METHOD OF PRODUCTION OF 1,4-BUTANEDIOL AND USE OF 1,4-BUTANEDIOL DERIVED FROM BIOMASS OBTAINABLE BY

专利摘要:
1,4-butanediol, its method of production and its use. an objective of the present invention is to provide a high quality 1.4bg capable of elaborating a pbt raw material with good color tone, by efficiently removing and refining the mixed impurities while producing a 1.4bg derived from biomass on an industrial scale. The present invention relates to a method of producing refined 1.4bg, where a solution containing 1.4bg crude is obtained from 1.4bg of the refined raw material obtained by removing bacterial cells, saline contents and water from the culture medium of fermentation, by a step of removing high-boiling components and/or low-boiling components by distillation and/or a step of converting an unsaturated compound to a hydride and the target product is obtained as a side stream in an additional distillation step.
公开号:BR112014030247B1
申请号:R112014030247-2
申请日:2013-06-03
公开日:2021-07-13
发明作者:Masaru Utsunomiya；Yusuke IZAWA；Norikazu Konishi；Kota Tanaka；Shinichiro Matsuzono；Takayuki Suzuki；Michael Japs；Mark Burk；Warren Clark
申请人:Mitsubishi Chemical Corporation；Genomatica, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a method of production of 1,4-butanediol. More specifically, the present invention relates to a method for producing high purity refined 1,4-butanediol by refining crude 1,4-butanediol obtained from biomass resources. BACKGROUND TECHNIQUE
[002] 1,4-Butanediol (hereinafter, sometimes referred to simply as "1,4BG") is a very useful substance used as a raw material for various solvents or derivatives.
[003] Conventionally, a variety of methods to industrially produce 1,4BG using petroleum or other fossil fuels as a feedstock is known. For example, there is a method where diacetoxybutene is obtained as an intermediate by an acetoxylation reaction using acetic acid and oxygen and using butadiene as a raw material and diacetoxybutene is hydrogenated and hydrolyzed to produce 1,4BG; a method where maleic acid, succinic acid, maleic anhydride and/or fumaric acid are used as the raw material and these materials are hydrogenated to obtain a crude product containing 1.4BG of hydrogenation; and a method where butynediol obtained using acetylene as a raw material, contacting it with an aqueous formaldehyde solution, is hydrogenated to produce 1,4BG.
[004] Recently, a method for producing a 1.4BG biomass derivative using a biomass resource as a feedstock has also been developed, in addition to the conventional method of producing 1.4BG using petroleum or other fossil fuels as a raw material. cousin. For example, there is a method where succinic acid obtained by fermenting a sugar is hydrogenated to obtain 1.4BG (Patent Document 1), and a method where 1.4BG is directly obtained by fermenting a biomass resource such as sugar (Patent Document Patent 2).
[005] When a product comparable with a petrochemical product produced from a fossil fuel such as oil is produced from a biomass resource, a refining process on an industrial scale (large scale process) is required to stably maintain the volume or production quality. For example, in the case where the biomass resource used as a raw material is sugar or the like, the target product is obtained by fermenting it with bacteria, but to maintain the quality equivalent to that of a product obtained by the conventional production process using a fossil fuel such as petroleum, a refining technique capable of highly removing impurities contained in the raw material or various by-products generated during fermentation is required.
[006] As an example of such a refining technique, a refining method with respect to biomass-derived 1,3-propanediol is described in Patent Document 3.
[007] Also, as a method for refining 1.4BG derived from biomass, a general refining method is described in Patent Document 4. REFERENCE TECHNIQUE DOCUMENT PATENT DOCUMENT
[008] Patent Document 1: JP-A-2009-077719 (the term "JP-A", as used in this application, means "unexamined published Japanese patent application")
[009] Patent Document 2: JP-T-2010-521182 (the term "JP-T" as used in this application means a published Japanese translation of the PCT patent application)
[0010] Patent Document 3: JP-T-2007-502325
[0011] Patent Document 4: Publication of U.S. Patent Application 2011/0003355 SUMMARY OF THE INVENTION PROBLEM THAT THE INVENTION MUST SOLVE
[0012] However, Patent Document 4 does not have, for example, a specific reference to detailed refining conditions or substances responsible for quality deterioration and is silent on the method for removing such substances, and the method can only be applied to a large-scale process in the industry.
[0013] Also, in the production of polybutylene terephthalate (hereinafter, sometimes referred to simply as "PBT"), which is one of the main uses of 1.4BG, when the 1.4BG derived from biomass is used as a material. raw material for the production of PBT, impurities derived from the raw material or various impurities generated in the course of fermentation of the biomass resource such as sugar can be mixed, as a result, the color tone may deteriorate compared to PBT starting from 1, Conventional 4BG derived from a fossil fuel such as petroleum.
[0014] Under these circumstances, the present invention has been made, and an object of the present invention is to provide a method for producing a high quality 1.4BG biomass derivative capable of elaborating a PBT raw material with good color tone, where the various impurities mixed together when producing the 1,4BG derived from biomass on an industrial scale can be efficiently removed and refined. MEANS TO SOLVE THE PROBLEM
[0015] The present inventors made intensive studies to achieve the object described above. As a result, it was found that in a distillation column used in the refining step when producing the 1.4BG derived from biomass on an industrial scale, fouling continues due to precipitation of a solid matter and deterioration in the quality of 1.4BG continues due to the production of tetrahydrofuran (hereinafter, sometimes referred to simply as "THF") and water; the above quality deterioration can be overcome by employing a refining process that goes through a specific refining step; and when producing PBT using biomass-derived 1.4BG, the concentration of a cyclic carbonyl compound having a number of 5 or 6 carbon atoms contained in raw 1.4BG is correlated with the color of PBT and the removal of the carbon compound. -cyclic bonila in the step of refining 1,4BG derived from biomass and controlling the concentration of the compound to fall within a specific range, the obtained PBT color tone can be improved. The present invention was made based on these findings.
[0016] That is, the essence of the present invention resides in the following<1> to <15>.
[0017] <1> A method for producing 1,4-butanediol, comprising biologically producing 1,4-butanediol in a culture medium for fermenting an organism capable of producing 1,4-butanediol, at least partially removing each one from a bacterial cell, a saline and water content of said fermentation culture medium to obtain a solution containing 1,4-butanediol of the refined raw material, thereby obtaining a solution containing crude 1,4-butanediol by one or further steps from steps (a) to (c) below, refining said solution containing crude 1,4-butanediol by step (d) below to obtain refined 1,4-butanediol: Step (a):
[0018] a step of distilling said solution containing 1,4-butanediol from the refined raw material in a distillation column to remove the components that are contained in said solution containing 1,4-butanediol from the refined raw material and spot boiling higher than 1,4-butanediol; Step (b):
[0019] a step of distilling said solution containing 1,4-butanediol from the refined raw material in a distillation column to remove the components that are contained in said solution containing 1,4-butanediol from the refined raw material and spot boiling lower than 1,4-butanediol; Step (c):
[0020] a hydrogenation step to convert at least partially the unsaturated compounds contained in said 1,4-butanediol-containing solution of the refined raw material into a hydride; and Step (d):
[0021] a step of distilling said solution containing 1,4-butanediol from the raw material in a distillation column and removing refined 1,4-butanediol from a side stream.
[0022] <2> The method for producing 1,4-butanediol as described in <1> above, wherein the concentration of a cyclic carbonyl compound having a number of 5 or 6 carbon atoms in the 1,4-butanediol raffinate obtained in said step (d) is 12 ppm by mass or less.
[0023] <3> The method for producing 1,4-butanediol as described in <1> or <2> above, which is a method for producing 1,4-butanediol by at least step (a) outside of said steps (a) to (c) and further goes through the following step (e): Step (e):
[0024] a step of distilling components of higher boiling point than 1,4-butanediol, which are separated in said step (a), in a distillation column and thereby separating and recovering 1,4-butanediol .
[0025] <4> The method for producing 1,4-butanediol as described in any one of <1> to <3> above, which is a method for producing 1,4-butanediol at least through the step (c) outside of said steps (a) to (c), wherein the 1,4-butanediol-containing solution of the refined raw material after going through the next step (f) is introduced in said step (c):Step (f ):
[0026] a step of salinization of said solution containing 1,4-butanediol of the refined raw material in contact with a base.
[0027] <5> The method for producing 1,4-butanediol as described in any one of <1> to <4> above, wherein the concentration of water in the 1,4-butanediol containing solution of the refined feedstock immediately before going through any step of said steps (a) to (c) or step (f) is from 0.01 to 20% by mass and the pH of this is 5 or more.
[0028] <6> The method for producing 1,4-butanediol as described in any one of <1> to <5> above, wherein in the hydrogenation step of said step (c), the hydrogenation is carried out using a solid catalyst supporting a nickel-containing metal on at least kieselguhr or silica.
[0029] <7> The method for producing 1,4-butanediol as described in any one of <4> to <6> above, wherein the base in said step (f) is a solid base.
[0030] <8> The method for producing 1,4-butanediol as described in any one of <1> to <7> above, wherein the components of lower boiling point than 1,4-butanediol in said step (b) contain 1-acetoxy-4-hydroxybutane and the concentration of 1-acetoxy-4-hydroxybutane in the 1,4-butanediol-containing solution of the raw material after removal of said lower boiling point components than 1 ,4-butanediol is from 0.1 to 50 ppm by mass.
[0031] <9> The method for producing 1,4-butanediol as described in any one of <1> to <8> above, wherein the bottom temperature of the distillation column in said step (b) is 120°C at 200°C.
[0032] <10> The method for producing 1,4-butanediol as described in any one of <1> to <9> above, wherein the bottom temperature of the distillation column in said step (a) is 150 to 200°C.
[0033] <11> The method for producing 1,4-butanediol as described in any one of <1> to <10> above, wherein the components of boiling point higher than 1,4-butanediol in said step (a) contain 2-pyrrolidone and the concentration of 2-pyrrolidone in the solution containing crude 1,4-butanediol after removal of said higher boiling point components than 1,4-butanediol is 20 ppm by mass or less .
[0034] <12> The method for producing 1,4-butanediol as described in any one of <1> to <11> above, wherein a heating source of the distillation column in said step (a) substantially contacts only with the bottom liquid, but it does not involve any contact with a part of the gas phase.
[0035] <13> The method for producing 1,4-butanediol as described in any one of <1> to <12> above, wherein the concentration of gamma-butyrolactone in the head distillate in said step (d ) is higher than the concentration of gamma-butyrolactone in refined 1,4-butanediol taken from a side stream.
[0036] <14> The method for producing 1,4-butanediol as described in any one of <1> to <13> above, comprising a step of controlling the valence of the carbonyl in the 1,4-butanediol containing solution of the material. raw refined just before going through any step of said steps (a) to (c) or step (f), to be 2.5 mg KOH/g or less.
[0037] <15> The method for producing 1,4-butanediol as described in any one of <1> to <14> above, wherein in at least one step of said steps (b) to (d), the valence of the carbonyl in said solution containing 1,4-butanediol of the refined raw material is reduced. ADVANTAGEOUS EFFECTS OF INVENTION
[0038] According to the present invention, high quality 1.4BG capable of elaborating from a PBT raw material with good color tone can be produced, by efficiently removing and refining mixed impurities while producing a 1.4BG derivative biomass on an industrial scale. BRIEF DESCRIPTION OF THE DRAWINGS
[0039] Fig. 1 is a systematic diagram of steps (a) to (f) which illustrates a preferred embodiment of the present invention.
[0040] Fig. 2 is a graph showing the relationship between the concentration of cyclic carbonyl C5, total C6 in 1.4BG and the color hue value of PBT obtained using 1.4BG.
[0041] Fig. 3 is a graph showing the relationship between the concentration of cyclic carbonyl C5, total C6 in 1.4BG and the rate of polycondensation when producing PBT using 1.4BG. HOW TO PERFORM THE INVENTION
[0042] The present invention is described in detail below, but the respective constituent requirements described below are a representative example of the embodiment of the present invention, and the present invention is not limited thereto.
[0043] Incidentally, a numerical range expressed using the expression "(numeric value) to (numeric value)" in the description of the present invention means a range that includes the numerical values before and after "a" as a lower limit and an upper limit, respectively. Furthermore, a lower limit or an upper limit in the description of the present invention means a range that includes a numerical value of the lower limit or the upper limit.
[0044] Incidentally, in the description of the present invention, the expression "% by weight", "ppm by weight" and "ratio by weight" have the same meanings as "% by mass", "ppm by mass" and " proportion by mass", respectively. Also, when simply referred to as "ppm", this indicates "ppm by weight".
[0045] The purification process in the production method for 1,4-BG of the present invention is preferably applied to a composition containing 1,4BG derived from biomass.
[0046] Biomass material includes a material in which the light energy of the sun is converted into a form of starch, cellulose or the like by the photonic synthesis of a plant and stored, the body of an animal that grows by eating plants, a product obtained by processing a vegetable body or an animal body and the like.
[0047] Specifically, wood, rice straw, rice bran, old rice, corn, sugar cane, cassava, sago palm, soybean pulp, corn cobs, tapioca waste, bagasse, vegetable oil waste , potatoes, buckwheat, soybeans, fats, old paper, papermaking waste, fish industry product waste, domestic animal faeces, sewage sludge, food waste and the like are mentioned. Among them, vegetable materials such as wood, rice straw, old rice, corn, sugar cane, cassava, sago palm, soy pulp, corn cobs, tapioca waste, bagasse, vegetable oil waste, potatoes, buckwheat, soybeans, fats, old papers and papermaking residues are preferred. The most preferred materials are wood, rice straw, old rice, corn, sugar cane, cassava, sago palm, potatoes, fats, old paper, paper manufacturing waste and the like and the most preferred materials are corn, cane sugar, cassava and sago palm.
[0048] Biomass materials generally contain nitrogen atom, many alkali metals and alkaline earth metals such as Na, K, Mg and Ca.
[0049] These biomass materials are induced to carbon sources by a known pre-treatment/saccharification step and the like, such as chemical treatment using an acid treatment, an alkaline or similar, biological using a microorganism and physical treatment, although the method is not particularly limited. Often the step includes a step for size reduction by pre-treatment to chop, trim or grind the biomass material, and if necessary, further includes a pulverization step using a crusher or a mill.
[0050] Biomass material that has been reduced in size in this way is usually induced to a carbon source by an additional pretreatment/saccharification step. Examples of the specific method are: chemical methods such as acid treatment using strong acid such as sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid, alkaline treatment, freezing ammonia vapor blasting method, extraction with a solvent, supercritical fluid treatment. co and treatment with an oxidizing agent; physical methods such as spraying, steam blasting method, microwave and electron beam irradiation treatment; and biological treatment such as hydrolysis by treatment with a microorganism or an enzyme.
[0051] In general, as the induced carbon source of the above biomass materials, the following fermentative carbohydrates and the like are used: hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose; pentoses such as arabinose, xylose, ribose, xylulose and ribulose; di- and polysaccharides such as pentosan, sucrose, starch and cellulose; fat such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monocutic acid, arachidic acid, eicosanoic acid, acid arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docohexaenoic acid, lignoceric acid, and selacoleic acid; and polyalcohols such as glycerin, mannitol, xylitol and ribitol. Among them, hexoses, pentoses or disaccharides such as glucose, fructose, xylose or sucrose are preferred and glucose is particularly preferred. Cellulose, which is the main component of papers, is also preferred as a plant-derived carbon source in a broader sense.
[0052] In the method of producing 1,4BG directly from a carbon source such as glucose by a fermentation process, transgenic E. coli, a coryneform bacteria, yeast, etc. can be used. For example, 1,4BG can be biologically produced in culture medium for organism fermentation by the method described in JP-T-2010-521182.
[0053] Furthermore, a composition containing 1.4BG that is biologically produced in this way in a culture medium for fermentation of an organism capable of producing 1.4BG can be obtained, for example, entirely or at least partially by separation and removal of the bacterial cells and saline contents by either separation means or two or more separation means of filtration, centrifugal separation and an ion exchange resin based on US Patent Application Publication No. 2011/0003355, and in addition, a solution containing 1 ,4BG of the refined raw material obtainable from the above 1,4BG-containing composition by at least partially removing the water in the composition.
[0054] In the present invention, the "composition containing 1,4BG" indicates a composition after removing the bacterial cells and saline contents from the fermentation culture medium in which 1,4BG is produced, and the residue after removing water from the composition containing 1.4BG above is referred to as "1.4BG containing solution of the refined raw material".
[0055] The method for removing the water contained in the composition containing 1.4BG after separation and removal of bacterial cells and saline contents from the fermentation culture medium is not particularly limited, but these are preferably removed by batch or continuous distillation. As the distillation column used for distillation/dewatering, a distillation column having from 2 to 100 trays as the theoretical tray is preferably used, and the number of theoretical trays is more preferably from 5 to 50.
[0056] The reflux ratio is arbitrated, but is preferably from 0.01 to 100. The reflux ratio is more preferably from 0.1 to 50, even more preferably from 0.2 to 20.
[0057] The reboiler as the heating region of a distillation column is not particularly limited, but is preferably a forced circulation reboiler or a falling film reboiler. Especially, the residence time in the region of contact with a bottom heating source is preferably shorter to avoid fouling, and a structure where the heating source is not placed in contact with a part of the gas phase or a structure where the amount contact is minimized, is preferred.
[0058] The top pressure of the distillation column is, in terms of absolute depression, preferably from 1 to 200 kPa, more preferably from 2 to 100 kPa, even more preferably from 5 to 50 kPa. As the top pressure is lower, the temperature in the column can be reduced, and the production of new impurities from biomass-derived components like amino acid and sugar can be thereby avoided, but if the top pressure is too low, the cooling becomes inefficient. Also, as the top pressure is higher, the volume of the column itself can be reduced, but if the top pressure is too high, the bottom temperature increases and impurities are likely to be produced.
[0059] The temperature in the distillation column is determined by the composition and pressure, but the temperature at the bottom where the temperature is highest is preferably from 120 to 200°C, more preferably from 140 to 190°C, even more preferably from 150 to 180°C. By making the bottom temperature of the distillation column higher than the lower limit above, the top temperature can also be high and the cost of cooling can be kept low. Also, by making the bottom temperature lower than the upper limit above, impurities due to a side reaction of biomass-derived components can be reduced.
[0060] The top temperature is preferably from 40 to 100°C, more preferably from 40 to 80°C, even more preferably from 40 to 60°C. By making the top temperature no lower than the lower limit above, the cooling cost can be kept low, and by making the top temperature no higher than the upper limit above, a side reaction in the column can be suppressed.
[0061] The preferred head distribution ratio (= (head distillate flow rate/feed flow rate) x 100) in the distillation column varies depending on the concentration of water in the composition containing 1.4BG, but is preferably of 2 to 40%, more preferably 5 to 30%, even more preferably 8 to 25%. If the head distribution ratio is too high, the 1.4BG loss is increased, whereas if the head distribution ratio is too small, a fairly large amount of water and low-boiling acid is transferred into the solution. containing 1.4BG fed to the next step, i.e. the 1.4BG containing solution of the refined raw material.
[0062] In this distillation column, the pH at the bottom is preferably controlled to be from 4 to 9, more preferably from 5 to 8. If the pH is too low, THF underproduction is increased in the distillation column and the operation becomes if difficult. If the pH is too high, a side reaction such as high boiling is promoted.
[0063] The bottom product obtained from the dewatering distillation column, that is, the solution containing 1.4BG of the refined raw material, is fed to the next refining step. A distillate containing water and a large number of components low boiling point can be discarded in state, but can be used for washing, etc. of other steps.
[0064] The solution containing 1.4BG of the refined raw material obtained by removing water from the composition containing 1.4BG by such a distillation operation is withdrawn from the bottom of the above distillation column. This 1.4BG containing solution of the refined raw material contains 1.4BG and components higher or lower in boiling point than 1.4BG.
[0065] The components in addition to 1.4BG, contained in the solution containing 1.4BG of the refined raw material, are gamma-butyrolactone, 1-acetoxy-4-hydroxybutane, tetrahydrofuran, acetic acid, butanol, butylaldehyde, butyric acid, 1,3-butanediol, 2,3-butanediol, 2-hydroxytetrahydrofuran, 2-(4-hydroxybutyloxy) tetrahydrofuran, water, nitrogen-containing components derived from amino acids and proteins, sugar and a decomposition product thereof .
[0066] This solution containing 1.4BG of the refined raw material can be converted by refining the present invention to a 1.4BG derived from high quality biomass capable of preparing a PBT raw material with good color tone, but in order To obtain 1.4BG by preparing a PBT raw material with good color tone, it is preferable to reduce the carbonyl valence of the solution containing 1.4BG of the refined raw material.
[0067] The carbonyl valence value of the solution containing 1.4BG of the refined raw material is preferably 2.5 mg KOH/g or less, more preferably 2.0 mg KOH/g or less, even more preferably 1, 5 mg KOH/g or less. As the valence value of carbonyl is lower, the refining cost of the present invention can be reduced and this is economically preferable.
[0068] The solution containing 1.4BG of the refined raw material in this order indicates 1.4BG of the refined raw material immediately before going through steps (a) to (c) and in case of going through step (f) described after, indicates 1.4BG of raw material refined just before going through step (f).
[0069] The method for reducing the carbonyl valence in the solution containing 1.4BG of the refined raw material is not particularly limited, but includes, for example, a method where the carbonyl valence is reduced in the biological production process of 1, 4BG in culture medium for fermenting organisms and a method where the carbonyl component is reduced together with water in the process of removing the water contained in the composition containing 1.4BG after separating and removing bacterial cells and saline contents of the culture medium from fermentation. In the present invention, the valence of the carbonyl in the 1.4BG-containing solution of the refined raw material is preferably reduced in at least one step of the steps described below (b) to (d).
[0070] The method for measuring the valence of carbonyl is as described in the Examples below.
[0071] The concentration of water in the solution containing 1.4BG of the refined raw material is not particularly limited, but normally, the upper limit is 20% by mass or less, preferably 18% by mass or less, more preferably 15% by mass or less. On the other hand, the lower limit is usually 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% by mass or more. If the concentration of water in the solution containing 1.4BG of the refined raw material is too high, the temperature of the top region steam recovery at a later stage reduces and becomes inappropriate. Also, if the concentration of water in the 1,4BG-containing solution of the refined raw material is excessively reduced, the distillation load for water removal is disadvantageously increased.
[0072] The solution containing 1.4BG of the refined raw material in this order indicates 1.4BG of the refined raw material immediately before going through steps (a) to (c) and in case of going through step (f) described below , indicates 1.4BG of refined raw material just before going through step (f).
[0073] Incidentally, the concentration of water in the 1.4BG-containing solution of the refined raw material introduced in the hereinafter described step (a) is preferably 1.5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less. Therefore, when the water concentration after dewatering the composition containing 1.4BG is more than the upper limit above, it is preferable to reduce the water concentration by further repeating the same distillation as above.
[0074] The pH of the solution containing 1.4BG of the refined raw material is preferably 5 or more, more preferably from 5.0 to 9.0, even more preferably from 5.2 to 8.0. A low pH of the 1.4BG-containing refined raw material solution means that the bottom liquid pH of the dewatering distillation column is low, and a problem of THF underproduction arises as described above. Also, if the pH of the solution containing 1.4BG of the refined raw material is too high, that is, the bottom liquid pH of the dewatering distillation column is too high, a side reaction such as the occurrence of product from high boiling point is promoted as described above.
[0075] The concentration of 1.4BG in the 1.4BG-containing solution of the refined raw material is not particularly limited, but normally, the lower limit is 80% by mass or more, preferably 82% by mass or more, more preferably 85% in bulk or more. On the other hand, the upper limit is usually 99.5% by mass or less, preferably 99.0% by mass or less, more preferably 98.0% by mass or less. Although the concentration varies depending on the type of purity mixed and cannot be indiscriminately specified, with a concentration not more than the upper limit above, the load of the fermentation step is reduced, and 1.4BG having the highest quality in the set can be obtained.
[0076] In the present invention, a solution containing crude 1.4BG is obtained from the 1.4BG containing solution of the refined raw material by passing through at least one method in addition to a method where the components of boiling point higher than 1 ,4BG in the 1,4BG-containing solution of the refined raw material are removed through at least one or more steps of steps (a) to (c) below, a method where the low-boiling components are removed, and a method where an unsaturated compound is converted to a hydride, and the solution containing crude 1.4BG is refined by the next step (d) whereby high purity refined 1.4BG is obtained.
[0077] Also, in the present invention, the following step (e) can be further performed, and the following step (f) can be performed before step (c). Step (a):
[0078] A step of distilling the solution containing 1.4BG from the refined raw material in a distillation column to remove components that are contained in the solution containing 1.4BG from the refined raw material and boiling point higher than 1, 4BG. Step (b):
[0079] A step of distilling the solution containing 1.4BG of the refined raw material in a distillation column to remove the components that are contained in the solution containing 1.4BG of the refined raw material and boiling point lower than 1 ,4BG.Step (c):
[0080] A hydrogenation step to convert at least partially unsaturated compounds contained in the 1.4BG-containing solution of the refined raw material into a hydride. Step (d):
[0081] A step of distilling the solution containing crude 1.4BG in a distillation column and removing refined 1.4BG from a side stream. Step (e):
[0082] A step of distilling components of higher boiling point than 1.4BG, which are separated in step (a), and thereby separating and recovering 1.4BG.Step (f):
[0083] A step of salinization of the solution containing 1.4BG of the refined raw material in contact with a base.
[0084] These steps (a) to (f) according to the present invention are described in detail below, but in the following description of each step, unless otherwise indicated, the distillation operation in a distillation column may be a batch system or a continuous system, and in view of productivity, a continuous system distillation operation is preferred. Also, the distillation can be single-stage distillation or multi-stage distillation, but in view of the separation performance, multi-stage distillation is preferred, and in the distillation column, a tray or a regular and/or irregular packing material can be used.
[0085] Steps (a) to (c) are preceding steps before introducing the solution containing 1.4BG of the refined raw material in step (d), and 1.4BG of the refined raw material is passed through one step, two steps or all steps from steps (a) to (c) and thereafter introduced in step (d). In case of carrying out two or more steps outside of steps (a) to (c), the order of steps is not particularly limited.
[0086] At the time of PBT production using, as a raw material, refined 1.4BG obtained in step (d), from the point of view that the color of the obtained PBT can be suppressed, the solution containing 1.4BG of the material The refined raw is preferably passed through all the steps of steps (a) to (c) and then introduced in step (d). In this case, the order of respective steps can be mixed, but the order is preferably step (a) ^ step (c) ^ step (b) ^ step (d).
[0087] Fig. 1 is a systematic diagram illustrating the order of the steps when all steps (a) to (f) are employed, which is a preferred embodiment of the present invention.
[0088] The operation at each step is described below along with this systematic diagram, but the present invention is not limited to the embodiment shown in Fig. 1, and one or two steps may be omitted outside of steps (a) to (c) or one or more steps outside of steps (e) and (f), or further steps can be added further.Step (a): a distillation step to remove components with a boiling point higher than 1.4BG
[0089] In step (a), components (higher boiling point component) higher in boiling point than 1.4BG are removed from the solution containing 1.4BG of the refined raw material in a distillation column (a hereinafter, sometimes referred to as "distillation column (a)"), whereby a solution containing crude 1.4BG free of higher boiling components is obtained as a head distillate of distillation column (a).
[0090] As described above, the concentration of water in the solution containing 1.4BG of the refined raw material introduced into the distillation column (a) is preferably 1.5% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less. By establishing the water concentration in the 1.4BG-containing solution of the refined raw material introduced into the distillation column (a) to be no more than the upper limit above, the occurrence of a situation where steam cannot be recovered from a condenser cooling due to an excessive reduction in the top temperature of the distillation column can advantageously be avoided. Therefore, when the water concentration in the solution containing 1.4BG of the refined raw material is greater than the upper limit above, the solution containing 1.4BG of the refined raw material is preferably introduced into the distillation column (a ) after removing the water by further repeating the distillation.
[0091] In step (a), among others, nitrogen-containing components derived from amino acid and protein and components with a boiling point higher than 1.4BG, which are peculiar to the fermentation process, such as sugar and a decomposition product from this, they are removed.
[0092] The component containing nitrogen as the amino acid is lightly boiled in amides, etc. by heating and especially amides having a carbon number of 4, such as 2-pyrrolidone, are sometimes allowed to be contained. These amides also become causative of coloring at the time of PBT production and are preferably separated at the same time by this distillation operation.
[0093] Among others, in the case where 1,4BG as raw material of PBT contains 2-pyrrolidone, changing the color at the time of production of PBT becomes conspicuous. Therefore, the high-boiling components are removed until the concentration of 2-pyrrolidone in the solution containing crude 1.4BG which is the distillate from distillation column (a) is preferably reduced to 100 ppm by mass or less, plus preferably 20 ppm by mass or less, even more preferably 10 ppm by mass. On the other hand, the lower limit of the concentration of 2-pyrrolidone in the distillate is preferably lower, but it is usually 0.01 ppm by mass or more, preferably 0.05 ppm by mass or more, more preferably 0.1 ppm by mass or more.
[0094] The concentration of the nitrogen atom containing compound such as 2-pyrrolidone can be controlled by the nitrogen atom concentration, and although not particularly limited the nitrogen atom concentration in the distillate is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 20 ppm by mass or less.
[0095] The distillation column (a) used is preferably a distillation column having, as theoretical tray, from 3 to 100 trays, more preferably from 5 to 50 trays.
[0096] The reflux ratio is arbitrated, but it is preferably from 0.01 to 100, more preferably from 0.1 to 50. First of all, a reflux ratio from 0.2 to 20 is preferred.
The reboiler as the heating region of the distillation column (a) is not particularly limited, but is preferably a forced circulation reboiler or a falling film reboiler. Especially, the residence time in the region of contact with a heating source at the bottom is preferably shorter to avoid fouling, and a structure where the heating source is not placed in contact with a part of the gas phase or a structure where the amount contact is minimized, is preferred. It is also possible to recover steam from a cooling condenser at the top of the distillation column (a).
[0098] The top pressure of the distillation column (a) is, in relation to the absolute pressure, preferably from 1 to 200 kPa, more preferably from 2 to 100 kPa, even more preferably from 5 to 50 kPa. As the head pressure is lower, the temperature in the column can be reduced, and the production of new impurities from biomass-derived components like amino acid and sugar can thereby be avoided. Also, as the top pressure is higher, the vapor recovery from the top region is more successful and in addition, the volume of the column itself can be reduced.
[0099] The temperature in the distillation column (a) is determined by the composition and pressure, but the temperature at the bottom where the temperature is highest is preferably from 150 to 200°C, more preferably from 160 to 195°C, even more preferably from 165 to 190°C. By making the bottom temperature of the distillation column (a) no less than the lower limit above, the top region steam recovery can be prevented from failing due to too low temperature, and making the bottom temperature no more than the upper limit above, the increase in by-product production volume can be avoided.
The top temperature is preferably from 140 to 190°C, more preferably from 150 to 185°C, even more preferably from 155 to 180°C. By making the top temperature not less than the lower limit above, the vapor recovery from the top region can be prevented from failing, and by making the top temperature no more than the upper limit above, the increase in the volume of production of by-products can be avoided.
[00101] The distillate obtained in the distillation column (a) removing components with a boiling point higher than 1.4BG is transferred to the next step. The bottoms product containing a large number of components with a boiling point higher than 1.4BG can be discarded in the state, but is preferably fed to the distillation step (e) of recovery of 1.4BG.
[00102] The fouling rate at the bottom of the distillation column (a) removing components of higher boiling point than 1.4BG can be greatly reduced by maintaining the concentration of 1.4BG in the bottoms of the distillation column (a) high, which contains a large number of components with a boiling point higher than 1.4BG. This is due to the excess concentration of a high-boiling component that promotes the precipitation of amino acid, protein or a solid component such as sugar. Therefore, the bottom product taken from the bottom of the distillation column (a) preferably contains 1.4BG to some extent, and the concentration of 1.4BG in the bottom product is preferably 40 to 99.2% by mass, plus preferably from 50 to 99.0% by mass, even more preferably from 55 to 98.8% by mass.
[00103] Incidentally, the head distribution ratio (= (head distillate flow rate/feed flow rate) x100) in the distillation column (a) is preferably from 50 to 98%, more preferably from 60 to 95%, even more preferably from 70 to 90%.
[00104] In this application, from the point of view that 1.4BG contained in the higher boiling point components than 1.4BG, which are separated in step (a), can still be recovered the production method preferably still has the following step (e), in addition to steps (a) to (d). Step (e): a step of separating and recovering 1.4BG from the components with a boiling point higher than 1.4BG, which are separated in step (a)
[00105] In step (e), components with a boiling point higher than 1.4BG, which are separated in step (a), i.e. the distillate from distillation column (a), are distilled in a column of distillation (hereinafter, sometimes referred to as "distillation column (e)") for separation and recovery of 1.4BG.
[00106] The distillation column (e) used in step (e) is preferably a distillation column having, as theoretical tray, from 2 to 50 trays, more preferably from 5 to 30 trays.
[00107] The reflux ratio is arbitrated, but it is preferably from 0.01 to 100, more preferably from 0.1 to 50. First of all, a reflux ratio from 0.2 to 20 is preferred. It is also possible to recover steam from a cooling condenser at the top of the distillation column (e).
[00108] The reboiler as the heating region of the distillation column (e) is not particularly limited, but is preferably a forced circulation reboiler or a falling film reboiler. Especially, the residence time in the region of contact with a heating source at the bottom is preferably shorter to avoid fouling, and a structure where the heating source is not placed in contact with a part of the gas phase or a structure where the amount contact is minimized, is preferred. Incidentally, unlike the distillation column (a) of step (a), when the interior of the distillation column (e) of step (e) is embedded, it is only possible to stop the distillation column (e) once and conduct a bypass operation all this time, even in the middle of the continuous operation of steps (a) to (d).
[00109] The top pressure of the distillation column (e) is, with respect to the absolute pressure, preferably from 0.1 to 100 kPa, more preferably from 0.2 to 50 kPa, even more preferably from 1 at 20 kPa. As the top pressure is lower, the temperature in the column can be reduced, allowing to prevent the production of new impurities from biomass-derived components such as amino acid and sugar, and at the same time, clogging due to the progress of polymerization at the bottom. can be avoided. Also, as the top pressure is higher, the volume of the column itself can be reduced.
[00110] The bottom temperature of the distillation column (e) is preferably from 150 to 200°C, more preferably from 160 to 195°C, even more preferably from 165 to 190°C. By making the bottom temperature of the distillation column (a) no less than the lower limit above, the top region steam recovery can be prevented from failing due to too low temperature, and making the bottom temperature no more than the upper limit above, the by-product may be prevented from increasing in its production volume or becoming a cause of fouling.
[00111] The top temperature is preferably from 140 to 190°C, more preferably from 150 to 185°C, even more preferably from 155 to 180°C. By making the top temperature not less than the lower limit above, the vapor recovery from the top region can be prevented from failing due to the very low temperature, and by making the top temperature no more than the upper limit above, the increase in by-product production volume can be avoided.
[00112] The distillate containing 1.4BG separated in the distillation column (e) is preferably made circulated in the distillation column (a) for recovery of 1.4BG. The bottoms product containing a greater number of high-boiling components concentrated in the distillation column (e) is discarded in the state, but is preferably incinerated to recover heat.
[00113] Almost all high boiling point components can be discharged by this distillation operation, but a larger number of high boiling point components including 2-pyrrolidone can still be discarded when distillation column (e) is set up to have theoretical trays in the range described above. In addition, a large amount of nitrogen content or sulfur content in the high-boiling components can be discharged.Step (c): a hydrogenation step of unsaturated compounds contained in the 1.4BG-containing refined raw material solution
[00114] In step (c), color-causing components of refined 1,4BG and/or color-causing components at the time of PBT production using refined 1,4BG as a raw material are eliminated. Specifically, a carbonyl compound such as ketone, aldehyde and ester, an unsaturated compound having an olefin moiety, etc. is converted to hydrides by a hydrogenation reaction, resulting in the disappearance of a carbonyl bond and an olefin moiety contained in the compound structures that are a causative component of the color. The hydrides obtained can be removed as an alcohol, etc. by distillation.
[00115] Out of these coloring components, a cyclic carbonyl compound having a number of 5 or 6 carbons, such as ketone and/or aldehyde, has a significantly adverse effect on color tone at the time of PBT production and therefore, in step (c), the cyclic carbonyl compound having a number of 5 or 6 carbon atoms is preferably converted to a hydride and reduced in its concentration, whereby a remarkable color tone improvement effect at the time of production of PBT is obtained. The "cyclic carbonyl compound having a number of 5 or 6 carbon atoms", as used in this application, denotes both a cyclic carbonyl compound having a number of 5 carbon atoms and a cyclic carbonyl compound having a number of 6 carbon atoms.
[00116] Also, the total amount of these carbonyl compounds can be controlled as a carbonyl valence, and the carbonyl valence can be reduced in step (c).
[00117] The cyclic carbonyl compound having a number of 5 or 6 carbon atoms is preferably a compound having a 5-membered ring structure or a 6-membered ring structure, more preferably having a cyclic skeleton containing oxygen atom. Specifically, the compound includes one or more compounds selected from the group consisting of compounds that represent structures by the following formulas (I), (II) and (III):

[00118] (wherein in formula (I), each of R1 to R4 independently represents a hydrogen atom, a methyl group, a formyl group or an acetyl group, any one of R1 to R4 is a formyl group or an acetyl group , and the total number of carbon atoms contained in the respective groups from R1 to R4 is 2 or less);

[00119] (wherein in formula (II), each of a plurality of X independently represents a carbon atom or an oxygen atom, the total number of oxygen atoms contained in the plurality of X is 1, each of R5 to R9 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in the respective groups from R5 to R9 is 1 or less); and

[00120] (wherein in formula (III), each of R10 to R13 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in the respective groups from R10 to R13 is 1 or less) .
[00121] More specifically, as examples of the compound having a structure represented by the formula (I), the compound having a number of 5 carbon atoms includes tetrahydro-2-furaldehyde, tetrahydro-3-furaldehyde and the like and the compound having a number of 6 carbon atoms includes 2-acetyltetrahydrofurano[1-(tetrahydrofuran-2-yl)ethanone], 3-acetyltetrahydrofurano[1-(tetrahydrofuran-3-yl)ethanone] , 5-methyltetrahydro-2-furaldehyde, 4-methyltetrahydro-2-furaldehyde, 3-methyltetrahydro-2-furaldehyde, 2-methyltetrahydro-3-furaldehyde, 4-methyltetrahydro-3-furaldehyde , 5-methyltetrahydro-3-furaldehyde, 2-(tetrahydrofuran-2-yl)acetaldehyde, 3-(tetrahydrofuran-2-yl)acetaldehyde, etc.
[00122] As examples of the compound having a structure represented by the formula (II), the compound having a number of 5 carbon atoms includes tetrahydro-4H-pyran-4-one and the like and the compound having a number of 6 carbon atoms include 3-methyltetrahydro-4H-pyran-4-one, 2-methyltetrahydro-4H-pyran-4-one, 2-formyl-tetrahydropyran, 3-formyl-tetrahydropyran, 4 -formyl-tetrahydropyran, etc.
[00123] As examples of the compound having a structure represented by the formula (III), the compound having a number of 5 carbon atoms includes dihydro-2H-pyran-3(4H)-one and the like and the compound which has a number of 6 carbon atoms includes 2-methyldihydro-2H-pyran-3(4H)-one, 4-methyldihydro-2H-pyran-3(4H)-one, 5-methyldihydro- 2H-pyran-3(4H)-one, 6-methyldihydro-2H-pyran-3(4H)-one, etc.
[00124] Preferably, as examples of the compound having a structure represented by the formula (I), the compound having a number of 5 carbon atoms is tetrahydro-2-furaldehyde, and the compound having a number of 6 carbon atoms. carbon is 2-acetyltetrahydrofurano[1-(tetrahydrofuran-2-yl)ethanone], 3-acetyltetrahydrofurano[1-(tetrahydrofuran-3-yl)ethanone] or 5-methyltetrahydro-2- furaldehyde; as the compound having a structure represented by formula (II), the compound having a number of 5 carbon atoms is tetrahydro-4H-pyran-4-one, and the compound having a number of 6 carbon atoms is 2- methyltetrahydro-4H-pyran-4-one or 2-formyl-tetrahydropyran; and as the compound having a structure represented by the formula (III), the compound having a number of 5 carbon atoms is dihydro-2H-pyran-3(4H)-one, and the compound having a number of 6 carbon atoms is 2-methyldihydro-2H-pyran-3(4H)-one, 4-methyldihydro-2H-pyran-3(4H)-one, 5-methyldihydro-2H-pyran-3( 4H)-one or 6-methyldihydro-2H-pyran-3(4H)-one.
[00125] More preferably, as the compound having a structure represented by formula (I), the compound having a number of 5 carbon atoms is tetrahydro-2-furaldehyde, and the compound having a number of 6 carbon atoms. carbon is 2-acetyltetrahydrofurano[1-(tetrahydrofuran-2-yl)ethanone]; as the compound having a structure represented by formula (II), the compound having a number of 5 carbon atoms is tetrahydro-4H-pyran-4-one, and the compound having a number of 6 carbon atoms is 2- methyltetrahydro-4H-pyran-4-one; and as the compound having a structure represented by the formula (III), the compound having a number of 5 carbon atoms is dihydro-2H-pyran-3(4H)-one, and the compound having a number of 6 carbon atoms is 2-methyldihydro-2H-pyran-3(4H)-one, 4-methyldihydro-2H-pyran-3(4H)-one or 5-methyldihydro-2H-pyran-3( 4H)-one.
[00126] These cyclic carbonyl compounds having a number of 5 or 6 carbon atoms are thought to be derived from the sugar used as a raw material for fermentation and are supposed to be produced in the fermentation step and/or in the step of refining by the cyclization of polyhydric alcohols having a number of 5 or 6 carbon atoms derived from pentose and/or hexose.
[00127] The concentration of the cyclic carbonyl compound having a number of 5 or 6 carbons is, in relation to the concentration in the solution introduced in the hydrogenation step (c), preferably from 0.001 to 2% by mass, more preferably from 0. 01 to 1% by mass, even more preferably from 0.02 to 0.5% by mass. When the concentration of the cyclic carbonyl compound having a number of 5 or 6 carbons in the solution introduced in the hydrogenation step (c) is not more than the upper limit above, the deterioration of the color tone at the time of PBT production is avoided. Also, in the case where the concentration is below the lower limit, although this is a preferred modality, the reaction conditions must be strict and therefore, from an economic point of view, the concentration is preferably not less than the lower limit above.
[00128] The cyclic carbonyl compound having a number of at least 5 or 6 carbon atoms is partially hydrogenated in step (c), As a result, the UV absorption value is reduced and the valence of the carbonyl is also reduced. Incidentally, in step (c), at least 10% or more of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms is preferably hydrogenated, and this proportion is more preferably 20% or more, even more preferably 40% or more. Also, the concentration in the solution passing through the hydrogenation step (c) is, as carbonyl compounds a total of cyclics having a number of 5 or 6 carbon atoms, preferably 0.1% by mass or less, more preferably 0 .08% by mass or less.
[00129] The method for hydrogenation in step (c) is not particularly limited, but the causative component described above which has a number of 5 or 6 carbon atoms, such as ketone, ester and aldehyde, can be hydrogenated in the presence of various hydrogenation catalysts. The hydrogenation catalyst is arbitrated although it is a catalyst capable of hydrogenating a cyclic carbonyl compound such as ketone and aldehyde, but it is preferred to use a solid catalyst containing at least one metal or two or more metals such as nickel (Ni), palladium (Pd ), ruthenium (Ru), platinum (Pt) and copper (Cu), and a catalyst containing Ni is most preferred.
[00130] The amount of the metal as Ni, Pd, Ru, Pt and Cu in the hydrogenation catalyst is preferably from 5 to 80% by mass, more preferably from 15 to 80% by mass, even more preferably from 50 to 80% by mass pasta. Incidentally, the form of the metal contained in the hydrogenation catalyst can be the metal itself or it can be a metal oxide. In the case where the proportion of metal oxide is high, a reductive activation treatment with a hydrogen gas can be carried out before starting the reaction, but the reaction can be started without such treatment.
[00131] The solid catalyst preferably contains a support, and the support includes silica, alumina, zirconia, kieselguhr and the like. Among others, the support preferably contains at least kieselguhr or silica.
[00132] The content of the support in the catalyst is preferably from 5 to 95% by mass, more preferably from 7 to 80% by mass, even more preferably from 10 to 60% by mass.
[00133] Although the solid catalyst for use in the present invention contains a metal such as Ni, Pd, Ru, Pt and Cu, the catalyst may contain other metals or metal oxides. For example, the catalyst may contain chromium, manganese, zinc, magnesium, sodium, rhenium and calcium, and especially a catalyst containing chromium and magnesium is preferred.
[00134] Such metal can also be contained as the metal itself or in the state of various salts such as oxide and hydroxide. For example, the magnesium oxide content in the catalyst is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 15% by mass, even more preferably from 1 to 10% by mass. One of these catalysts can be used alone, or two or more of these can be mixed and used.
[00135] The reaction temperature at the time of carrying out the hydrogenation of step (c) is not particularly limited, but is preferably from 0 to 200°C, more preferably from 30 to 150°C, even more preferably from 40 to 120°C. If this temperature is too high, deterioration of the catalyst is promoted, and in addition, the amount of high-boiling by-products is increased. If the reaction temperature is too low, the reaction just goes on.
[00136] The hydrogen pressure in hydrogenation is not particularly limited, but, in terms of gauge pressure, it can be from 0.1 to 100 MPa and is preferably from 0.5 to 10 MPa, more preferably from 1 to 6 MPa. If this pressure is too low, the reaction rate is low and productivity is reduced. If the pressure is too high, the use of a reactor material in a large amount and increase in the compressor load are involved, and the construction cost increases too much.
[00137] The hydrogenation reaction is preferably carried out by passing the solution containing 1.4BG of the refined raw material (in Fig. 1, the solution obtained by the additional treatment, in step (f), the distillate containing 1.4BG of the step (a)) for a reactor where a layer packed with the solid catalyst described above is formed, and at this time, the reaction time is, in terms of residence time based on the empty column, preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and is preferably 100 hours or less, more preferably 50 hours or less, even more preferably 10 hours or less. If this residence time is too short, the reaction just goes on, and if the residence time is too long, the layer packed with the catalyst becomes long and due to the increase in reactor installation cost and increase in the amount of catalyst , profitability deteriorates significantly.
[00138] As determined from the residence time based on the empty column, the amount of packed catalyst is, relative to the flow rate per minute of the introduced solution, preferably 0.05 times volume or more, more preferably 0.1 times volume or more, even more preferably 0.5 times by volume or more, and is preferably 100 times by volume or less, more preferably 50 times by volume or less, even more preferably 10 times by volume or less. If the amount of the packed catalyst is too small, the reaction just proceeds, and if the amount of the packed catalyst is too large, the catalyst cost increases by significantly deteriorating profitability.
[00139] As for the reaction mode, all general packed layer type hydrogenation reactors using various solid catalysts, such as fixed bed, drip bed, suspension bed (slurry) and multitube system, can be used, but a fixed bed reactor or a drip bed reactor is preferred. As a reactor, one reactor can be used, or a plurality of reactors can be used. Also, a filter selected so as not to transfer catalyst dust to further steps is preferably provided at the exit of the hydrogenation reactor.
[00140] In the case where a large amount of a hydrogenation catalyst powder or a molten metal is transferred to further steps, a 1,4BG dehydrogenation reaction can proceed in the heating region or the like to produce 2-hydroxytetrahydrofuran or 2-(4-hydroxybutyloxy)tetrahydrofuran.
[00141] In step (c), there is a fear of catalyst deterioration due to long-term continuous operation. Among others, the impurities in the 1,4BG-containing composition produced by a fermentation process contain components including chlorine, sulfur and the like. In order to remove these chlorine and sulfur components, it is preferable to carry out step (f) before step (c) beforehand. Step (f): a step of salinization of the solution containing 1.4BG of the raw material refined in contact with a base
[00142] In the present invention, the hydrogenation step (c) described above is preferably provided to remove cyclic carbonyl compounds that have a number of 5 or 6 carbon atoms, which are a causative component of the coloration, but as for the catalyst of hydrogenation, the deterioration of the catalyst is accelerated by a strong acid such as hydrochloric acid and sulfuric acid. On the other hand, composition containing crude 1,4BG produced by a fermentation process sometimes contains chlorine contents like hydrochloric acid or sulfur contents like sulfuric acid. Therefore, a step (f) of contacting a solid base or a soluble base such as amine with the 1.4BG-containing solution of the refined raw material to remove those contents is preferably provided in one stage before going through step (c ).
[00143] As the base usable in step (f), a base that dissolves in the solution containing 1.4BG of the refined raw material or solution containing 1.4BG crude, such as various amines, can be used, and specifically, the base is preferably trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tridecanylamine, triphenylamine, diphenylmethylamine, diphenylethylamine, diphenylbutylamine, dimethylphenylamine, diethylphenylamine, dibutylphenylamine, tricyclopentylamine, tricyclohexylamine, tricyclohexylamine 4-diazabicyclo[2.2.2]octan, 1,8-diazabicyclo[5.4.0]-7-undecane, 1,5-diazabicyclo[4.3.0]-5-nonene, 2,5-diazabicyclo[2.2.1] heptane and the like, more preferably tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, dimethylphenylamine, tricyclohexylamine, pyridine, 1,4-diazabicyclo[2.2.2]octan, 1,8-diazabicyclo[5.4.0]-7-undecane or 1,5-diazabicyclo[4.3.0]-5-nonene, even more preferred namely trioctylamine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecane or 1,4-diazabicyclo[2.2.2]octane.
[00144] However, in step (f), a solid base capable of being easily separated after contact with the solution containing 1.4BG from the refined raw material or solution containing crude 1.4BG is preferably used instead of a base that dissolves in solution containing 1.4BG of the refined raw material or solution containing 1.4BG crude. The solid base can exert its effects and be used as long as it is a solid form compound that has basicity, but the base is preferably at least one member selected from an anion exchange resin, a compound containing the triazine ring and has a group amino or a substituted amino group, a polyamide and an inorganic base.
[00145] Anion exchange resin as a solid base is not particularly limited, and a commercially available product can be used. Also, the structure type is not particularly limited, and all gel types, an MR (macroreticular) type, a porous type and a high porosity type can be used, but among others, a styrene or acrylic based resin that has a quaternary ammonium salt as a functional group is preferred.
[00146] The compound containing the triazine ring which has an amino group or a substituted amino group preferably includes a melamine resin, CTU guanamine (3,9-bis[2-(3,5-diamino-2,4- 6- triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane), CMTU guanamine (3,9-bis[1-(3,5-diamino-2,4,6- triazaphenyl)methyl]-2,4,8,10-tetraoxaspiro[5.5]undecane) and the like. Two or more of these can be used in combination.
[00147] Polyamide includes, for example, nylon 6, nylon 12, nylon 4/6, nylon 6/6, nylon 6/10 and nylon 6/12. Two or more of these can be used in combination.
[00148] The inorganic base includes an alkali metal compound and an alkaline earth metal compound and specifically includes, for example, a metal oxide such as CaO and MgO, a metal hydroxide such as Ca(OH)2 and Mg(OH) 2, a metal carbonate like Na2CO3, K2CO3, CaCO3 and MgCO3 and an inorganic acid metal salt like borate and phosphate of the above compound. Two or more of these can be used in combination.
[00149] Among these solid bases, a compound containing the triazine ring that has an amino group or a substituted amino group and an anion exchange resin is more preferred, and an anion exchange resin is even more preferred.
[00150] In step (f), the temperature at the time of contact of a base with the solution containing 1.4BG of the refined raw material or solution containing 1.4BG crude is preferably from -20 to 200°C, more preferably from 0 to 120°C, even more preferably from 30 to 100°C. If the temperature is too low, a special apparatus such as a freezing device is needed and the competition energy of the process is reduced, whereas if the temperature is too high, deterioration of the solid base continues.
[00151] The contact time is preferably from 1 minute to 100 hours, more preferably from 10 minutes to 20 hours, even more preferably from 20 minutes to 10 hours. If the contact time is too short, it is difficult to sufficiently remove the component which deteriorates the catalyst, whereas if the contact time is too long, the process becomes inefficient.
[00152] The solid base which is placed in contact with the 1.4BG-containing solution of the refined raw material or the solution containing crude 1.4BG can be used in a ratio of 0.01 to 100 in terms of the mass to the ratio. solution containing 1.4BG of the refined raw material or solution containing 1.4BG crude, and the proportion is preferably from 0.1 to 20, more preferably from 0.2 to 10.
[00153] The method of contacting the solution containing 1.4BG of the refined raw material or solution containing 1.4BG raw can be in batch or in continuous mode, but in view of the ease of operation, a continuous flow system is particularly preferred.Step (b): a distillation step to remove the boiling point components lower than 1.4BG
[00154] In step (b), the solution containing 1.4BG of the refined raw material (in Fig. 1, the processing solution from step (c)) is distilled in a distillation column (hereinafter, referred to sometimes as "distillation column (b)"), whereby components with a boiling point lower than 1.4BG are removed. Components with a boiling point lower than 1.4BG, which are removed in the distillation column (b), include color causing components.
[00155] The objective of this step (b) is to sufficiently remove both low-boiling components to obtain high-purity 1.4BG as well as to remove a small amount of color-causing components. By this operation, among others, the color causative component itself, a form of hydrogenation of the color causative component, and in addition, components with a boiling point lower than 1.4BG, such as acetic acid, butyric acid, water, tetrahydrofuran, 2-hydroxytetrahydrofuran, gamma-butyrolactone, 1-acetoxy-4-hydroxybutane, 1,3-butanediol, 2,3-butanediol and 2-(4-hydroxybutyloxy) tetrahydrofuran are removed or quantitatively reduced .
[00156] Especially, as for the cyclic carbonyl compound that has a number of 5 or 6 carbon atoms, which is a causative component of color described in the hydrogenation step of step (c), in the case of the execution of step (c) before step (b), most of the compound must be removed by the distillation of step (b), and the concentration of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms in the bottoms of the distillation column (b) is preferably 100 ppm or less, more preferably 20 ppm or less, even more preferably 10 ppm or less, and it is particularly preferable to remove the compound at a concentration no more than the lower detection limit. The "no more than the lowest detection limit", as used in this application, means a value detectable by a general gas chromatography. Specifically, the compound is preferably removed at a concentration of 2 ppm or less.
[00157] Also, the total amount of these carbonyl compounds can be controlled as a carbonyl valence, and the carbonyl valence can be reduced in step (b).
[00158] In addition, the concentration of, among others, 1-acetoxy-4-hydroxybutane in a solution containing crude 1,4BG after removal of the low boiling point components by the distillation column of step (b), i.e., in the bottoms product from the distillation column (b), is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 20 ppm by mass or less, and is preferably 0.1 mass ppm or more , more preferably 0.2 ppm by mass or more, even more preferably 0.5 ppm by mass or more. By making the concentration of 1-acetoxy-4-hydroxybutane no more than the upper limit above, deterioration of color tone at the time of PBT production can be avoided, and making the concentration of 1-acetoxy-4-hydroxybutane be no less than the lower limit above, high refining as the reflux ratio increases is not required and this is economically advantageous.
[00159] The distillation column (b) used for removal of components with a boiling point lower than 1.4BG is preferably a distillation column having, as a theoretical tray, from 5 to 100 trays, more preferably from 10 to 50 trays.
[00160] The reflux ratio is arbitrated, but it is preferably from 0.01 to 100, more preferably from 0.1 to 50. Above all, a reflux ratio from 0.2 to 20 is preferred.
The reboiler as the heating region of the distillation column (b) is not particularly limited, but is preferably a forced circulation reboiler or a falling film reboiler. Especially, the residence time in the region of contact with a heating source at the bottom is preferably shorter to avoid fouling, and a structure where the heating source is not placed in contact with a part of the gas phase or a structure where the amount contact is minimized, is preferred. It is also possible to recover steam from a cooling condenser at the top of the distillation column (b).
[00162] The top pressure of the distillation column (b) is, in terms of absolute pressure, preferably from 1 to 200 kPa, more preferably from 2 to 100 kPa, even more preferably from 5 to 50 kPa. As the head pressure is lower, the temperature in the column can be reduced, and the production of new impurities due to an impurity reaction in the column can thereby be avoided. Also, as the top pressure is higher, the vapor recovery from the top region is more successful and in addition, the volume of the column itself can be reduced.
[00163] The temperature in the distillation column (b) is determined by composition and pressure, but the temperature at the bottom part where the temperature is highest is preferably 200°C or less, more preferably 180°C or less, even more preferably 170°C or less, and is preferably 120°C or more, more preferably 130°C or more, even more preferably 140°C or more. If the bottom temperature is too high, 1.4BG and a small amount of impurities are reacted to the bottom to increase the fouling rate, and if the bottom temperature is too low, high vacuum is required, which is economically undesirable.
[00164] The temperature at the top where the temperature gets lower is 40°C or more, more preferably 50°C or more, even more preferably 60°C or more. If the temperature of the top region is too low, the cost of cooling becomes immense. Also, if the temperature is high at both the top and the top of the column, a cyclic carbonyl compound that has a number of 5 or 6 carbon atoms, which is a causative component of the color, is at high boiling with 1,4BG, and the high-boiling cyclic carbonyl compound having a number of 5 or 6 carbon atoms is transferred in high-boiling form to the next step. Furthermore, if the temperature is high, the low boiling point component tends to be also increased in the bottom liquid. Therefore, the temperature at the top is also preferably 160°C or less, more preferably 140°C or less, even more preferably 130°C or less.
[00165] The bottom product obtained in the distillation column (b) removing the components with a boiling point lower than 1.4BG is transferred to the next step. The distillate from the distillation column (b), containing a large number of components with a boiling point lower than 1.4BG, can be discarded in the state, or the low-boiling components can be further separated from the distillate and fed to a 1,4BG recovery distillation step.Step (d): a distillation step to obtain refined 1,4-butanediol
[00166] In step (d), the solution containing crude 1.4BG obtained by at least one step outside of steps (a) to (c) is distilled in a distillation column (hereinafter, sometimes referred to as "column of distillation (d)"), and refined 1,4-butanediol is withdrawn as a side stream product. Depending on the case, the process sometimes goes through at least any one of steps (e) and (f) in addition to steps (a) through (c).
[00167] In step (d), the refined 1.4BG is obtained as a side stream of the distillation column (d), but 1.4BG containing a small amount of low boiling components such as acetic acid, butyric acid, water, tetrahydrofuran, 2-hydroxytetrahydrofuran, gamma-butyrolactone, 1-acetoxy-4-hydroxybutane, 1,3-butanediol, 2,3-butanediol and 2-(4-hydroxybutyloxy)tetrahydrofuran is top distilled from the distillation column (d), and 1.4BG containing a small amount of high-boiling components is discharged from the bottom.
[00168] This head distillate and immobile product from the bottom of the distillation column (d) are preferably recovered in the preceding step individually or after being mixed. Especially, the color causative component that has a significant effect on the quality of refined 1,4BG, as a cyclic carbonyl compound that has a number of 5 or 6 carbon atoms, is a low-boiling component and therefore this is discharged in a higher concentration by the head distillate than by the side stream.
[00169] From the point of view of reducing the color causing components, it is important that the concentration of gamma-butyrolactone in the head distillate of the distillation column (d) is higher than the concentration of gamma-butyrolactone in the 1,4BG refined from a side stream. The concentration of gamma-butyrolactone in the head distillate is preferably on the order of 1.1 to 500 times the concentration of gamma-butyrolactone in the refined 1,4BG from the sidestream. Also, the total amount of carbonyl compounds can be controlled as a carbonyl valence, and the carbonyl valence can be reduced in step (d).
[00170] The concentration of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms, in the refined 1,4BG taken out as a side stream, is preferably 20 ppm by mass or less, more preferably 12 ppm by mass or less , even more preferably 8 ppm by mass or less.
[00171] Furthermore, the water concentration and the purity of 1.4BG have to be controlled. Preferably, the sidestream water concentration is 500 mass ppm or less, and the purity of 1.4BG is 99.5% mass or more.
[00172] While the distillation column (d) is a distillation column capable of satisfying these quality items, refined 1.4BG can be obtained by performing the distillation with arbitrary trays and conditions, but the distillation column (d) used for to obtain refined 1.4BG is preferably a distillation column having, as a theoretical tray, from 5 to 100 trays, more preferably from 10 to 50 trays.
[00173] The side stream withdrawal position when obtaining refined 1.4BG as a side stream is preferably located in the upper part relative to the liquid feed tray of raw material and in addition, in the direction of the height of the distillation column ( b), the side stream is preferably withdrawn at a position greater than 50% of the height of the distillation column (b), for example, at a position of 50 to 90% of the theoretical trays at the bottom of the distillation column (b), based on the theoretical distillation column trays (b).
[00174] Especially, the distance between the liquid raw material feed tray and the side stream withdrawal position is, in terms of the theoretical tray, 2 trays or more, preferably 3 trays or more, and, for example, is preferably from 3 to 20 trays. Incidentally, the number of theoretical trays of the portion above the side stream withdrawal position is preferably from 1 to 50, more preferably from 2 to 20, even more preferably from 3 to 10.
[00175] The reflux ratio of the distillation column (d) is arbitrated but is preferably from 0.01 to 100, more preferably from 0.1 to 50. First of all, a reflux ratio from 0.2 to 20 is preferential.
[00176] The reboiler as the heating region of the distillation column (d) is not particularly limited, but is preferably a forced circulation reboiler or a falling film reboiler. Especially, the residence time in the region of contact with a bottom heating source is preferably shorter to avoid fouling, and a structure where the heating source is not placed in contact with a part of the gas phase or a structure where the amount of contact is minimized, it is preferred. It is also possible to recover steam from a cooling condenser at the top of the distillation column (d).
[00177] The top pressure of the distillation column (d) is, in terms of absolute pressure, preferably from 1 to 200 kPa, more preferably from 2 to 100 kPa, even more preferably from 2 to 50 kPa. As the head pressure is lower, the temperature in the column can be reduced, and the production of new impurities due to an impurity reaction in the column can thereby be avoided. On the other hand, as the top pressure is higher, the vapor recovery from the top region is more successful and in addition, the volume of the column itself can be reduced.
[00178] The temperature in the distillation column (d) is determined by composition and pressure, but the temperature at the bottom where the temperature is highest is preferably 120 to 200°C, more preferably 130 to 180°C, even more preferably from 140 to 170°C.
[00179] The temperature at the top where the temperature is lower is 40°C or more, more preferably 50°C or more, even more preferably 60°C or more. If the bottom temperature is too high, 1.4BG and a small amount of impurities can be reacted at the bottom to deteriorate the quality of the refined 1.4BG, and if the bottom temperature is too low, high vacuum is required, which is economically unwanted.
[00180] Also, if the temperature is high in both the top and top of the column, a component such as acetal that results from high boiling with 1.4BG of a cyclic carbonyl compound that has a number of 5 or 6 carbon atoms, which is a causative component of the color, can decompose to increase the concentration of the cyclic carbonyl compound that has a number of 5 or 6 carbon atoms in the refined 1,4BG. Furthermore, if the temperature is high, the low boiling point component tends to be also increased in the bottom liquid. Therefore, the temperature at the top of the distillation column (d) is also preferably 160°C or less, more preferably 150°C or less, even more preferably 145°C or less. If the temperature of the top region is too low, the cost of cooling becomes immense.
[00181] As described above, in case of passing all steps (a) to (c), the order of steps is not particularly limited, but from the point of view that coloring can be suppressed at the time of PBT production using 1,4BG refined as a raw material, the solution containing 1.4BG of the refined raw material is preferably refined, as shown in Fig. 1, in order of steps (a), (c) and (b) and then introduced in step (d). Step (f) is not particularly limited although it is before step (c), but step is preferably immediately before step (c). Step (e) is preferably used in conjunction with step (a). Incidentally, the 1.4BG loss can be reduced by circulating the distillate from the head of step (d) to the previous stage of step (f) and circulating the immobile bottom product in step (e).EXAMPLES
[00182] The present invention is described in greater detail below by referring to Examples, but the present invention is not limited to these Examples while the essence of the present invention is observed.
The following are the analyzes of 1,4-butanediol (1,4BG), tetrahydrofuran (THF), gamma-butyrolactone (hereinafter referred to as "GBL"), 1-acetoxy-4-hydroxybutane (hereinafter designated as "14HAB"), 2-(4-hydroxybutyloxy) tetrahydrofuran (hereinafter referred to as "BGTF"), 2-pyrrolidone (hereinafter referred to as "2P") and 2-hydroxytetrahydrofuran (hereinafter referred to as "BGTF") "OTF") were performed by gas chromatography on a gas chromatographic analyzer "Model Shimadzu GC-2014" produced by Shimadzu Corporation using the PEG-20M column (polar) produced by Science GL.
[00184] The concentrations of 1.4BG, THF, GBL, 14HAB, BGTF, 2P and OTF were calculated by the corrected area percentage method computed from the effective carbon coefficient making a correction with the amount of water according to the method of Karl Fisher (measured by "CA-03", produced by Mitsubishi Chemical Corporation).
[00185] Incidentally, the amount of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms is small and so the sample was injected into the gas chromatographic analyzer without dilution by a solvent. Also, the amount of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms was calculated from the ratio between the area value of 1.4BG and the area value of the cyclic carbonyl compound without making a correction for the coefficient. of effective carbon.
[00186] The cyclic ketone and/or aldehyde, each having a number of 5 or 6 carbon atoms, can be detected by GC-MS and/or GC-IR and can be discriminated from other components in the refined 1,4BG. These are supposed to be 2-acetyltetrahydrofuran and 2-methyldihydro-2H-pyran-3(4H)-one.
[00187] 2-Acetyltetrahydrofuran (hereinafter, referred to as "ATF"):
[00188] GC-MS (EI): 86, 71, 43, 29
[00189] GC-IR: 2980, 2885, 1734, 1454, 1360, 1176, 1080, 925 cm-1
[00190] 2-Methyldihydro-2H-pyran-3(4H)-one (hereinafter, referred to as "MHPO")
[00191] GC-MS (EI): 114, 71, 42, 29
[00192] GC-IR: 2956, 2851, 1742, 1240, 1115 cm-1
[00193] Hereinafter, the total of ATF and MHPO is defined as the total of cyclic carbonyl compounds that have a number of 5 or 6 carbon atoms and are referred to as "total cyclic carbonyl C5,C6". Also, the boiling point component higher than 1.4BG is referred to as the "high boiling point component", and the boiling point component lower than 1.4BG is referred to as the "low boiling point component". boiling".
[00194] The concentration in terms of nitrogen atom of a compound containing nitrogen in the sample was determined by burning the sample in an argon/oxygen atmosphere and analyzing the generated flue gas by means of a nitrogen trace analyzer (Model TN- 10, produced by Mitsubishi Chemical Analytech Co., Ltd.) employing a combustion/reduced pressure chemiluminescence method.
[00195] As for the analysis of sulfur and chlorine concentrations in the sample, the sample was collected in a vessel made of platinum and heated in a tubular furnace made of quartz ("Model AQF-100", produced by Mitsubishi Chemical Corporation) and after chlorine contents and sulfur contents of absorption in the flue gas by an aqueous solution of 0.03% hydrogen peroxide, chloride ion and sulfate ion in the absorption solution were measured by ion chromatograph ("Model ICS 1000", produced by Dionex) to determine concentrations.
[00196] The absorbance of the sample at a measured wavelength of 260 nm (hereinafter, simply referred to as "absorbance") was measured using "UV-2400" produced by Shimadzu Corporation (using a closed cell made of synthetic quartz which has a light path length of 1 mm and a light path width of 10 mm) by visible and ultraviolet spectroscopy. In this order, pure water was used for the blank measurement.
[00197] The carbonyl valence of the sample was calculated according to the following formula by reacting a carbonyl compound with hydroxylamine hydrochloride (25°C, 1 hour) and quantitatively determining the hydrochloric acid produced by the neutralization titration with methanolic KOH N/10. For the titration, an automatic titrator (Automatic Titrator AUT-501, produced by DKK-Toa Corporation) was used.Carbonyl valence (mg KOH/g) = (A-B)xfx5.6/S
[00198] where A is the titer (mL) of 0.1 mol/L potassium hydroxide in this test, B is the titer (mL) of 0.1 mol/L potassium hydroxide in the blank test, f is the 0.1 mol/L potassium hydroxide factor, and S is the sample amount (g). PRODUCTION OF SOLUTION CONTAINING 1.4BG OF REFINED RAW MATERIAL PRODUCTION EXAMPLE 1
[00199] A composition containing 1,4BG was biologically produced in culture medium for fermenting organisms based on the description in JP-T-2010-521182. From this 1.4BG-containing composition, according to the method described in US Patent Application Publication No. 2011/0003355, the bacterial cells and saline contents were entirely or each at least partially removed by filtration, centrifugal separation and a resin of ion exchange and then the water was removed by distillation. The constituents of the composition containing 1.4BG at this time are shown in Table 1. The pH of the composition containing 1.4BG was 6.3.
[00200] In order to separate additional water from the composition containing 1.4BG, dehydration by distillation was carried out using an Oldershaw distillation column which has 30 theoretical trays. In this application, by setting the top pressure of the distillation column to 10.8 kPa and the reflux ratio to 1.0 and controlling the top temperature and bottom temperature to be constant at 48°C and 175°C, respectively , the above 1.4BG-containing composition was continuously introduced into the position of the 20th tray counted from the bottom at a flow rate of 105 ml/hour, and the water was distilled from the top at a flow rate of 10 ml/hour. Simultaneously with the water distillation, the dehydrated solution containing crude 1.4BG (solution containing 1.4BG of the refined raw material) was continuously withdrawn as a bottom bottom product at 95 ml/hour. The water concentration in the solution containing 1.4BG of the refined raw material was 0.025% by mass (250 ppm by mass). The constituents of the solution containing 1.4BG of the refined raw material obtained are shown in Table 1. Incidentally, the pH of the solution containing 1.4BG of the refined raw material was 5.5.

[00201] Refining of Solution Containing 1.4BG of the Refined Raw Material EXAMPLE 1 Step (a): separation by distillation of the high-boiling component
[00202] With respect to the 1.4BG-containing solution of the continuously refined raw material obtained after dehydration distillation in Production Example 1, the components of boiling point higher than 1.4BG, which are contained in the solution containing 1, 4BG of refined raw material were removed in a distillation column.
[00203] As the distillation column of step (a), an Oldershaw distillation column having 30 theoretical trays was used. This Oldershaw distillation column is a distillation column where the heat source is placed in contact substantially only with the bottom liquid and is not involved in contact with a part of the gas phase, and the situation of being placed in contact substantially only with the bottom liquid includes, for example, a state of allowing contact with a heating medium in a region below the gas-liquid interface at the bottom, and a state of eliminating a part of the gas phase by spraying the bottom with a liquid, but the situation above is not limited to these modalities.
[00204] By setting the top pressure to 15.7 kPa and the reflux ratio to 1.0 and controlling the top temperature and bottom temperature to be constant at 176°C and 184°C, respectively, the composition containing 1.4BG of the refined raw material was continuously introduced into the 10th tray position counted from the bottom at a flow rate of 86 mL/hour. Continuous top distillation was performed at 74 mL/hour, and continuous bottom removal was performed at 12 mL/hour. A continuous operation for 210 hours can be carried out stably without producing a solid matter. A solution containing crude 1.4BG after removal of higher boiling point components than 1.4BG was obtained from the top (head distillate). The constituents of the product still from the bottom and the head distillate (solution containing 1.4BG crude) from the distillation column (a) are shown in Table 2.

[00205] Incidentally, in step (a), the separation by distillation can be carried out at a lower bottom temperature and a top temperature than their respective temperatures above by reducing the top pressure of the distillation column (a), but establishment of the bottom and top temperature, top temperature heat recovery of the top can be performed. Especially, the heat of condensation of the distillate is preferably recovered as a pressurized steam. The recovered heat can be used for the heat source of other distillation columns and the like. Step (e): Distillation to recover 1.4BG from high boiling components separated in step (a)
[00206] Although an example by single-stage distillation is described below, for more efficient recovery of 1.4BG and separation of high-boiling components, continuous distillation is preferred, and more preferably, multi-stage distillation is performed . It is also preferred to properly conduct reflux.
[00207] In a 500 mL glass flask equipped with a condenser made of glass for distillation, 252.4 g of the immobile bottom product (the constituents of the liquid are shown in the column "Immovable Bottom Product" in Table 2) taken from the bottom in step (a) were loaded, and the single-stage batch distillation was carried out at a pressure of 4.9 kPa and a temperature inside the flask of 153 to 169°C. As a result, a distillate containing 235.2 g of 1.4BG was separated and recovered. In the flask, 15.5 g of a concentrated liquid of high boiling components was obtained as a distillation residue. The constituents of the separated and recovered distillate and distillation residue are shown in Table 3.

Step (f): step of contacting the solution containing gross 1.4BG with the base
[00208] A 100 mL volume stainless steel reactor was filled with 85 mL of a weakly basic anion exchange resin (trademark: DIAION, Model WA20, a styrene-based resin that has a quaternary ammonium salt as a functional group) (hereinafter, sometimes referred to simply as "WA20"), and the distillate (constituents of the liquid: "Head Distillate" column in Table 2) obtained in step (a) above was continuously passed through the upper part. from the reactor by an upward flow at 170 mL/hour, thereby performing a contact treatment. Incidentally, at the moment of contact of the anion exchange resin with the distillate, the temperature was 40°C, and the pressure was the ordinary pressure.
[00209] The chloride ion concentration (total chlorine concentration) and sulfide ion concentration (total sulfur concentration) in the distillate before contact with the anion exchange resin and the chloride ion concentration (total chlorine concentration) and concentration of sulfide ion (total sulfur concentration) in the distillate after contact with the anion exchange resin, which was obtained from the reactor outlet, were measured by an ion chromatograph, and the results of these are shown in Table 4. In the Table, "WA20" indicates the weakly basic anion exchange resin described above.

[00210] It is seen from Table 4 that the sulfur concentration and the chlorine concentration in the solution containing crude 1.4BG can be reduced by step (f). Step (f) can reduce the catalyst deterioration rate of the catalyst used in the hydrogenation reaction of the next step (c) and can be expected to produce an effect of increasing the life of the catalyst. Step (c): solution hydrogenation step containing 1.4BG crude Step (c-1) hydrogenation reaction catalyst: a case of nickel-chromium catalyst supported by diatomite (continuous flow reactor)
[00211] A stainless steel flow reactor having a reaction volume of 120 mL was filled with 60 mL of a nickel-chromium catalyst supported by diatomite in pellet form (supported amount: 12% by mass of nickel , 1.5% by mass of chromium), and the solution containing crude 1.4BG after contact with the anion exchange resin, which was obtained from the reactor outlet in step (f), was passed through it at 30 mL/hour from the lowest part of the reactor to carry out a hydrogenation reaction of unsaturated compounds in the solution containing crude 1.4BG.
[00212] Incidentally, the reactor was filled with nickel-chromium catalyst supported by diatomite by supplying, in order, a stainless steel filter, a layer of beads, a layer of catalyst, a layer of beads and a steel filter stainless steel in the direction of the inlet to the outlet of the flow reactor. The reaction conditions for the hydrogenation reaction were established at a reaction temperature of 80°C and a hydrogen pressure of 2.0 MPa (gauge pressure).
[00213] The solution containing crude 1.4BG after hydrogenation reaction was sampled with the time of reactor exit and analyzed by gas chromatography and absorbance. The results are shown in Table 5.

[00214] It is seen from Table 5 that by passing the solution containing crude 1.4BG through step (c), a cyclic carbonyl compound having a number of 5 or 6 carbon atoms is converted to a corresponding alcohol by hydrogenation. Furthermore, the absorbance was also reduced, and this reveals that the cyclic carbonyl compound having a number of 5 or 6 carbon atoms is correlated with the color component for 1.4BG, particularly with the color hue value b at the time of PBT production, and the concentration of the coloring component can be reduced by the hydrogenation reaction.Step (c-2) the hydrogenation reaction catalyst: a case of silica supported nickel catalyst (batch reactor)
[00215] A stainless steel autoclave having a reaction volume of 100 mL was filled with 2 g of a nickel catalyst supported on silica in pellet form (supported amount: a total of nickel and nickel oxide: 52% in mass), 40 g of the solution containing crude 1.4BG resulting from contact with the anion exchange resin, which was obtained from the reactor outlet in step (f), were placed in this, and the autoclave was then sealed in a hydrogen pressure of 0.99 MPa (gauge pressure) and stirred in an oil bath at 110°C for 4 hours. Subsequent to carrying out the reaction, the solution containing crude 1.4BG after the hydrogenation reaction in the flask is sampled and analyzed by gas chromatography and absorbance. The results are shown in Table 6.

Step (b): separation by distillation of low boiling component
[00216] In the separation of low boiling point components from the solution containing crude 1.4BG which was hydrogenated in the case of step (c-1), an Oldershaw distillation column which has 30 theoretical steps was used. The separation by distillation of low boiling point components was carried out in the following three cases of distillation condition. Step (b-1): standard distillation condition
[00217] By setting the top pressure at 4.0 kPa and the reflux ratio at 50.0 and controlling the top temperature and bottom temperature at constant temperatures of 139°C and 163°C, respectively, the solution containing Crude 1.4BG (carbonyl valence: 1.8 mg KOH/g) which was hydrogenated in the case of step (c-1) was continuously introduced into the position of the 20th tray counted from the bottom at a flow rate of 110 mL/ hour. Continuous top distillation was performed at 1.3 mL/hour, and continuous bottom removal was performed at 108.7 mL/hour, thereby removing the low boiling components in the solution containing crude 1.4BG . The constituents of the liquid distillate from the top (head distillate) and the bottom product from the bottom part (bottom still product) are shown in Table 7. Step (b-2): Augmented condition 1 to remove the component from low boiling point
[00218] By setting the top pressure at 4.0 kPa and the reflux ratio at 50.0 and controlling the top temperature and bottom temperature at constant temperatures of 143°C and 164°C, respectively, the solution containing Crude 1.4BG (carbonyl valence: 1.8 mg KOH/g) which was hydrogenated in the case of step (c-1) was continuously introduced into the position of the 20th tray counted from the bottom at a flow rate of 110 mL/ hour. Continuous top distillation was performed at 5.4 mL/hour, and continuous bottom removal was performed at 104.6 mL/hour, thereby removing the low boiling components in the solution containing crude 1.4BG . The constituents of the liquid distillate from the top (head distillate) and the bottom product from the bottom part (bottom still product) are shown in Table 7. Step (b-3): Augmented condition 2 to remove the component from low boiling point
[00219] By setting the top pressure at 4.0 kPa and the reflux ratio at 50.0 and controlling the top temperature and bottom temperature at constant temperatures of 145°C and 165°C, respectively, the solution containing Crude 1.4BG (carbonyl valence: 1.8 mg KOH/g) which was hydrogenated in the case of step (c-1) was continuously introduced into the position of the 20th tray counted from the bottom at a flow rate of 110 mL/ hour. Continuous top distillation was performed at 10.1 mL/hour, and continuous bottom removal was performed at 100.2 mL/hour, thereby removing the low boiling components in the solution containing crude 1.4BG . The constituents of the top distillate (head distillate) and the bottom product from the bottom (bottom still product) are shown in Table 7. Step (b-4): high temperature condition
[00220] By setting the top pressure at 18.1 kPa and the reflux ratio at 50.0 and controlling the top temperature and bottom temperature at constant temperatures of 178°C and 186°C, respectively, the solution containing Gross 1.4BG (carbonyl valence: 1.8 mg KOH/g) which was hydrogenated in the case of step (c-1) was continuously introduced into the position of the 20th tray counted from the bottom at a flow rate of 105 mL/ hour. Continuous top distillation was performed at 10 mL/hour, and continuous bottom removal was performed at 95 mL/hour, thereby removing the low boiling components in the solution containing crude 1.4BG. The constituents of the liquid distilled from the top (head distillate) and the bottom product from the bottom (bottom still product) are shown in Table 7.


[00221] As evident from Table 7, by performing the distillation and separation of low boiling components, a cyclic carbonyl compound having a number of 5 or 6 carbon atoms can be removed from the solution containing 1.4BG crude, and the absorbance and valence of the carbonyl can be reduced.
[00222] In step (d) described below, a cyclic carbonyl compound having a number of 5 or 6 carbon atoms is regenerated from a part of low-boiling components and high-boiling components into the immobile product of the bottom in Table 7 and therefore, a cyclic carbonyl compound having a number of 5 or 6 carbon atoms, which is not present in the bottom immobile product, is mixed into the refined 1.4BG (Table 8 to Table 12).
[00223] Therefore, it is required that you do not transfer low boiling point components and high boiling point components in step (d). It is seen from Table 7 that the low-boiling components in the bottom still product can be sufficiently removed by increasing the amount of low-boiling components distilled in steps (b-2) and (b-3). In the case of high temperature condition, it is considered that a significant increase of high boiling point components occurs at the top of the column as well as at the top, and in the high temperature distillation of step (b-4) , a higher concentration of high-boiling components remains in the bottom immobile product. These high boiling components are supposed to be acetals, ketals and hemiacetals of the cyclic carbonyl compound having a number of 5 or 6 carbon atoms. Therefore, separation by distillation of low boiling components at a lower temperature may be preferred.Step (d): Refining Distillation of High Purity 1,4-Butanediol
[00224] In obtaining high purity 1.4BG by distilling the solution containing crude 1.4BG (the constituents of the liquid are shown in the Fund Immovable Product (b-1) in Table 7) obtained in step (b-1) of step (b) above, an Oldershaw distillation column that has 25 theoretical trays was used. By setting the top pressure at 2.5 kPa and the reflux ratio at 10.0 and controlling the top temperature and bottom temperature at constant temperatures of 137°C and 157°C, respectively, the solution containing 1.4BG crude was continuously introduced into the 10th tray position counted from the bottom at a flow rate of 76 ml/hour. At this time, a continuous operation for 55 hours was carried out performing continuous distillation of the top at 1 mL/hour, continuous removal of a side stream in the 20th tray counted from the bottom at 73 mL/hour and continuous removal of the bottom at 2 mL/ hour. The constituents and absorbance of head distillate, side stream (refined 1.4BG) and bottom still product are shown in Table 8. COMPARATIVE EXAMPLE 1
[00225] All were carried out in the same manner except that in Example 1, refined 1,4BG was removed from the top not performing the withdrawal of a side stream in step (d). The head distillate flow rate was 73 mL/hour. The results are shown in Table 8.

EXAMPLE 2
[00226] The operation was carried out in the same manner as in Example 1 except that in step (d), the top temperature and bottom temperature were controlled at constant temperatures of 137°C and 158°C, respectively, the solution containing 1 ,4BG crude was continuously introduced into the position of the 10th tray counted from the bottom at a flow rate of 78 mL/hour, the continuous distillation of the upper part was carried out at 12 mL/hour, the continuous withdrawal of a side stream in the 20th tray counted of the fundus was performed at 64 mL/hour, and continuous withdrawal of the fundus was performed at 2 mL/hour. The constituents and absorbance of head distillate, side stream (refined 1.4BG) and bottom still product are shown in Table 9.
EXAMPLE 3
[00227] The operation was carried out in the same manner as in Example 1 except that the distillation was carried out using the bottom immovable product from step (b-2) of step (b) (the constituents of the liquid are shown in the Bottom Immovable Product from Step (b-2) in Table 7) as the raw material from step (d) to obtain high purity refined 1.4BG. The constituents and absorbance of head distillate, side stream (refined 1.4BG) and bottom immobile product are shown in Table 10.
EXAMPLE 4
[00228] The operation was carried out in the same manner as in Example 1 except that the distillation was carried out using the immovable product from the bottom of step (b-3) of step (b) (the constituents of the liquid are shown in the Immovable Product of the Bottom from Step (b-3) in Table 7) as the raw material from step (d) to obtain high purity refined 1.4BG. The constituents of head distillate, side stream (refined 1.4BG) and bottom still product are shown in Table 11.
REFERENCE EXAMPLE 1
[00229] 650 g of immovable product from the bottom of step (b-3) of step (b) (the constituents of the liquid are shown in the Immovable Product of the Bottom of Step (b-3) in Table 7) was used as the matter - prime from step (d), and the distillate was separated into a plurality of fractions by batch distillation under a top pressure condition of 0 to 0.9 kPa to obtain 3 batches of refined 1,4-butanediol. Of these batches, the constituents of the batch initially obtained (Fr. 1, 147 g) are shown in Table 12.
PBT PRODUCTION
[00230] In the production of PBT below, several analyzes were performed by the following methods. Analysis of THF, Water
[00231] A distillate in an esterification reaction was determined by the amount of water by the Karl Fisher method (measured by "CA-03", produced by Mitsubishi Chemical Corporation), and the remainder except water was considered as organic components. The amount of THF in the organic components was determined by the gas chromatography method described above and taken as the production volume of THF. The production volume of THF was expressed in mol % in relation to terephthalic acid, and the value obtained was taken as the conversion ratio. Intrinsic Viscosity (IV) of PBT
Intrinsic viscosity was determined using an Ubbelohde viscometer by the following procedure. That is, using a varied solvent of phenol/tetrachloroethane (mass ratio: 1/1), the decay time in seconds was measured at 30°C in a PBT solution that has a concentration of 1.0 g/ dL and only in the solvent, and the viscosity was determined according to the following formula

[00233] where nsp=(n/no)-1, n is the decay time in seconds of the PBT solution, n is the decay time in seconds of the solvent, C represents the PBT concentration (g/dL) of the PBT solution, and KH is the Huggins constant. A value of 0.33 was adopted for KH. Concentration of the Terminal Carboxyl Group (equivalent/ton) of PBT
[00234] 0.5 g of PBT was dissolved in 25 ml of benzyl alcohol, the resulting solution was titrated using a 0.01 mol/L sodium hydroxide benzyl alcohol solution, and the concentration was calculated according to the following formula :Terminal carboxyl group concentration = (AB)x0.1 x^yy (equivalent 4oQ)
[00235] where A is the amount (μL) of the benzyl alcohol solution of 0.01 N sodium hydroxide required for the titration, B is the amount (μL) of the benzyl alcohol solution of sodium hydroxide 0, 01 mol/L required for blank titration, W is the amount (g) of the PBT sample, and f is the 0.01 mol sodium hydroxide factor/LV Color shade b
[00236] A columnar powder measuring cell having an internal diameter of 30 mm and a depth of 12 mm was filled with PBT in pellet form. Using a colorimeter, Color Meter ZE2000 (produced by Nippon Denshoku Industries Co., Ltd.), the color was measured at four places by the reflection method by rotating the measurement cell every 90°, and the value was determined as a value. simple mean of the obtained values. The color tone was evaluated by the value of b in the L, a, b color system. A lower value indicates that the color tone is better with less yellowing. PRODUCTION EXAMPLE 2
[00237] PBT was produced by the following method using, as 1.4BG, the refined 1.4BG (the constituents of the liquid are shown in the Side Stream of Example 1 in Table 8) obtained in Example 1.
[00238] A reaction vessel equipped with an active device, a nitrogen inlet, a heating device, a thermometer, a distillation tube and an exhaust port for evacuation was charged with 113 g of terephthalic acid, 183 g of 1 .4BG and 0.7 g of a 1.4BG solution having previously dissolved in this 6% by mass of tetrabutyl titanate as a catalyst, and a nitrogen atmosphere was created within the system by vacuum purging with nitrogen.
[00239] After heating the interior of the system to 150°C with stirring, the temperature was increased to 220°C over 1 hour under atmospheric pressure, and an esterification reaction was further carried out for 2 hours by distilling the water produced.
[00240] Thereafter, 1.3 g of a 1.4BG solution of magnesium acetate 1% by mass of tetrahydrate, obtained by dissolving magnesium acetate tetrahydrate in water and further dissolving the resulting solution in 1.4BG (ratio of magnesium acetate tetrahydrate mass, water and 1.4BG: 1:2:97) were added.
[00241] Thereafter, the temperature was maintained at 220°C for 0.25 hours and then maintained up to 245°C over 0.75 hours. On the other hand, the pressure was reduced to 0.07 kPa over 1.5 hours from the initiation of polymerization, and a polycondensation reaction was carried out for 0.8 hour under the same reduced pressure. The reaction system was returned to ordinary pressure to thereby complete the polycondensation. The PBT obtained was stripped from the bottom of the reaction tank and passed under water at 10°C, and the tape was cut by a cutter to obtain PBT in pellet form.
[00242] The period from the initiation of pressure reduction after adding magnesium acetate to carrying out the polycondensation was taken as the polycondensation time, and the intrinsic viscosity/polycondensation time was defined as the polycondensation rate. The polycondensation rate was 0.37 dL/g/hour. As for the THF conversion ratio, the amount of THF was analyzed in a sample obtained by cooling and collecting a distillate during the esterification reaction by a dry ice trap, and the value obtained was expressed by mol % by charged terephthalic acid and found to be 57.0 mol%. The hue value of PBT color b was 2.7. PRODUCTION EXAMPLE 3
[00243] PBT was produced completely by the same method except that in Production Example 2, the refined 1.4BG obtained in Example 2 (the constituents are shown in the Side Stream in Table 9) was used in place of the refined 1.4BG obtained in Example 1. The hue value of color b of the PBT obtained was 2.2. PRODUCTION EXAMPLE 4
[00244] PBT was produced completely by the same method except that in Production Example 2, the refined 1.4BG obtained in Example 3 (the constituents are shown in the Side Stream in Table 10) was used in place of the refined 1.4BG obtained in Example 1. The obtained PBT b color hue value was 1.7. PRODUCTION EXAMPLE 5
[00245] PBT was produced completely by the same method except as in Production Example 2, the refined 1.4BG obtained in Example 4 (the constituents are shown in the Side Stream in Table 11) was used in place of the refined 1.4BG obtained in Example 1. The color hue value b of the PBT obtained was 1.6. PRODUCTION EXAMPLE 6
[00246] PBT was produced completely by the same method except that in Production Example 2, the refined 1,4BG obtained in Comparative Example 1 (constituents are shown in the Head Distillate of Comparative Example 1 in Table 8) was used in place of Refined 1.4BG obtained in Example 1. The color hue value b of the PBT obtained was 3.0. PRODUCTION EXAMPLE 7
[00247] PBT was produced completely by the same method except that in Production Example 2, the refined 1,4BG obtained in Reference Example 1 (constituents are shown in Distillate Fr. 1 of Reference Example 1 in Table 12) was used in place of the refined 1.4BG obtained in Example 1. The hue value of the color b of the PBT obtained was 4.9.
[00248] The results of various analyzes of Production Examples 2 to 7 are all shown in Table 13 together with the constituents of the refined 1,4BG used. Also, Figs. 2 and 3 show, respectively, the relationship of the cyclic carbonyl concentration C5, C6 total in the 1.4BG of the raw material with the value of the shade of color b at the time of PBT production obtained and the relationship with the rate of poly. condensation.

[00249] It can be confirmed from Table 13 and Fig. 2 that when the cyclic carbonyl concentration C5,C6 total (total concentration of cyclic carbonyl compounds having a number of 5 or 6 carbon atoms) in the 1,4- Raw material BG is 13ppm, PBT color b tone value increases enormously. That is, the removal of these cyclic carbonyl compounds which have a number of 5 or 6 carbon atoms is important for the production of PBT with good color tone.
[00250] It is seen from Fig. 3 that as the cyclic carbonyl concentration C5,C6 total (total concentration of cyclic carbonyl compounds having a number of 5 or 6 carbon atoms) in the 1,4-BG of the raw material is lower, the polycondensation rate (dL/g/hour) is improved. EXAMPLES 5 TO 7
[00251] The same experiment as in Production Example 1 was performed three times, and dehydration distillation was conducted each time, whereby 3 batches of the solution containing 1.4BG of the refined raw material were produced (in Table 14, shown as "1.4BG Raw Material). In each Example, refining was carried out in the same manner as in Example 1 except using the above 3 batches as the raw material. The modification in each of the carbonyl valence and absorbance between the respective steps and the color tone of PBT produced in the same manner as in Production Example 2 using refined 1.4BG as the raw material is shown in Table 14.

[00252] It is seen from Table 14 that the carbonyl valence of refined 1.4BG can be reduced by reducing the carbonyl valence of raw 1.4BG and the b color hue value of the obtained PBT can be kept in an appropriate range using a refined 1.4BG having a low carbonyl valence. It is also seen that the carbonyl valence of 1.4BG can be reduced by hydrogenation or refining by distillation. In addition, it is understood that when the carbonyl valence of 1.4BG is reduced, the UV absorbance indicative of 1.4BG staining may also be reduced.STAGE DISTILLATION COLUMN DISTILLATION EXPERIMENT (A) REFERENCE EXAMPLE 2
[00253] In the bottom region of the Oldershaw distillation column of step (a) of Example 1, fouling proceeds sometimes due to precipitation of a solid matter. To avoid this problem, it is preferable to carry out the distillation at a relatively low temperature of approximately 145°C or not to heat part of the gas phase at the bottom which is a heating region. Specifically, the liquid level of the oil bath used as the heating source of the distillation column can be kept at a lower position than the liquid level of the bottom liquid that gathers at the bottom of the distillation column. On the other hand, as for the heating of the gas phase part, which promotes the precipitation of a solid matter, for example, the liquid level of the oil bath can be kept higher than the bottom liquid that gathers in the part of bottom of the distillation column to maintain, in addition to the bottom liquid, the wall temperature of the gas phase part in the bottom part at a temperature close to that of the heating source.
[00254] Next, a distillation experiment was carried out in three cases, a case where part of the gas phase is heated to a high temperature (245°C) by modifying the position of the liquid level of an oil bath as a source of heating in the bottom part of the distillation column of step (a) of Example 1, a case where part of the gas phase is heated under a low temperature condition of 145°C, and a case where heating is performed at a high temperature. temperature (245°C) but part of the gas phase is not heated. The results are shown in Table 15. Incidentally, the liquid introduced is the solution containing 1.4BG of the refined raw material having the constituents shown in Table 1.

[00255] As evident from Table 15, compared to a case where part of the gas phase is heated to a high temperature, the amount of a precipitated solid matter can be greatly reduced creating a low temperature condition of 145°C or similar or a condition where part of the gas phase is not heated despite the high temperature.
[00256] Incidentally, as for the distillation column of step (a) in the process on an industrial scale, in order not to heat part of the gas phase, it is preferable to use, as a heating source, a forced circulation boiler or a reboiler of descending film. First of all, a power circulation reboiler is more preferred, because the liquid phase can be more completely maintained by using a back pressure valve at the time of exit from the heat exchanger and thereby increasing the pressure inside the heat exchanger . HYDROGENATION REACTION OF SOLUTION CONTAINING CHLORINE REFERENCE EXAMPLE 3
[00257] In 1,4BG produced by Mitsubishi Chemical Corporation, 10% by mass of 1,4-dihydroxy-2-butene, which is a reagent produced by TCI, was dissolved. In the resulting solution, the total chlorine concentration was 79 ppm by mass, and the total sulfur concentration was 0.1 ppm by mass. A hydrogenation experiment was carried out using this solution under the same reaction conditions as in step (c-1) of Example 1 except that the reaction temperature was set at 100°C and the hydrogen pressure was set at 3.5 MPa (gauge pressure), as a result, very rapid progress of catalyst deterioration was confirmed as shown in Table 16 (no treatment with WA20).
[00258] On the other hand, a solution obtained by subjecting the solution having a total chlorine concentration of 79 ppm by mass and a total sulfur concentration of 0.1 ppm by mass to a treatment with an anion exchange resin (WA20) which corresponds to step (f) under the conditions that the amount of ion exchange resin used was 300 mL, the treatment flow rate was 215 g/hour and the contact temperature was 55°C, it even had a concentration of total chlorine of 0.1 ppm by mass and a total sulfur concentration <0.1 ppm by mass (below the detection limit), and a hydrogenation experiment was carried out on this treated solution under the same hydrogenation conditions as the above. Then, catalyst deterioration was not confirmed as shown in Table 16 (treated with WA20).
[00259] The Ni concentration in the liquid during the flow evaluation was analyzed and compared by ICP-OES, as a result, in the solution treated with WA20, the Ni concentration in the liquid was below the detection limit until after the reaction, but in the solution not treated with WA20, a Ni concentration of 5 ppm by mass was detected.
[00260] In the Solution Before the Hydrogenation Reaction of Table 5, the chlorine concentration is approximately 0.4 ppm by mass, but considering a long-term operation, it is understood that in addition to an anion exchange resin such as WA20, a solid base or soluble bases such as various amines, elution of a catalyst component by an acid is preferably avoided.
EFFECT OF THE SIDE CURRENT OF THE FOSSILIZATION PROCESS REFERENCE EXAMPLE 4
[00261] Butadiene, acetic acid and oxygen were continuously reacted at a pressure of 6 MPa and a temperature of 60 to 99°C in the presence of a catalyst containing palladium and tellurium supported on silica. As oxygen, air diluted with nitrogen (oxygen concentration: 21% vol) was used. Acetic acid and high boiling materials were removed by distilling off the reaction solution to obtain a reaction product mainly composed of diacetoxybutene.
[00262] This reaction product was continuously fed together with hydrogen to a later stage hydrogenation reactor filled with a catalyst containing palladium supported on activated carbon and an earlier stage reactor filled with a catalyst containing ruthenium supported on silica, by means of of this by carrying out the hydrogenation. The later stage hydrogenation reaction of saturation of a carbon-carbon double bond was carried out at a pressure of 2 MPa and a temperature of 40 to 70°C, and the earlier stage hydrogenation reaction to cause the hydrogenation of an aldehyde group or the hydrogenolysis of an acetal compound was carried out at a pressure of 2 MPa and a temperature of 90 to 110°C.
[00263] The hydrogenated reaction product obtained above was passed as a varied solution with water at 40 to 60°C through a hydrolysis reactor filled with DIAION SK1B (a product of Mitsubishi Chemical Corporation, sulfonic acid type cation exchange resin, DIAION is a registered trademark of the same company) undergo a hydrolysis reaction. The obtained hydrolysis reaction solution was continuously distilled at a bottom temperature of 158°C and a top pressure of 15 kPa to distill water and acetic acid from the top and obtain a bottom liquid from the bottom. The bottom liquid was continuously distilled at a bottom temperature of 191°C, a top pressure of 21 kPa and a reflux ratio of 30 using a distillation column having several theoretical trays of 100 and thereby divided into three head liquid streams, side stream and bottom liquid.
[00264] The bottom stream obtained above was continuously fed together with hydrogen at a pressure of 0.9 MPa and a temperature of 100°C to a reactor filled with a catalyst containing palladium supported on activated carbon to carry out the hydrogenolysis of an acetal compound and the like. The resulting reaction solution was continuously distilled at a bottom temperature of 181°C, a top pressure of 20 kPa and a reflux ratio of 0.62 using a distillation column having several theoretical 10 trays. (=second distillation).
[00265] The reaction product was fed to the 3rd counting tray from the top, water and tetrahydrofuran were distilled from the top, and a bottom liquid containing 1,4-butanediol and high-boiling materials were obtained from the bottom. This bottom liquid was then continuously distilled at a bottom temperature of 160°C, a top pressure of 5.7 kPa and a reflux ratio of 0.65 using a packed column having several theoretical trays of 20 (=third distillation).
[00266] The bottom liquid was fed to the 12th counting tray from the top, the 1,4-butanediol was distilled from the top, and the high boiling materials were drained as a mixture with 1,4-butanediol from the bottom. The weight ratio of head distillate and bottom distillate was 98:2. The 1,4-butanediol obtained above was continuously fed to the 9th counted tray from the top of a packed column which has several theoretical trays of 20 and distilled at a bottom temperature of 160°C, a top pressure of 5.7 kPa and a reflux ratio of 63, 1,4-butanediol containing 1,4-butanediol monoacetate was top distilled, high purity refined 1,4-butanediol was obtained as the side stream product, and 1,4-butanediol containing high-boiling components were removed from the bottom (=fourth distillation). The weight ratio of head distillate and side stream was 1:99. REFERENCE EXAMPLE 5
[00267] PBT was produced completely by the same method except that in Production Example 2, the refined 1.4BG (side stream) obtained in Reference Example 4 was used in place of the refined 1.4BG obtained in Example 1. The value of shade of color b of the obtained PBT was 1.4. REFERENCE EXAMPLE 6
[00268] PBT was produced completely by the same method except that in Production Example 2, 1.4BG obtained by adding 1% of the best liquid in the fourth distillation to the refined 1.4BG (side stream) obtained in Reference Example 4 was used instead of the refined 1.4BG obtained in Example 1. The color hue value b of the PBT obtained was 2.0.
[00269] It is seen from Reference Examples 5 and 6 and Examples above that even in the production of 1.4BG by a bioprocess, a PBT color tone at an equivalent level to this in the fossilization process can be achieved by taking a side stream .
[00270] Although the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made thereto without departing from the spirit and scope of the invention. This patent application is based on Japanese Patent Application (Patent Application No. 2012-128065) filed on June 5, 2012 and Japanese Patent Application (Patent Application No. 2013037301) filed on February 27, 2013, the contents of which are incorporated into this application by way of reference.

权利要求:
Claims (19)
[0001]
1. Method for producing 1,4-butanediol, characterized in that it comprises biologically producing 1,4-butanediol in a culture medium for fermenting an organism capable of producing 1,4-butanediol, at least partially removing each one of a bacterial cell, a salt and water content of said fermentation culture medium to obtain a solution containing 1,4-butanediol of refined raw material, thereby obtaining a solution that presents 1,4-butanediol crude through the realization of Step (c) of hydrogenating unsaturated compounds in solution in combination with one or more Steps (a), (b) or (d) to obtain refined 1,4-butanediol: Step (a): a step of distilling said solution containing 1,4-butanediol from refined raw material in a distillation column to remove components which are contained in said solution containing 1,4-butanediol from refined raw material and which are higher in boiling point than in boiling point. 1,4-butanediol; Step (b): a distillation step said solution containing 1,4-butanediol of refined raw material in a distillation column to remove components which are contained in said solution containing 1,4-butanediol of refined raw material and which are lighter at the boiling point of that 1,4-butanediol; Step (c): a hydrogenation step of converting at least partially unsaturated compounds contained in said 1,4-butanediol-containing refined feedstock solution into at least partially saturated compounds; eStep (d): a step of distilling said solution containing crude 1,4-butanediol in a distillation column and withdrawing refined 1,4-butanediol from a side stream.
[0002]
2. Method according to claim 1, characterized in that the concentration of a carbonyl cyclic compound having a carbon atom number of 5 or 6 in the refined 1,4-butanediol obtained in said step (d) is 12 ppm by mass or less.
[0003]
3. Method according to claim 1 or 2, characterized in that it is a method for producing 1,4-butanediol, which passes through Step (a) and additionally passes through the following Step (e): Step (e): a step of distilling components higher at boiling point than 1,4-butanediol which are separated in said Step (a) in a distillation column and thereby separating and recovering 1, 4-butanediol.
[0004]
4. Method according to any one of claims 1 to 3, characterized in that the refined raw material containing 1,4-butanediol solution, after passing through the following Step (f), is introduced in said Step (c):Step (f): a step of putting said solution presenting 1,4-butanediol of refined raw material in contact with a base.
[0005]
5. Method according to any one of claims 1 to 4, characterized in that the concentration of water in the solution containing 1,4-butanediol of refined raw material, immediately before passing through any of the steps of said Steps (a) to (c), or through Step (f), is from 0.01 to 20% by mass and the pH of it is 5 or more.
[0006]
6. Method according to any one of claims 1 to 5, characterized in that in the hydrogenation step of said Step (c), hydrogenation is performed using a solid catalyst having a nickel-containing metal supported at least on diatomite or silica.
[0007]
7. Method according to any one of claims 4 to 6, characterized in that the base in said Step (f) is a solid base.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that the components lighter at the boiling point than 1,4-butanediol in said Step (b) contain 1-acetoxy-4-hydroxybutane and the concentration of 1-acetoxy-4-hydroxybutane in the solution containing crude 1,4-butanediol, after removing said components lighter at the boiling point than 1,4-butanediol, is from 0.1 to 50 ppm in large scale.
[0009]
9. Method according to any one of claims 1 to 8, characterized in that the bottom temperature of the distillation column in said Step (b) is 120 to 200°C.
[0010]
10. Method according to any one of claims 1 to 9, characterized in that the bottom temperature of the distillation column in said Step (a) is 150 to 200°C.
[0011]
11. Method according to any one of claims 1 to 10, characterized in that the components higher at the boiling point than 1,4-butanediol in said Step (a) have 2-pyrrolidone, and the concentration of 2-pyrrolidone in the solution having crude 1,4-butenediol after removing said components higher in the boiling point than 1,4-butenediol is 20 ppm by mass or less.
[0012]
12. Method according to any one of claims 1 to 11, characterized in that a heating source of the distillation column in said Step (a) only comes into contact with the bottom liquid but does not involve any contact with a part of the gas phase.
[0013]
13. Method according to any one of claims 1 to 12, characterized in that the concentration of gamma-butyrolactone in the suspension distillate of the distillation column in said Step (d) is higher than the concentration of gamma- butyrolactone in refined 1,4-butanediol taken from a lateral stream.
[0014]
14. Method according to any one of claims 1 to 13, characterized in that it comprises a step of controlling the valence of the carbonyl in the solution containing 1,4-butanediol of refined raw material immediately before passing through any of step from said Steps (a) to (c) or through Step (f), to be 2.5 mg KOH/g or less.
[0015]
15. Method according to any one of claims 1 to 14, characterized in that in at least one step of said Steps (b) to (d), the valence of the carbonyl in said solution containing 1,4-butanediol of refined raw material is reduced.
[0016]
16. Method according to claim 1, characterized in that it comprises performing the steps in the order of (a)-(c)-(b)-(d).
[0017]
17. Method according to claim 1, characterized in that it comprises performing the steps in the order of (a)-(e)-(c)-(b)-(d) or (a)-(e) -(f)-(c)-(b)-(d).
[0018]
18. Method according to claim 1, characterized in that it comprises performing the steps in the order of (a)-(f)-(c)-(b)-(d).
[0019]
19. Use of a biomass-derived 1,4-butanediol, obtainable by a method as defined in any one of claims 1 to 18, characterized in that it is for the manufacture of polybutylene terephthalate (PBT) featuring a color hue value b less than 2.7.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-27| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012-128065|2012-06-05|

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JP2012128065|2012-06-05|

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JP2013-037301|2013-02-27|

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JP2013037301|2013-02-27|

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PCT/JP2013/065367|WO2013183592A1|2012-06-05|2013-06-03|Production method for 1, 4-butanediol|

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