KR20090026908A - Process for producing of tetrahydrofuran from 1,4-butanediol - Google Patents

Process for producing of tetrahydrofuran from 1,4-butanediol Download PDF

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KR20090026908A
KR20090026908A KR1020070091985A KR20070091985A KR20090026908A KR 20090026908 A KR20090026908 A KR 20090026908A KR 1020070091985 A KR1020070091985 A KR 1020070091985A KR 20070091985 A KR20070091985 A KR 20070091985A KR 20090026908 A KR20090026908 A KR 20090026908A
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catalyst
butanediol
tetrahydrofuran
reaction
iron phosphate
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KR1020070091985A
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Korean (ko)
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이은구
백용호
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주식회사 효성
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Priority to CN2008100906665A priority patent/CN101386610B/en
Publication of KR20090026908A publication Critical patent/KR20090026908A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

Abstract

A tetrahydrofuran is provided to be manufactured from 1,4-butanediol with a reaction yield using a simple impartiality having less risk. A tetrahydrofuran is manufactured by dehydrating 1,4-butanediol under presence of iron phosphate catalyst. A dehydrating temperature is 150~300°C. An iron phosphate catalyst is used independently or by being supported using carrier. The iron phosphate catalyst is pre-processed at a temperature of 200~400°C by using inert gas before the reaction.

Description

1,4-부탄디올로부터 테트라하이드로퓨란을 제조하는 방법{Process for producing of tetrahydrofuran from 1,4-butanediol}Process for producing of tetrahydrofuran from 1,4-butanediol

본 발명은 철인산염 촉매 존재하에 1,4-부탄디올로부터 테트라하이드로퓨란을 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing tetrahydrofuran from 1,4-butanediol in the presence of an iron phosphate catalyst.

테트라하이드로퓨란(Tetrahydrofuran, THF)은 유기화합물의 용매나 고분자 합성의 원료로 사용되는 등 여러 분야에서 널리 사용되는 화합물이다. 최근에는 여러 가지 합성 고분자의 원료 및 첨가제로 사용되면서 그 사용량이 점차 증가하고 있다.Tetrahydrofuran (THF) is a compound widely used in various fields, such as being used as a solvent for organic compounds or as a raw material for polymer synthesis. Recently, the amount of use is gradually increasing as it is used as a raw material and additive of various synthetic polymers.

테트라하이트로퓨란은 다양한 방법에 의해 제조되고 있다. 가장 일반적인 제조 방법은 1,4-부탄디올을 탈수화시켜 테트라하이드로퓨란을 제조하거나 또는 퓨란을 수소화 반응시켜 테드라하이드로퓨란을 제조하는 것이다. Tetrahytrofuran is produced by various methods. The most common production method is to produce tetrahydrofuran by dehydrating 1,4-butanediol or to produce tetradrafurfuran by hydrogenating furan.

그 중에서 1,4-부탄디올을 탈수화시켜 테트로하이드로퓨란을 제조하는 방법은 산촉매하에 1,4-부탄디올을 반응시키는 단계와 반응 후 생성된 일정량의 수분을 함유한 테트로하이드로퓨란에서 물을 분리하는 단계로 이루어져 있다. 이러한 공정의 효율은 반응단계에서 사용되는 산촉매의 성능에 의해 결정되기 때문에 효과적인 1,4-부탄디올의 탈수반응 촉매를 개발하는 것이 무엇보다도 중요하다.Among them, 1,4-butanediol is dehydrated to prepare tetrahydrofuran by reacting 1,4-butanediol under an acid catalyst and separating water from tetrahydrofuran containing a certain amount of water generated after the reaction. Consists of steps. Since the efficiency of this process is determined by the performance of the acid catalyst used in the reaction step, it is important to develop an effective 1,4-butanediol dehydration catalyst.

미국 특허 제4,665,205호에는 1,4-부탄디올의 탈수화 반응 촉매로서 황산과 같은 무기산을 촉매로 이용하는 방법이 제안되어 있다. 동특허의 방법은 촉매가 무기산이므로 공정상 위험이 있으며, 무기산에 의해 반응 장치가 부식되는 문제가 있다.U.S. Patent 4,665,205 proposes a method of using an inorganic acid such as sulfuric acid as a catalyst as a catalyst for dehydration of 1,4-butanediol. Since the catalyst is an inorganic acid, the method of the patent has a risk in process, and there is a problem in that the reaction apparatus is corroded by the inorganic acid.

다른 탈수화 반응의 촉매로 미국 특허 제6,204,399호는 알루미나 촉매, 일본 특허공개 평9-059191호는 실리카-알루미나 촉매, 미국 특허 제4,136,099호는 알루미나를 담체한 텅스텐 산화물 촉매, 그리고 일본 특허공개 소61-126080호는 헤테로폴리산 촉매를 제안하고 있다. 이러한 여러 가지 산촉매 존재 하에 1,4-부탄디올로부터 테트라하이드로퓨란을 제조하는 방법이 또한 제시되어 있다. 제시된 촉매상에서 1,4-부탄디올의 탈수반응 공정은 촉매의 활성이나 수명 면에서 문제점이 있다.As catalysts for other dehydration reactions, U.S. Pat.No. 6,204,399 is an alumina catalyst, Japanese Patent Application Laid-Open No. Hei 9-059191, a silica-alumina catalyst, U.S. Pat. -126080 proposes a heteropolyacid catalyst. Also disclosed is a process for preparing tetrahydrofuran from 1,4-butanediol in the presence of these various acid catalysts. The dehydration process of 1,4-butanediol on the catalysts presented presents problems in terms of catalyst activity and lifetime.

따라서 본 발명은 테트라하이드로퓨란의 제조시 발생하는 낮은 반응 수율 및 공정의 위험성 문제를 동시에 해결할 수 있는 높은 반응수율로 안전하고 간편하게 테트라하이드로퓨란을 제조하는 방법을 제공하고자 한다.Accordingly, the present invention is to provide a method for safely and simply preparing tetrahydrofuran with a high reaction yield that can simultaneously solve the problem of low reaction yield and process risks occurring during the production of tetrahydrofuran.

상기 과제를 해결하기 위하여, 본 발명의 적절한 실시 형태에 따르면, 1,4-부탄디올을 촉매 존재하에 탈수반응시켜 테트라하이드로퓨란을 제조하는 방법에 있어서, 촉매로 철인산염 촉매를 이용하는 테트라하이드로퓨란의 제조 방법이 제공된다. In order to solve the above problems, according to a preferred embodiment of the present invention, in the method for producing tetrahydrofuran by dehydrating 1,4-butanediol in the presence of a catalyst, the production of tetrahydrofuran using an iron phosphate catalyst as a catalyst A method is provided.

본 발명의 다른 적절한 실시 형태에 따르면, 철인산염 촉매 존재하 1,4-부탄디올의 반응은 150~300℃의 온도에서 실시될 수 있다. According to another suitable embodiment of the present invention, the reaction of 1,4-butanediol in the presence of an iron phosphate catalyst may be carried out at a temperature of 150 to 300 ° C.

본 발명의 또 다른 적절한 실시 형태에 따르면, 철인산염 촉매는 단독 또는 담체에 담지시킨 것을 사용할 수 있다. According to another suitable embodiment of the present invention, the iron phosphate catalyst may be used alone or supported on a carrier.

본 발명의 또 다른 적절한 실시 형태에 따르면, 철인산염 촉매는 1,4-부탄디올의 탈수반응 전에 불활성 기체를 이용하여 200~400℃의 온도에서 전처리된 것일 수 있다. According to another suitable embodiment of the present invention, the iron phosphate catalyst may be pretreated at a temperature of 200 ~ 400 ℃ using an inert gas before the dehydration of 1,4-butanediol.

본 발명에 따르면 철인산염 촉매를 사용하는 간단하고 위험성이 적은 공정을 이용해 높은 반응수율로 테트라하이드로퓨란을 제조할 수 있다.According to the present invention, tetrahydrofuran can be prepared in a high reaction yield using a simple and low risk process using an iron phosphate catalyst.

본 발명은 고효율의 반응활성을 지닌 철인산염 촉매 상에서 1,4-부탄디올로부터 테트라하이드로퓨란을 제조하는 방법에 관한 것이다. The present invention relates to a method for preparing tetrahydrofuran from 1,4-butanediol on an iron phosphate catalyst having high efficiency of reaction activity.

철인산염 촉매는 반응 활성 및 선택도(selectivity)가 뛰어나며, 촉매 수명이 매우 우수한 것을 특징으로 하며, 일반적으로 철인산염 촉매는 단독으로 사용이 가능하며, 알루미나, 실리카, 타이타니아, 제올라이트 및 활성탄 등의 담체에 담지시켜 사용하는 것도 가능하다. The iron phosphate catalyst is characterized by excellent reaction activity and selectivity and excellent catalyst life. Generally, the iron phosphate catalyst can be used alone, and supports such as alumina, silica, titania, zeolite and activated carbon It is also possible to use on the support.

본 발명에서 사용되는 철인산염 촉매는 1M의 질산철(Fe(NO3)3) 수용액에 1M의 인산(H3PO4) 또는 인산암모늄(NH4H2PO4)을 Fe:P의 비율이 1 내지 1.5가 되도록 첨가하여 90℃에서 2시간 교반한 후, 24시간 건조기에서 건조하여 철인산염(FePO4) 촉매를 제조한다. 본 발명에서 철인산염 촉매는 단독으로 또는 담체에 담지시켜 사용할 수 있다. The iron phosphate catalyst used in the present invention is a 1M solution of iron nitrate (Fe (NO 3 ) 3 ) in which 1M phosphoric acid (H 3 PO 4 ) or ammonium phosphate (NH 4 H 2 PO 4 ) is a ratio of Fe: P. 1 to 1.5 was added and stirred at 90 ° C. for 2 hours, followed by drying in a dryer for 24 hours to prepare an iron phosphate (FePO 4 ) catalyst. In the present invention, the iron phosphate catalyst may be used alone or supported on a carrier.

철인산염 촉매는 전처리(pretreatment) 과정 없이 반응에 사용 가능하나, 수소나 질소, 헬륨, 아르곤 등의 불활성 기체 하에서 200 ~ 400℃의 온도로 처리하면 촉매활성을 증가시킬 수 있다. 이때 200℃ 미만의 온도에서는 촉매 표면에 존재하는 수분 및 불순물이 효과적으로 제거되지 않으며, 400℃를 초과하면 철인산염 촉매의 분해가 일어나 반응 활성이 저하된다.The iron phosphate catalyst can be used for the reaction without pretreatment, but under inert gas such as hydrogen, nitrogen, helium or argon Treatment with a temperature of 200 ~ 400 ℃ can increase the catalytic activity. At this time, moisture and impurities present on the surface of the catalyst are not effectively removed at a temperature below 200 ° C., and when the temperature exceeds 400 ° C., the iron phosphate catalyst is decomposed to lower the reaction activity.

본 발명에 따른 테트라하이드로퓨란을 제조하기 위하여 기상 또는 액상 반응기를 사용할 수 있고, 제조 방법은 다음과 같다.Gas phase or liquid phase reactor may be used to prepare tetrahydrofuran according to the present invention, and the preparation method is as follows.

기상 고정층 반응기를 사용하여 제조하는 방법은 철인산염 촉매를 관형반응기에 충진한 후, 200~300℃의 온도에서 불활성 가스를 흘려보내면서 촉매를 활성화시킨다. 150~300℃의 반응온도, 바람직하게는 200~250℃의 반응온도에서 공간속도(liquid hourly space velocity) 3 ~ 10에서 불활성 가스와 함께 1,4-부탄디올을 흘려보내면서 반응시킨다.In the method using the gas phase fixed bed reactor, the iron phosphate catalyst is charged into the tubular reactor, and then the catalyst is activated while flowing an inert gas at a temperature of 200 to 300 ° C. The reaction is carried out by flowing 1,4-butanediol together with an inert gas at a liquid hourly space velocity of 3 to 10 at a reaction temperature of 150 to 300 ° C, preferably 200 to 250 ° C.

테트라하이드로퓨란을 액상 슬러리 반응기를 사용하여 제조하는 방법은 200~300℃의 온도에서 활성화시킨 철인산염 촉매를 1,4-부탄디올 중량 대비 0.1~20 wt%와 1,4-부탄디올을 액상반응기에 충진한 후 150~300℃의 반응온도, 바람직하게는 200~250℃의 반응온도로 가열하여 반응시킨다.Tetrahydrofuran is prepared by using a liquid slurry reactor. The iron phosphate catalyst activated at a temperature of 200 to 300 ° C. is filled with 0.1 to 20 wt% of 1,4-butanediol and 1,4-butanediol in a liquid phase reactor. After the reaction is heated to a reaction temperature of 150 ~ 300 ℃, preferably 200 ~ 250 ℃.

상기 반응에서의 반응온도는 150~300℃가 적당하며, 특히 200~250℃의 온도에서 반응이 효율적으로 일어난다. 150℃ 미만에서는 반응이 잘 진행되지 않으며, 300℃ 초과에서는 테트라하이드로퓨란의 열분해로 인해 선택도가 저하된다.The reaction temperature in the reaction is suitably 150 ~ 300 ℃, especially the reaction occurs efficiently at a temperature of 200 ~ 250 ℃. The reaction does not proceed well below 150 ° C., and above 300 ° C., the selectivity is lowered due to the thermal decomposition of tetrahydrofuran.

본 발명에 따른 테트라하이드로퓨란의 제조 공정을 도 1을 참조로 설명하면 다음과 같다.Hereinafter, a process of preparing tetrahydrofuran according to the present invention will be described with reference to FIG. 1.

도 1에 개략적으로 나타낸 바와 같이, 1,4-부탄디올은 라인1(L1)을 통하여 철인산염 촉매가 충진된 액상 또는 기상 반응기(11)로 도입되며, 반응기(11)에서 일정 시간동안 체류한 1,4-부탄디올은 테트라하이드로퓨란으로 전환된다. 반응기(11)를 나온 생성물은 테트라하이드로퓨란, 물 및 1,4-부탄디올로 구성되어 있으며, 이들 생성물 중 미반응 1,4-부탄디올은 1차 분리기(12)를 통과하면서 분리되어 다시 반응기(11)로 라인3(L3)을 통하여 리싸이클(recycle)된다. 1차 분리기(12)를 나온 생성물은 테트라하이드로퓨란과 물로 구성되어 있으며, 이들은 공비 혼합물(azerotropic mixture)로 2차 분리기(13)를 통과하면서 고순도의 테트라하이드로퓨란이 얻어진다.As schematically shown in FIG. 1, 1,4-butanediol is introduced into a liquid or gas phase reactor 11 filled with an iron phosphate catalyst via line 1 (L1), and is allowed to remain in the reactor 11 for a period of time. , 4-butanediol is converted to tetrahydrofuran. The product exiting reactor (11) consists of tetrahydrofuran, water, and 1,4-butanediol, of which unreacted 1,4-butanediol is separated while passing through the primary separator (12), and then the reactor (11). ) Is recycled through line 3 (L3). The product leaving the primary separator 12 consists of tetrahydrofuran and water, which are passed through the secondary separator 13 in an azeotropic mixture to obtain high purity tetrahydrofuran.

이하, 본 발명을 하기 실시 예에 의거하여 좀 더 상세하게 설명하고자 한다. 단, 하기 실시 예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

실시 예1Example 1

기상 촉매 반응을 수행하기 위하여 직경 2 mm, 길이 520 mm의 고정층 관형반응기를 사용하였다. 먼저 3 g의 철인산염 촉매를 충진한 후 헬륨가스를 이용하여 300℃에서 2시간 동안 촉매를 활성화시켰다. 1,4-부탄디올은 실린지 펌프(Syringe pump)를 사용하여 주입했으며, 헬륨과 혼합하여 5.0 liter/h의 유속으로 반응기로 투입했다. 반응 조건은 대기압, 200℃하에서 수행하였으며, 반응 생성물은 포로팩(Poropak) QS 컬럼과 불꽃이온화 검출기(FID)가 장착된 가스크로마토그래피를 이용하여 직접(on-line) 방식으로 분석하였다. 정상상태(Steady-state)에 도달한 후 반응기를 통과한 생성물을 분석한 결과 테트라하이드로퓨란의 수율은 99.5%였다.A fixed bed tubular reactor of diameter 2 mm and length 520 mm was used to carry out the gas phase catalytic reaction. First, 3 g of iron phosphate catalyst was charged and the catalyst was activated at 300 ° C. for 2 hours using helium gas. 1,4-butanediol was injected using a syringe pump, mixed with helium and introduced into the reactor at a flow rate of 5.0 liter / h. The reaction conditions were performed under atmospheric pressure at 200 ° C., and the reaction products were analyzed on-line using gas chromatography equipped with a Poropak QS column and a flame ionization detector (FID). After reaching the steady-state, the product passed through the reactor was analyzed and the yield of tetrahydrofuran was 99.5%.

실시 예2Example 2

마그네틱 교반기와 환류장치가 장착된 500 ml의 3구 반응기에서 액상촉매 반 응을 수행하였다. 반응 전에 촉매는 헬륨가스를 이용하여 250℃에서 2시간 동안 촉매를 활성화시켰으며, 이렇게 전처리한 철인산염 촉매 1 g과 1,4-부탄디올 100 g을 반응기에 투입하였다. 반응온도 200℃ 하에서 1시간 동안 반응을 수행하였으며, 반응 생성물은 응축기를 통하여 응축시킨 후 이를 다시 증류하여 미반응 1,4-부탄디올을 분리하고 실시 예1과 같은 가스크로마토그래피를 이용하여 분석하였다. 생성물을 분석한 결과 테트라하이드로퓨란의 반응 수율은 99.5%였다.Liquid catalyst reaction was carried out in a 500 ml three-necked reactor equipped with a magnetic stirrer and a reflux apparatus. Before the reaction, the catalyst was activated with helium gas at 250 ° C. for 2 hours, and 1 g of the pretreated iron phosphate catalyst and 100 g of 1,4-butanediol were added to the reactor. The reaction was carried out at a reaction temperature of 200 ° C. for 1 hour, and the reaction product was condensed through a condenser and then distilled to separate unreacted 1,4-butanediol and analyzed by gas chromatography as in Example 1. As a result of analyzing the product, the reaction yield of tetrahydrofuran was 99.5%.

비교 예1 ~ 3Comparative Examples 1 to 3

산성 알루미나, 헤테로폴리산의 일종인 텅스토인산 및 실리카-알루미나 촉매 각각 1 g과 1,4-부탄디올 100 g을 사용하여 40분간 반응시키는 것을 제외하고 실시 예2와 같이 실시하였다. 반응 후 각각의 반응 수율 결과를 표 1에 나타내었다.The reaction was carried out as in Example 2 except that the reaction was performed for 40 minutes using 1 g of acidic alumina, tungstophosphoric acid, a kind of heteropoly acid, and 100 g of 1,4-butanediol, respectively. Each reaction yield after the reaction is shown in Table 1.

실시 예1Example 1 실시 예2Example 2 비교 예1Comparative Example 1 비교 예2Comparative Example 2 비교 예3Comparative Example 3 촉매catalyst 철인산염Iron phosphate 철인산염Iron phosphate 산성알루미나Acid Alumina 텅스토인산 촉매Tungstoic acid catalyst 실리카- 알루미나Silica-alumina 반응 수율(%)Reaction yield (%) 99.599.5 99.599.5 76.176.1 83.483.4 73.273.2

도 1은 본 발명에 따른 1,4-부탄디올의 탈수반응에 의한 테트라하이드로퓨란을 제조하는 공정 흐름을 개략적으로 나타낸 블록도이다. 1 is a block diagram schematically showing a process flow for preparing tetrahydrofuran by dehydration of 1,4-butanediol according to the present invention.

Claims (4)

1,4-부탄디올을 촉매 존재하에 탈수반응시켜 테트라하이드로퓨란을 제조하는 방법에 있어서, 촉매로서 철인산염 촉매를 이용하는 것을 특징으로 하는 테트라하이드로퓨란의 제조방법. A method for producing tetrahydrofuran by dehydrating 1,4-butanediol in the presence of a catalyst, wherein the iron phosphate catalyst is used as a catalyst. 제1항에 있어서, 상기 반응온도는 150~300℃인 것을 특징으로 하는 테트라하이드로퓨란의 제조방법. The method of claim 1, wherein the reaction temperature is 150 ~ 300 ℃ method of producing tetrahydrofuran. 제1항에 있어서, 철인산염 촉매는 단독으로 사용하거나, 담체를 이용하여 담지시킨 것임을 특징으로 하는 테트라하이드로퓨란의 제조방법.The method for producing tetrahydrofuran according to claim 1, wherein the iron phosphate catalyst is used alone or supported by a carrier. 제1항에 있어서, 철인산염 촉매는 반응 전에 불활성 기체를 이용하여 200~400℃의 온도에서 전처리한 것임을 특징으로 하는 테트라하이드로퓨란의 제조방법. The method of claim 1, wherein the iron phosphate catalyst is a method of producing tetrahydrofuran, characterized in that pre-treatment at a temperature of 200 ~ 400 ℃ using an inert gas before the reaction.
KR1020070091985A 2007-09-11 2007-09-11 Process for producing of tetrahydrofuran from 1,4-butanediol KR20090026908A (en)

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