchanger to obtain a condensed liquid, and a part thereof can be returned to the gas phase portion in the reactor as reflux. . The composition of the condensed liquid may contain THF or by-produced water at any concentration, but is preferably in the range of 30 to 95% by weight, particularly preferably 50 to 85% by weight. Further, this reaction produces meterwise generation of by-product water. Therefore, the concentration of water in the condensate is usually in the range of 1 to 50% by weight, preferably 5 to 30% by weight, particularly preferably 15 to 25% by weight.
該凝縮液之一部分可作為迴流而回到反應器內之氣相部,此時之迴流比較佳為0.001以上、且30以下,更佳為0.01~10的範圍,特佳為0.1~5的範圍。又,在迴流比過高的情況,由於必要蒸發量增加,故用於加熱的熱源成本增大而經濟性惡化,在迴流比過少的情況,則無法得到固形物析出減低效果,且高沸點成分因分離惡化而混入至餾出凝縮液中。 A part of the condensate can be returned to the gas phase portion in the reactor as reflux, and the reflux at this time is preferably 0.001 or more and 30 or less, more preferably 0.01 to 10, and particularly preferably 0.1 to 5. . Further, when the reflux ratio is too high, since the amount of evaporation is required to increase, the cost of the heat source for heating is increased and the economy is deteriorated. When the reflux ratio is too small, the solid matter precipitation reducing effect cannot be obtained, and the high boiling point component is not obtained. It is mixed into the distillate condensate due to deterioration of separation.
被導入至熱交換器之含有THF及副產生水之生成氣體於 導入時的溫度,較佳為10~200℃、特佳60~100℃的範圍。 a gas containing THF and by-produced water introduced into the heat exchanger The temperature at the time of introduction is preferably in the range of 10 to 200 ° C and particularly preferably 60 to 100 ° C.
本發明中,亦可由一連串之THF製造製程內(不僅是反應器,亦包括反應器後段之精製系統),將其流體連續或斷續地排出至製程系統外。又,在排出該流體時,亦可暫時停止供給原料1,4BG而停止THF製造再予以排出。所排出之液可藉由焚燒等進行產物廢棄處理。又,所排出之液由於含有酸觸媒、或陽離子交換樹脂等之固體酸溶出份,故亦可於經中和處理後進行焚燒等產物廢棄處理。 In the present invention, a series of THF manufacturing processes (not only the reactor, but also the refining system in the latter stage of the reactor) can be used to continuously or intermittently discharge the fluid out of the process system. Further, when the fluid is discharged, the supply of the raw materials 1, 4BG may be temporarily stopped, and the production of the THF may be stopped and discharged. The discharged liquid can be disposed of by incineration or the like. Further, since the discharged liquid contains a solid acid-dissolved portion such as an acid catalyst or a cation exchange resin, it may be subjected to a product disposal treatment such as incineration after the neutralization treatment.
最好充分確保脫水環化反應中之反應器內之反應液的1,4BG濃度。具體而言,較佳係控制為30~99重量%、更佳40~90重量%、再更佳50~80重量%。若反應液之1,4BG濃度為上述上限以下,則可抑制且減低屬於高沸點成分之聚合物的組成急遽上升。若於反應器內聚合物過度蓄積,則發生製程內之固形物析出,因污垢所造成的堵塞將妨礙運轉。另一方面,若反應液之1,4BG濃度過低,則表示不需回收未反應原料或二聚物等之高沸份,其過度廢棄,而原料消費量變大。 It is preferable to sufficiently ensure the 1,4 BG concentration of the reaction liquid in the reactor in the dehydration cyclization reaction. Specifically, it is preferably controlled to be 30 to 99% by weight, more preferably 40 to 90% by weight, still more preferably 50 to 80% by weight. When the concentration of 1,4 BG of the reaction liquid is not more than the above upper limit, the composition of the polymer which is a high-boiling component can be suppressed and reduced. If the polymer is excessively accumulated in the reactor, solid matter is precipitated in the process, and clogging due to the dirt will hinder the operation. On the other hand, when the concentration of 1,4BG in the reaction liquid is too low, it means that it is not necessary to recover a high boiling point such as an unreacted raw material or a dimer, and it is excessively discarded, and the amount of raw material consumed becomes large.
本發明中,如上述般,為了於胺及醯胺中之至少一者與脫水環化反應之副產生水的存在下,減低來自原料1,4BG之BGTF而有效控制副產生固形物的生成,較佳係於脫水環化反應中,反應器內之反應液中的胺及醯胺中之至少一者的量依氮濃度計為1~10000重量ppm,又,此反應液中之水分濃 度較佳為0.1~10重量%。 In the present invention, as described above, in order to reduce the BGTF derived from the raw material 1,4BG in the presence of at least one of the amine and the guanamine and the by-product of the dehydration cyclization reaction, the generation of the solid matter is effectively controlled. Preferably, in the dehydration cyclization reaction, the amount of at least one of the amine and the guanamine in the reaction liquid in the reactor is from 1 to 10,000 ppm by weight based on the nitrogen concentration, and the water in the reaction solution is concentrated. The degree is preferably from 0.1 to 10% by weight.
若脫水環化反應中之反應器內之反應液的胺及醯胺中之至少一者的量依氮濃度計少於1重量ppm,則無法充分獲得BGTF減低效果、副產生固形物之生成防止效果,若大於10000重量ppm,則防礙THF之生產性。 When the amount of at least one of the amine and the guanamine of the reaction liquid in the reactor in the dehydration cyclization reaction is less than 1 ppm by weight based on the nitrogen concentration, the BGTF reduction effect and the formation of the by-produced solid matter cannot be sufficiently obtained. The effect, if it is more than 10,000 ppm by weight, hinders the productivity of THF.
同樣地,若脫水環化反應中之反應器內之反應液的水分濃度少於0.1重量%,則無法充分獲得BGTF減低效果、副產生固形物之生成防止效果,若大於10重量%,則妨礙脫水環化反應。更佳之水分濃度為1重量%~6重量%。 In the same manner, when the water concentration of the reaction liquid in the reactor in the dehydration cyclization reaction is less than 0.1% by weight, the BGTF reduction effect and the formation prevention effect of the by-produced solid matter cannot be sufficiently obtained, and if it is more than 10% by weight, the hindrance is hindered. Dehydration cyclization reaction. More preferably, the water concentration is from 1% by weight to 6% by weight.
本發明中,脫水環化反應中之反應器內之反應液的胺及醯胺中之至少一者的量係依氮濃度計為1~10000重量ppm、較佳1~4000重量ppm、更佳11~650重量ppm,水分濃度較佳為0.1~10重量%、更佳0.1~5重量%、再更佳0.1~3重量%。 In the present invention, the amount of at least one of the amine and the guanamine in the reaction liquid in the reactor in the dehydration cyclization reaction is from 1 to 10,000 ppm by weight, preferably from 1 to 4,000 ppm by weight, more preferably, based on the nitrogen concentration. 11 to 650 ppm by weight, the water concentration is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, still more preferably 0.1 to 3% by weight.
尚且,在脫水環化反應中之反應器內之反應液中僅含有胺、而不含醯胺的情況,反應液中之胺量係依氮濃度計為1~10000重量ppm、較佳8~800重量ppm、更佳11~650重量ppm。 Further, in the case where the reaction liquid in the reactor in the dehydration cyclization reaction contains only an amine and does not contain guanamine, the amount of the amine in the reaction liquid is from 1 to 10,000 ppm by weight, preferably from 8 to 5% by weight. 800 ppm by weight, more preferably 11 to 650 ppm by weight.
另外,在脫水環化反應中之反應器內之反應液中僅含有醯胺、而不含胺的情況,反應液中之醯胺量係依氮濃度計為1~10000重量ppm、較佳8~800重量ppm、更佳20~650重量ppm。 Further, in the case where the reaction liquid in the reactor in the dehydration cyclization reaction contains only decylamine and does not contain an amine, the amount of guanamine in the reaction liquid is 1 to 10000 ppm by weight, preferably 8 in terms of nitrogen concentration. ~800 ppm by weight, more preferably 20 to 650 ppm by weight.
另外,在脫水環化反應中之反應器內之反應液中含有胺與 醯胺的情況,反應液中之胺與醯胺的合計量係依氮濃度計為1~10000重量ppm、較佳8~800重量ppm、更佳11~650重量ppm。 In addition, the reaction liquid in the reactor in the dehydration cyclization reaction contains an amine and In the case of guanamine, the total amount of the amine and the guanamine in the reaction liquid is from 1 to 10,000 ppm by weight, preferably from 8 to 800 ppm by weight, more preferably from 11 to 650 ppm by weight, based on the nitrogen concentration.
通常,脫水環化反應開始時之原料液中之胺及醯胺中之至少一者的含量為1~1000重量ppm,雖不致小於脫水環化反應中之反應液之胺及醯胺中之至少一者之量的下限,但在因長時間運轉或原料液中之胺及醯胺中之至少一者之濃度增加,而胺及醯胺中之至少一者的量增加的情況,較佳係藉由排出反應液,將脫水環化反應中之反應液之胺及醯胺中之至少一者的量抑制為上述上限以下。 Usually, the content of at least one of the amine and the guanamine in the raw material liquid at the start of the dehydration cyclization reaction is 1 to 1000 ppm by weight, which is not less than at least the amine and the guanamine of the reaction liquid in the dehydration cyclization reaction. The lower limit of the amount of one, but in the case where the concentration of at least one of the amine and the guanamine in the raw material liquid is increased due to long-term operation, and the amount of at least one of the amine and the guanamine is increased, it is preferred to By discharging the reaction liquid, the amount of at least one of the amine and the guanamine of the reaction liquid in the dehydration cyclization reaction is suppressed to the above upper limit or lower.
另外,在水分濃度超出上述適當範圍時,較佳係藉由水分添加或水分餾出而進行濃度調整。 Further, when the water concentration exceeds the above-mentioned appropriate range, it is preferred to carry out concentration adjustment by water addition or water distillation.
尚且,本發明中,所謂脫水環化反應開始時,係指將原料液導入至反應器中而開始加熱的時候,所謂脫水環化反應中,係指此加熱開始後,將反應器內之反應液溫度維持為既定反應溫度的期間。 Further, in the present invention, when the dehydration cyclization reaction is started, when the raw material liquid is introduced into the reactor to start heating, the term "dehydration cyclization reaction" refers to the reaction in the reactor after the start of the heating. The liquid temperature is maintained for a predetermined reaction temperature.
另外,所謂脫水環化反應中之反應器內之反應液,係指原料1,4BG或酸觸媒、THF、水、原料1,4BG中之來自雜質的高沸點化合物、BGTF、胺及醯胺中之至少一者、以及由THF與1,4BG所生成之副產物等的混合溶液。 In addition, the reaction liquid in the reactor in the dehydration cyclization reaction means a raw material 1, 4BG or an acid catalyst, THF, water, a high boiling point compound derived from impurities in the raw material 1, 4BG, BGTF, an amine, and a guanamine. At least one of them, and a mixed solution of by-products such as THF and 1,4BG.
以下,藉由實施例更詳細說明本發明,但在不超過其要旨 之前提下,本發明並不限定於以下實施例。 Hereinafter, the present invention will be described in more detail by way of examples, without exceeding the gist thereof. The present invention is not limited to the following embodiments.
尚且,以下之水分分析係使用卡耳費雪法而進行。 Further, the following moisture analysis was carried out using the Karl Fischer method.
1,4-丁二醇、四氫呋喃及2-(4-羥基丁氧基)-四氫呋喃的分析係藉由氣體層析而進行,並藉由色譜的波峰面積比率予以算出。亦即,算出由100重量%減去水分濃度(重量%)的值,將減去水分濃度後之重量%份乘以氣體層析中各成分的面積比率。 The analysis of 1,4-butanediol, tetrahydrofuran and 2-(4-hydroxybutoxy)-tetrahydrofuran was carried out by gas chromatography and calculated from the peak area ratio of the chromatogram. That is, the value obtained by subtracting the water concentration (% by weight) from 100% by weight is calculated, and the weight % after subtracting the water concentration is multiplied by the area ratio of each component in the gas chromatography.
氮分析係使試料於氬/氧環境內燃燒,對所產生之燃燒氣體藉由使用了燃燒/減壓化學發光法的微量氮計(三菱化學Analytech公司製,TN-10型)進行分析。 In the nitrogen analysis, the sample was burned in an argon/oxygen atmosphere, and the generated combustion gas was analyzed by a trace nitrogen meter (TN-10 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using a combustion/decompression chemiluminescence method.
另外,作為用於使胺存在於1,4-丁二醇中的陰離子交換樹脂,係使用屬於具有聚乙二胺骨架的弱鹼性陰離子交換樹脂的三菱化學(股)製「DIAION(註冊商標)WA20」。藉由使用此陰離子交換樹脂,可於1,4-丁二醇中使含有2~20個來自乙烯胺之構成單位的多胺存在。 In addition, as an anion exchange resin for allowing an amine to be present in 1,4-butanediol, "DIAION" (registered trademark) is used by Mitsubishi Chemical Corporation, which is a weakly basic anion exchange resin having a polyethylenediamine skeleton. )WA20". By using this anion exchange resin, a polyamine having 2 to 20 constituent units derived from vinylamine can be present in 1,4-butanediol.
於1000mL之玻璃製燒瓶中填裝粗製1,4BG350g、陰離子交換樹脂35g,於室溫下攪拌2小時後,將陰離子交換樹脂濾除。於所得濾液320g中添加水70g後,測定液中之BGTF濃度,結果為0.2206重量%。此時,此液中之水分濃度為24.7重量%,1,4BG濃度為74.99重量%,由陰離子交換樹脂所溶出之多胺含量係依氮原子換算濃度計為110重量 ppm,pH為8.6。 A 1000 mL glass flask was charged with 350 g of crude 1,4 BG and 35 g of an anion exchange resin, and the mixture was stirred at room temperature for 2 hours, and then the anion exchange resin was filtered off. After adding 70 g of water to 320 g of the obtained filtrate, the concentration of BGTF in the liquid was measured and found to be 0.2206% by weight. At this time, the water concentration in the liquid was 24.7 wt%, the concentration of 1,4 BG was 74.99 wt%, and the polyamine content eluted from the anion exchange resin was 110 wt% in terms of concentration in terms of nitrogen atom. Ppm, pH 8.6.
於1000mL之不銹鋼製高壓釜中填充此溶液,將高壓釜內以氮氣置換後,依170℃加熱2小時。進行加熱處理液之分析,結果BGTF濃度減低為0.1522重量%。以此加熱處理液(水分濃度24.7重量%,1,4BG濃度75.0重量%,氮濃度110ppm,BGTF濃度0.1522重量%)作為原料液而進行THF製造。 This solution was filled in a 1000 mL stainless steel autoclave, and the inside of the autoclave was replaced with nitrogen, and then heated at 170 ° C for 2 hours. Analysis of the heat treatment liquid revealed that the BGTF concentration was reduced to 0.1522% by weight. THF was produced by heating the treatment liquid (water concentration: 24.7 wt%, 1,4 BG concentration: 75.0 wt%, nitrogen concentration: 110 ppm, BGTF concentration: 0.1522 wt%) as a raw material liquid.
於設置了用於餾出之玻璃製冷卻管的玻璃製500mL燒瓶反應器中,加入該加熱處理液370.3g(1,4BG量277.7g),並填裝對甲苯磺酸1.51g(相對於反應液為0.41重量%),使用油浴將內液溫度加熱至145℃。當內液溫度穩定於145℃後,將藉冷卻管所凝縮之含有THF的餾出液抽出至玻璃製貯槽中。 In a glass 500 mL flask reactor provided with a glass cooling tube for distillation, 370.3 g (1,4 BG amount 277.7 g) of the heat treatment liquid was added, and 1.51 g of p-toluenesulfonic acid was charged (relative to the reaction). The liquid was 0.41% by weight), and the temperature of the internal liquid was heated to 145 ° C using an oil bath. After the internal liquid temperature was stabilized at 145 ° C, the THF-containing distillate condensed by the cooling tube was taken out to a glass storage tank.
含有THF之餾出液量為340.2g。餾出液之組成係THF58.1重量%,水41.2重量%。THF之產率為88.9%,THF之生成速度為51.1g/hr。又,燒瓶反應器內之殘液為25.4g,水分濃度為1.3重量%,氮濃度為1603重量ppm。燒瓶反應器內之殘液中之固形物量為0.6mg。副產生固形物之產率(重量ppm)/THF產率為2。將結果整合示於表1。 The amount of the distillate containing THF was 340.2 g. The composition of the distillate was 58.1% by weight of THF and 41.2% by weight of water. The yield of THF was 88.9%, and the rate of formation of THF was 51.1 g/hr. Further, the residual liquid in the flask reactor was 25.4 g, the water concentration was 1.3% by weight, and the nitrogen concentration was 1,603 ppm by weight. The amount of solids in the raffinate in the flask reactor was 0.6 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 2. The results are shown in Table 1.
於1000mL之玻璃製燒瓶中填裝粗製1,4BG600g、陰離子交換樹脂60g,於室溫下攪拌2小時後,將陰離子交換樹脂 濾除。於所得濾液520g中添加水105g後,測定液中之BGTF濃度,結果為0.2206重量%。此時,此液中之水分濃度為21.0重量%,1,4BG濃度為78.71重量%,由陰離子交換樹脂所溶出之多胺含量係依氮原子換算濃度計為110重量ppm,pH為8.6。 The 1000 mL glass flask was filled with crude 1,4BG 600 g and anion exchange resin 60 g, and stirred at room temperature for 2 hours, then anion exchange resin was added. Filter out. After adding 105 g of water to 520 g of the obtained filtrate, the concentration of BGTF in the liquid was measured and found to be 0.2206% by weight. At this time, the water concentration in the liquid was 21.0% by weight, the 1,4BG concentration was 78.71% by weight, and the polyamine content eluted from the anion exchange resin was 110 ppm by weight in terms of nitrogen atom concentration, and the pH was 8.6.
於1000mL之不銹鋼製高壓釜中填充此溶液,將高壓釜內以氮氣置換後,依170℃加熱2小時。進行加熱處理液之分析,結果BGTF濃度減低為0.1544重量%。 This solution was filled in a 1000 mL stainless steel autoclave, and the inside of the autoclave was replaced with nitrogen, and then heated at 170 ° C for 2 hours. Analysis of the heat treatment liquid revealed that the BGTF concentration was reduced to 0.1544% by weight.
於設置了用於餾出之玻璃製冷卻管的玻璃製1000mL燒瓶反應器中,加入該加熱處理液517g,依壓力0.2kPa、內液溫度102℃實施單蒸餾。餾出液中,以初餾分離出173.1g,得到以1,4BG為主成分的本餾液316.9g。此時之釜殘液為21.9g。本餾液中之1,4BG濃度為99.4重量%,水分為0.310重量%,氮濃度為57重量ppm,BGTF濃度為0.1943重量%。以此本餾液作為原料液而進行THF製造。 In a glass 1000 mL flask reactor provided with a glass cooling tube for distillation, 517 g of the heat treatment liquid was added, and single distillation was carried out at a pressure of 0.2 kPa and an internal liquid temperature of 102 °C. In the distillate, 173.1 g of the first fraction was separated by preliminary distillation to obtain 316.9 g of the present fraction containing 1,4 BG as a main component. The residual liquid at this time was 21.9 g. The concentration of 1,4BG in the distillate was 99.4% by weight, the moisture was 0.310% by weight, the nitrogen concentration was 57 ppm by weight, and the BGTF concentration was 0.1943% by weight. The THF was produced by using this distillate as a raw material liquid.
於設置了用於餾出之玻璃製冷卻管的玻璃製500mL燒瓶反應器中,加入該餾出液300.2g(1,4BG量298.4g),並填裝對甲苯磺酸1.50g(相對於反應液為0.5重量%),使用油浴與實施例1同樣地於145℃進行反應蒸餾,將含有THF的餾出液271.0g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液27.3g。燒瓶反應器內之殘液中之固形物量為0.2mg。副產生固形物之產率(重量ppm)/THF產率為1。 In a glass 500 mL flask reactor provided with a glass cooling tube for distillation, 300.2 g of the distillate (1,4 BG amount: 298.4 g) was added, and 1.50 g of p-toluenesulfonic acid was added (relative to the reaction). The liquid was 0.5% by weight), and the reaction distillation was carried out at 145 ° C in the same manner as in Example 1 using an oil bath. 271.0 g of a THF-containing distillate was taken out to a glass storage tank, and 27.3 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.2 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 1.
將此時的反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
於1000mL之玻璃製燒瓶中填裝粗製1,4BG600g、陰離子交換樹脂60g,於室溫下攪拌2小時後,將陰離子交換樹脂濾除。將所得濾液4.0g藉粗製1,4BG400g稀釋,調製成以氮原子換算濃度計含有1.1重量ppm之由陰離子交換樹脂溶出之多胺的原料1,4BG(水分濃度0.029重量%,1,4BG濃度99.7重量%,氮濃度1.1重量ppm,BGTF濃度0.2902重量%)。又,測定pH的結果為7.0。 A 1000 mL glass flask was charged with 600 g of crude 1,4 BG and 60 g of an anion exchange resin, and the mixture was stirred at room temperature for 2 hours, and then the anion exchange resin was filtered off. 4.0 g of the obtained filtrate was diluted with 400 g of crude 1,4BG to prepare a raw material 1,4 BG (water concentration: 0.029% by weight, 1, 4 BG concentration: 99.7) containing 1.1 ppm by weight of a polyamine eluted from an anion exchange resin in terms of a nitrogen atom concentration. Weight %, nitrogen concentration 1.1 ppm by weight, BGTF concentration 0.2902% by weight). Further, the pH was measured and found to be 7.0.
於設置了用於餾出之玻璃製冷卻管的玻璃製500mL燒瓶反應器中,加入該原料1,4BG300.0g,並填裝對甲苯磺酸1.50g(相對於反應液為0.5重量%),使用油浴與實施例1同樣地於145℃進行反應蒸餾,將含有THF的餾出液271.0g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液28.8g。燒瓶反應器內之殘液中之固形物量為0.9mg。副產生固形物之產率(重量ppm)/THF產率為3。 In a glass 500 mL flask reactor provided with a glass cooling tube for distillation, 30 GB of the raw material 1, 4BG was added, and 1.50 g of p-toluenesulfonic acid (0.5% by weight based on the reaction liquid) was charged. The reaction distillation was carried out at 145 ° C in the same manner as in Example 1 using an oil bath, and 271.0 g of a distillate containing THF was taken out to a glass storage tank, and 28.8 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.9 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 3.
尚且,脫水環化反應開始時之反應器內之原料液中的氮濃度為1.1重量ppm。 Further, the concentration of nitrogen in the raw material liquid in the reactor at the start of the dehydration cyclization reaction was 1.1 ppm by weight.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了使用BGTF濃度為0.3236重量%、含有依氮原子換算濃度計為56.0重量ppm之4-羥基哌啶(簡稱為「4OHP」) 的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。又,脫水環化反應開始時之反應器內之原料液中的氮濃度為56.0重量ppm。於以下實施例及比較例中,脫水環化反應開始時之反應器內之原料液中的氮濃度,係與原料1,4BG之氮原子換算濃度幾乎相等。 In addition to the use of a BGTF concentration of 0.3236% by weight, a concentration of 56.0 ppm by weight of 4-hydroxypiperidine (abbreviated as "4OHP") The same procedure as in Example 3 was carried out except that 1,4 BG was used as the raw material 1, 4BG. Further, the concentration of nitrogen in the raw material liquid in the reactor at the start of the dehydration cyclization reaction was 56.0 ppm by weight. In the following examples and comparative examples, the concentration of nitrogen in the raw material liquid in the reactor at the start of the dehydration cyclization reaction was almost equal to the concentration of the nitrogen atom in the raw material 1,4 BG.
將含有THF之餾出液265.1g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液27.5g。燒瓶反應器內之殘液中的固形物量為0.3mg。副產生固形物之產率(重量ppm)/THF產率為1。 265.1 g of a distillate containing THF was taken out to a glass storage tank, and 27.5 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.3 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 1.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了使用含有依氮原子換算濃度計為10.0重量ppm之4-羥基哌啶(4OHP)的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG containing 40.0 ppm by weight of 4-hydroxypiperidine (4OHP) in terms of a nitrogen atom was used as the raw material 1,4BG.
將含有THF之餾出液263.0g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液36.9g。燒瓶反應器內之殘液中的固形物量為0.8mg。副產生固形物之產率(重量ppm)/THF產率為3。 263.0 g of a distillate containing THF was taken out into a glass storage tank, and 36.9 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.8 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 3.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了使用含有依氮原子換算濃度計為1.1重量ppm之4-羥基哌啶(4OHP)的1,4BG作為原料1,4BG以外,其餘與實 施例3同樣進行。 Except that 1,4BG containing 4-hydroxypiperidine (4OHP) in a concentration of 1.1 ppm by weight in terms of nitrogen atom was used as the raw material 1, 4BG, Example 3 was carried out in the same manner.
將含有THF之餾出液260.9g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液39.2g。燒瓶反應器內之殘液中的固形物量為0.6mg。副產生固形物之產率(重量ppm)/THF產率為2。 260.9 g of a distillate containing THF was taken out to a glass storage tank, and 39.2 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.6 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 2.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了取代4-羥基哌啶而使用含有依氮原子換算濃度計為10.0重量ppm之1-胺基癸烷的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG containing 10.0 ppm by weight of 1-aminononane in terms of a nitrogen atom was used instead of 4-hydroxypiperidine as the raw material 1, 4BG.
將含有THF之餾出液274.6g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液25.3g。燒瓶反應器內之殘液中的固形物量為1.2mg。副產生固形物之產率(重量ppm)/THF產率為4。 274.6 g of a distillate containing THF was taken out to a glass storage tank, and 25.3 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 1.2 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 4.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了取代4-羥基哌啶而使用含有依氮原子換算濃度計為10.0重量ppm之三正丁基胺的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG containing 10.0 ppm by weight of tri-n-butylamine in terms of a nitrogen atom was used as the raw material 1, 4BG instead of 4-hydroxypiperidine.
將含有THF之餾出液264.9g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液35.1g。燒瓶反應器內之殘液中的固形物量為0.8mg。副產生固形物之產率(重量ppm)/THF產率為 3。 264.9 g of a distillate containing THF was taken out to a glass storage tank, and 35.1 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.8 mg. The yield of by-product solids (ppm by weight) / THF yield is 3.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了取代4-羥基哌啶而使用含有依氮原子換算濃度計為10.0重量ppm之2-吡咯啶酮(簡稱為「2P」)的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 except that 1,4 BG containing 20.0 ppm by weight of 2-pyrrolidone (abbreviated as "2P") in terms of a nitrogen atom was used as a raw material 1, 4BG, in place of 4-hydroxypiperidine. get on.
將含有THF之餾出液265.8g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液34.2g。燒瓶反應器內之殘液中的固形物量為0.9mg。副產生固形物之產率(重量ppm)/THF產率為3。 265.8 g of a distillate containing THF was taken out to a glass storage tank, and 34.2 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 0.9 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 3.
將此時之反應結果整合示於表1。 The reaction results at this time are shown in Table 1.
除了使用BGTF濃度為0.3236重量%、氮濃度為0.1重量ppm以下之1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG having a BGTF concentration of 0.3236% by weight and a nitrogen concentration of 0.1 ppm by weight or less was used as the raw material 1, 4BG.
將含有THF之餾出液260.9g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液34.7g。燒瓶反應器內之殘液中的固形物量為140mg。副產生固形物之產率(重量ppm)/THF產率為54。 260.9 g of a distillate containing THF was taken out into a glass storage tank, and 34.7 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 140 mg. The yield of the by-produced solids (ppm by weight) / THF yield was 54.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用含有依氮原子換算濃度計為0.5重量ppm之由陰 離子交換樹脂溶出之多胺的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 In addition to using a concentration of 0.5 ppm by weight in terms of nitrogen atoms, The 1,4 BG of the polyamine eluted from the ion exchange resin was used as the raw material 1, 4BG, and the same procedure as in Example 3 was carried out.
將含有THF之餾出液272.1g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液27.9g。燒瓶反應器內之殘液中的固形物量為180mg。副產生固形物之產率(重量ppm)/THF產率為62。 272.1 g of a distillate containing THF was taken out to a glass storage tank, and 27.9 g of a residue was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 180 mg. The yield of the by-produced solids (ppm by weight) / THF yield was 62.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用含有依氮原子換算濃度計為0.5重量ppm之4-羥基哌啶(4OHP)的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4BG containing 4-hydroxypiperidine (4OHP) in an amount of 0.5 ppm by weight in terms of a nitrogen atom was used as the raw material 1,4BG.
將含有THF之餾出液267.6g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液32.4g。燒瓶反應器內之殘液中的固形物量為110mg。副產生固形物之產率(重量ppm)/THF產率為39。 267.6 g of a distillate containing THF was taken out to a glass storage tank, and 32.4 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 110 mg. The yield of the by-produced solids (ppm by weight) / the yield of THF was 39.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用依Na原子換算濃度計含有10.0重量ppm之方式添加了2N-NaOH水溶液的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG in which a 2N-NaOH aqueous solution was added in an amount of 10.0 ppm by weight in terms of Na atomic concentration was used as the raw material 1, 4BG.
將含有THF之餾出液274.0g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液26.0g。燒瓶反應器內之殘液中的固形 物量為120mg。副產生固形物之產率(重量ppm)/THF產率為43。 274.0 g of a distillate containing THF was taken out to a glass storage tank, and 26.0 g of a residue was obtained in a flask reactor. Solids in the raffinate in the flask reactor The amount is 120 mg. The yield of the by-produced solids (ppm by weight) / THF yield was 43.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用含有依氮原子換算濃度計為10.0重量ppm之25%氨水溶液的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG containing 25% by weight of a 25% by weight aqueous solution of ammonia was used as the raw material 1, 4BG.
將含有THF之餾出液268.4g抽出至玻璃製貯槽中,於燒瓶反應器內得到殘液31.6g。燒瓶反應器內之殘液中的固形物量為210mg。副產生固形物之產率(重量ppm)/THF產率為76。 268.4 g of a distillate containing THF was taken out to a glass storage tank, and 31.6 g of a residual liquid was obtained in a flask reactor. The amount of solids in the raffinate in the flask reactor was 210 mg. The yield of the by-produced solids (ppm by weight) / THF yield was 76.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用含有依氮原子換算濃度計為2000重量ppm之2-吡咯啶酮的1,4BG作為原料1,4BG以外,其餘與實施例3同樣進行。 The same procedure as in Example 3 was carried out except that 1,4 BG containing 2-pyrrolidone having a concentration of 2000 ppm by weight in terms of a nitrogen atom was used as the raw material 1, 4BG.
本例中,THF之餾出速度為12g/h(實施例之1/4以下),THF化反應明顯被抑制。 In this example, the distillation rate of THF was 12 g/h (1/4 or less of the examples), and the THF reaction was remarkably suppressed.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
除了使用含有依氮原子換算濃度計為15000重量ppm之4-羥基哌啶的1,4BG作為原料1,4BG以外,其餘與實施例3 同樣進行。 Except that 1,4 BG containing 1,5000 ppm by weight of 4-hydroxypiperidine in terms of nitrogen atom concentration was used as the raw material 1, 4BG, and Example 3 was used. The same goes on.
本例中,即使內液溫度達到145℃,仍未得到餾出物。其後,雖將內液溫度加熱至160℃,但即使內液溫度達到160℃仍未得到餾出物。 In this example, even if the internal liquid temperature reached 145 ° C, no distillate was obtained. Thereafter, although the temperature of the inner liquid was heated to 160 ° C, the distillate was not obtained even if the inner liquid temperature reached 160 °C.
將此時之反應結果整合示於表2。 The reaction results at this time are shown in Table 2.
由實施例1~9與比較例1~5可知,藉由使用含有既定量之胺及醯胺中之至少一者的含1,4BG原料液,雖然反應速度稍降低,但可大幅減低阻礙運轉之副產生固形物的選擇率,可維持生產量、改善THF產率。 It is understood from Examples 1 to 9 and Comparative Examples 1 to 5 that by using a 1,4 BG-containing raw material liquid containing at least one of a predetermined amount of an amine and a guanamine, although the reaction rate is slightly lowered, the hindrance operation can be greatly reduced. The by-product ratio of the solid matter is maintained to maintain the production amount and improve the THF yield.
另外,由比較例6、7可知,若含1,4BG原料液之胺及醯胺中之至少一者的量較多,則THF的生產性降低,若過多,則無法進行反應。 Further, as is clear from Comparative Examples 6 and 7, when the amount of at least one of the amine and the guanamine containing the 1,4 BG raw material liquid is large, the productivity of THF is lowered, and if it is too large, the reaction cannot be performed.
以上詳細地並參照特定實施態樣說明了本發明,但在不脫離本發明之精神與範圍之下,熟悉該項技術者當知可加以各種變更或修正。本申請案係根據2011年7月4日申請之日本專利申請案(特願2011-148327)、2011年7月4日申請之日本專利申請案(特願2011-148328)、2011年7月8日申請之日本專利申請案(特願2011-151716)、2011年7月13日申請之日本專利申請案(特願2011-154862)、2011年8月1日申請之日本專利申請案(特願2011-168645)、2011年11月1日申請之日本專利申請案(特願2011-240422)及2011年11月2日申請之日本專利申請案(特願2011-241572),將其內容取入於此作為參照。 The present invention has been described in detail above with reference to the specific embodiments thereof, and it is to be understood that various modifications and changes can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on July 4, 2011 (Japanese Patent Application No. 2011-148327), Japanese Patent Application No. 2011-148328, filed on July 4, 2011, and July 8, 2011 Japanese patent application filed by Japan (Japanese Patent Application No. 2011-151716), Japanese patent application filed on July 13, 2011 (Japanese Patent Application No. 2011-154862), Japanese Patent Application filed on August 1, 2011 (Special Wish) 2011-168645), the Japanese patent application filed on November 1, 2011 (Japanese Patent Application No. 2011-240422) and the Japanese patent application filed on November 2, 2011 (Japanese Patent Application No. 2011-241572), This is for reference.
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TW101123875A TWI535711B (en) | 2011-07-04 | 2012-07-03 | Method of producing tetrahydrofuran |
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TW (1) | TWI535711B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI619700B (en) * | 2012-10-18 | 2018-04-01 | Mitsubishi Chem Corp | Method for producing tetrahydrofuran |
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WO2013005749A1 (en) | 2011-07-04 | 2013-01-10 | 三菱化学株式会社 | Method for producing tetrahydrofuran |
KR101998433B1 (en) | 2011-07-08 | 2019-07-09 | 미쯔비시 케미컬 주식회사 | Composition containing 1,4-butanediol |
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JPS59140223A (en) * | 1983-02-01 | 1984-08-11 | Polyplastics Co | Production of polytetramethylene terephthalate |
JPH02167274A (en) * | 1988-12-21 | 1990-06-27 | Tokuyama Soda Co Ltd | Production of cyclic ether |
JP3232177B2 (en) * | 1993-10-21 | 2001-11-26 | 東燃化学株式会社 | Method for producing tetrahydrofuran |
DE10237954A1 (en) * | 2002-08-20 | 2004-03-04 | Basf Ag | Continuous production of tetrahydrofuran (THF), useful for the production of poly-THF, comprises reaction of a 1,4-butanediol reaction mixture containing 2-(4-hydroxybutoxy)tetrahydrofuran at a non-predried heteropolyacid catalyst |
GB0421928D0 (en) * | 2004-10-01 | 2004-11-03 | Davy Process Techn Ltd | Process |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI619700B (en) * | 2012-10-18 | 2018-04-01 | Mitsubishi Chem Corp | Method for producing tetrahydrofuran |
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JP2013116881A (en) | 2013-06-13 |
JP5949227B2 (en) | 2016-07-06 |
TW201305124A (en) | 2013-02-01 |
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