TWI280957B - Removal of impurities formed during the production of 1,3-propanediol - Google Patents

Abstract

This invention describes improvements upon a process for the production of 1,3-propanediol (PDO) wherein an aqueous solution of 3-hydroxypropanal (HPA) is formed and the HPA is subjected to hydrogenation to produce a crude PDO mixture. One improvement on this process comprises treating the crude PDO mixture with an acidic zeolite, an acid form cation exchange resin, or a soluble acid to convert the MW176 cyclic acetal to more volatile materials which can be easily separated from PDO by distillation. Another improvement involves removing water from the crude 1,3-propanediol mixture, contacting the resulting mixture with a solid acid purifier at a temperature of from about 50 to about 250 DEG C to convert the MW132 cyclic acetal to more volatile cyclic acetals, and separating the more volatile cyclic acetals from the 1,3-propanediol by distillation or gas stripping.

Description

28 〇 957 〇 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 】 】 】 】 】 】 】 】 】 】 】 】 】 制备 制备 制备 制备 制备 制备 制备 制备 制备And HpA, chlorination to prepare a PDO mixture' and then pour the pD〇 mixture to produce purified PDO. [Prior Art] Several companies have developed technologies for the production of HX based on Ethylene Ethylene. The ethylene bromide system is reacted with a synthesis gas (other than (iv)), which is a mixture of gas-forming carbon monoxide and hydrogen, and T is obtained by steam reforming of natural gas or partial oxidation of hydrocarbons. The idealized reaction of ethylene oxide (E0) and syngas, which produces PD0, can be expressed as follows:

H〇 + CO + 2 H2 present PDO

U.S. Patent Nos. 4,873,378, 4,873,379 and 5, 〇53, 562, and the use of 2: 丨 (mole) synthesis gas in (10) to 12 generations and about 1 〇〇〇 pound per square leaf gauge pressure ((iv) g a single-step reaction under (6900 kPa) yields "PD0 and previous precursors to a π molar percent yield. The catalyst system used consists of ruthenium, multiple phosphines and various acids and water as promoters. U.S. Patent Nos. 5, 3, 766 and 5, 21, 318 to Union Carbide, the reaction of E0 with syngas in the presence of a spent catalyst, U()QC and about 1 ggq squared. Under the time gauge pressure U900 kPa, a selectivity of up to 45 mol% is achieved, and the combined formation rate of 1280957 疋PDO and 3-hydroxypropionaldehyde is quite low, at G.G5 to G.G7 per liter per hour. The preferred result is achieved by increasing the ratio of the acid-suppressing agent to the ruthenium catalyst. U.S. Patent Nos. 5,256,827, 5, 3, 4,686 and 5,304,691 to Shell Oil, the use of the third. _ 合 姑 基 based catalyst from P 制备 and synthesis gas to prepare PDO. Syngas (1: i molar ratio In the range of 9 〇 to 105 ° C and 1400 to 1500 psig ( 〇 〇 〇 〇 〇 〇 ) 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 And the EO conversion rate is in the range of 21 to 34. Later studies have reported an increase in the selectivity and conversion rate. U.S. Patent No. 5,527,973 describes a purification which includes a by-product of the inclusion of (4) by-products. The method of forming the aqueous solution containing a few bases has a value less than ... Η and is added afterwards: the enthalpy is increased to above 7 in the liquid. The solution is then heated to steam from it. Most of the water is removed, and the remaining test solution is heated to distill most of the @PD from the test solution, thereby obtaining a rigid composition having a lower content of the base than the starting composition. - The method has several steps, and the method capable of providing a lower step of reducing the recorded content is a commercially advantageous PDO MW132 acid-reducing system in the form of hydroformylation and hydrogenation reaction as unwanted by-products. It is difficult to separate from PD〇 with simple steaming because He appears to be similar to the volatility of PDO. The formation of the latter will reduce the yield and purity of the coffee. Therefore, if there is a kind of # Mwu2 acid reduction: 1280957, the reaction becomes easier to split from the PD Other materials engraved are highly advantageous. The present invention provides such a chemical method, /, [invention] In a specific example, the present invention is an improvement in the preparation method of 帛m alcohol (PD〇) 3-water-based (tetra) (HPA) aqueous solution, and hydrogenation of the hydrazine to prepare a package of pD 水, water, MW 176 acetal (so called because it is an acetal and has a knife of about 176 a crude mixture of a monk and a low volatile material, wherein the crude PD0 mixture is dehydrated, typically by distillation, to produce a first column comprising water and certain highly volatile materials such as ethanol and/or processing solvent. a distillate stream, and a dehydrated crude pD〇 mixture comprising PDO, MW 176 acetal, and a low volatility material as a first distillate bottoms stream, and wherein the dehydrated crude PD 〇 mixture is steamed to produce Some high waves The second substance overhead distillate stream comprising MW1 76 PD〇 acetal intermediate distillate stream and of a second distillate comprising a low-volatility substances pD〇 the liquid bottom stream is deposited. Most of the recyclable PD〇 is in the intermediate library, which is up to 99.9% by weight of PDO. The second distillate bottoms stream may contain up to 50% by weight of PDO, but this PDO is difficult to separate from low volatility. There may be traces of MW176 acetal in the distillate bottoms stream. In this particular embodiment, the improvement includes 1) a crude PDO mixture prior to dewatering and/or 2) a dehydrated crude PDO mixture prior to distillation and/or 3) a middle distillate stream (in this third embodiment, Another 10 1280957 distillation may be required to transfer PDO from PDO and the ancient ice administration α * sand 咏 父 尚 尚 尚 尚 MW 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 J J J J J J J J J J J J J J J J J J J J J Clay)) contact at 40 j 15 ° C to convert the MW176 cyclic acetal to another chemical species that can be more easily separated from the PDQ by distillation. The procedure can produce other color-generating impurities and PD〇. The generation of oligomers is minimized. In another embodiment of the invention, 1) and / or 2) and / or 3) are in the form of a cation exchange resin (usually a sulfonic acid) with an acid form at a temperature of 15 Torr. Contact at temperatures between 〇. In another embodiment, the stream is treated with a soluble acid, such as HJ04, at a temperature of 2 Torr to 1 Torr (e.g., preferably _ in a corrosion resistant column. Crude PDO The contacting of the mixture with the solid acid purifying agent is carried out in a continuous procedure or batch by standard methods and operations in which the liquid stream is contacted with the solid catalyst or adsorbent. In this way, the separation of impurities such as MW 176 acetal is largely eliminated. Difficulty, it is possible to treat PD 两 to two puritys with high recovery efficiency. In another specific example, the present invention provides a method for preparing hydrazine, 3-propylene glycol, comprising the steps of: _ a) forming 3- propyl group An aqueous solution of the tray, b) hydrogenating the 3-hydroxypropanal to form a first crude 1,3-propanediol mixture comprising hydrazine, 3-propylene glycol, water and MW132 cyclic acetal, and the first crude 1,3-propanediol Distilling the mixture to remove water and low boiling impurities to form a second crude 1,3-propanediol mixture, d) contacting the second crude 1,3-propanediol mixture with the acid form cation exchange resin at a temperature of 50 to 150 °C To MW132 The cyclic acid 11 11280957 is converted to a more volatile cyclic acetal and/or other degradation products, and e) the more volatile cyclic condensation is separated from the iota, 3-propanediol by distillation or stripping. Aldehyde and / or other degradation products. In the best mode of this embodiment, the steps and e) are carried out together (for example in the same vessel or column) such that the volatile cyclic acetals and/or other degradation products are formed from the oxime when they are formed. , Hongpropylene glycol is separated. In another mode of this specific example, an acidic zeolite may be used in place of the acid form cation exchange resin. In this case, a preferred temperature is from 8 Torr to 200 Torr C. [Embodiment] Detailed Description of the Invention The aqueous solution of 3-hydroxypropanal (HpA) which is the starting material of the present invention can be produced by a variety of different methods. U.S. Patent Nos. 4,873,378, 4,873,379, 5,053,562, 5, 〇3, 766, 5, 210, 318, 5, 256, 827, 5, 3, 4, 686 and 5, 3, 4, 691 The numbers are hereby incorporated by reference in their entirety by reference to the same extent as the same. HpA can also be prepared by hydration of acrylaldehyde in the presence of an acidic catalyst. The method of achieving this result is described in U.S. Patent Nos. 5,426,249, 5, 〇15,789, 5'171'898, 5,276,201, 5,334,778, and 5,364,987, all of which are incorporated by reference. The preferred method for carrying out the entire process of the present invention is described in U.S. Patent No. 5,m' 524, the disclosure of which is incorporated herein by reference in its entirety in a reactor, such as a bubble column or a stirred tank, at a syngas of 200 to 5000 psi (138 Torr to 34,5 kPa) (hydrogen·carbon monoxide ratio of 1 ·· 5 to 25 : 1 ), in the presence of a hydroformylation catalyst at a concentration of from 50 to 11 ° C at a concentration of from 5 to 15% by weight, more preferably from 5 to 1 %, of the epoxy Ethane () is added. The hydroformylation reaction effluent is preferably a small amount of water, in a water-to-solvent ratio of 2:1 to 1:20, at 5 to 55 ° C, greater than 50 lbs / Extracted under a carbon monoxide atmosphere of square 吋 (350 kPa). Solvent layer containing more than 90% of the active form of the catalyst Returning to the hydroformylation reactor. The HP A system is extracted in the aqueous layer at a concentration of up to 45% by weight. The catalyst can be removed from the aqueous HPA solution by any known means, including first oxidizing the catalyst. The ion exchange resin can be a weak acid or strong acid ion exchange resin. Examples include: AMBERLYST 15, 35 and XN-1010, AMBERLITE IR-118, IRC76, A1200, DOWEX 50 X 2-100 and 5 X 8-100, XL- 383 and -386, plus BIO RAD AG50W-X2 and AMBERSEP 252H resin' or other strong acid (continued acid) or weak acid (tannic acid) resins (AMBERLYST, AMBERLITE, DOWEX, BIO RAD and AMBERSEP All are registered trademarks. After neutralizing the aqueous solution of 3-light thiophene, the aqueous solution is hydrogenated. This can be achieved by a fixed hydrogenation catalyst bed, typically from 1 Torr to 2000 psi (690 to 13,800). The hydrogenation reaction in a hydrogen gas of kPa is carried out. 13 1280957 The hydrogenation catalyst can be any of those described in U.S. Patent No. 5,786,524, the disclosure of which is incorporated herein by reference, including Catalyst of rhodium, platinum or palladium. The initial hydrogenation is preferably carried out at 4 to 80 C, and the temperature is preferably increased to i 2 to 75. 〇 to excite reactive components such as cyclic acetals. The reaction is returned to pD〇. Finally, water and entrained light (low boiling) solvent and high volatility (low boiling) impurities, crude PDO, are distilled off and the lower volatile components are also separated as a bottoms stream during the distillation. MW132 acetal To carry out the second embodiment of the present invention, the dehydrated (distilled) crude product stream containing MW132 acetal and PD0 is treated as follows to recover PD oxime in high yield and high purity. The crude pd〇 as described above may exhibit a high content of M W13 2 cyclic acetal impurities. This impurity is undesirable and will limit PDO recovery efficiency during subsequent distillation. It can be formed by the reaction of PDO with hydrazine. Reaction #1 m

PDO G ΗΡΑ ir,, 'οι】 MW132 acetal formed under the acid-catalyzed decomposition of MW132 acetal 2·Extended ethyl-1,3-dioxolidine cyclic acid (EDCA) known ratio PDO is more volatile. The following chemical formula explains the dehydration of the MW1 32 acetal to form a 2-ethylidene- 3,2-dioxane cyclic acetal (EDCA) which can be easily separated from the PDO by distillation in 1280957. Acidic zeolites and acid-type cation exchange resins (such as those used to remove cobalt) can be used to purify PDO by reacting MW132 acetal to form EDCA: Reaction #2

Acetal 132

Thus, the dehydrated crude PDO stream containing the undesired mw132 cyclic acetal is contacted with an acid form cation exchange resin or acidic zeolite under conditions conducive to the reaction scheme for the conversion of MW132 acetal to edca as indicated above. This step is combined with EDCA by co-distillation or by removal using a stripping gas such as nitrogen or steam. In the case where the steaming and reaction are combined in the same processing unit to separate the reactants from the newly formed product knives, the co-evaporation and the reaction may employ any well-known method for performing "reactive distillation." An inert gas such as nitrogen is used to extract the reaction mixture of MW132 acetal (EDCA) more volatile degradation products (collaborative extraction and reaction), and thus prevent the re-formation of MW132 through chemical equilibrium. The use of water vapor (steam) is 7 A common commercial measure for the hot and inert extraction of gases. In this case, the extraction is again carried out in the same processing unit as the one used for the reaction of the MW132 acetal. The reaction product is taken out at the time of formation to drive the chemical equilibrium 15 1280957 Eliminating or reducing the appearance of Mw 132. In this manner, the acid catalyzed reaction plus the combination of extraction in the same processing step promotes the reactants in the same manner as the acid catalyzed reaction and distillation, in the same manner as the reactive vaporization. Separation. In general, it has been found that water can suppress the reverse conversion and removal of MW132 acetal, but 'because of incomplete removal, sorption in a solid catalyst or due to the dehydration reaction itself (the above #〇, usually a small amount of water is present) And it is possible to remove a portion of the MW 132 through the reversal of reaction #1. ΗΡΑ 'If formed in this manner, it may be further dehydrated to a highly volatile acrolein which can be easily extracted or distilled from the reaction mixture. The synergistic combination of the acid-catalyzed reaction with the separation (distillation or extraction) of the volatile reaction products leads to a decrease in the MW1 32 impurity contained in the product PD〇. There is a need for synergistic distillation or inertness. Gas extraction drives the chemical equilibrium away from the thermodynamically preferred MW132 cyclic acetal. In the above procedure, acid formed zeolite can also be used to catalyze the degradation of MW132 acetal. The use of acid form cation exchange resin with synergistic separation produces MW132 acetal It is almost completely converted. The reaction is preferably carried out at a temperature of from 5 Torr to 15 Torr, and more preferably at a temperature of from 80 to 120 cc. The contact of the resin catalyst is carried out in batch mode or in a continuous column using a well-known reactor design method to ensure almost complete conversion of M W13 2 . For example, 10% by weight of acid resin can be used at 80 to i2. Batch contact is carried out for 1 to 5 hours to produce complete conversion. Alternatively, it may be in a continuous reaction vessel, preferably in a column, at an hourly rate of 1 to 1, with a weight hourly. Space velocity)'' (16 1280957 pure PDO feed weight per hour - "WHSV" per weight of acid resin) completes the contact. With zeolite, the activity of the reverse conversion is lower, making it necessary to increase the temperature or increase Contact time with zeolite. The reaction with acidic zeolite is preferably carried out at 70 to 250 ° C, more preferably at a temperature of 90 to 170 ° C, by batch or continuous contact. Similar contact times can be used or Weight per hour space velocity. For either system, the temperature must be optimized in combination with the contact time of the solid acid purifying agent (acid form cation exchange resin or acid zeolite) to limit Undesirable color imparts the production of impure impurities and minimizes the production of PDO dimers and higher oligomers. A preferred catalyst is an ion exchange resin (acid form cation exchange resin) having a strong acid cation exchange. These include gel-type or giant network type (macroporous) ion exchange resins having sulfonic acid functional groups in which the sulfonic acid functional groups are bonded directly or indirectly to the organic polymer backbone. Examples include Rohm and Haas AMBERLITE Or AMBERLYST A200, A252,: [R-118, IR120, A15, A35, XN-1010, or A1200 resin with uniform particle size; Dow MSCM, M-31, or DOWEX 50·series resin, SYBRON C-249, C -267, CFP-110 resin; PUROLITE C-100 or C-150 tree; RESINTECH CG8; IWT C-211, SACMP; IWT C-381; or other commensurate commercial strong acid cation exchange resin. Another example of a cation exchange resin is a NAFION acidified perfluorinated sulfonic acid polymer (SYBRON, PUROLITE, RESINTECH and NAFION are registered trademarks). Suitable zeolite catalysts include one or more modified zeolites, preferably those which are acidic. Such zeolites should contain pore sizes that are large enough to allow the acyclic or aliphatic 17 1280957 compound to enter. Preferred zeolites include, for example, zeolites of the following structural types: MFI (e.g., ZSM-5), MEL (e.g., ZSM-11), FER (e.g., magnesium sodium needle zeolite and ZSM-35), FAU (e.g., zeolite). Y), BEA (eg, beta), MFS (eg, ZSM-57), NES (eg, NU_87), MOR (eg, mordenite), CHA (eg, chabazite), MTT (eg, ZSM) -23), MWW (for example, MCM-22 and SSZ-25), EUO (for example, EU-1, ZSM-50 and TPZ-3), OFF (for example, bismuth aluminite), MTW (for example, ZSM- 12) and zeolites such as zeolites ITQ-1, ITQ-2, MCM-56, MCM-49, ZSM-48, SSZ-3 5, SSZ-39 and mixed crystal phases, such as PSH-3 zeolite. References to the structural types and synthesis of various zeolites can be found in "Atlas of Zeolite Structure Types" (represented by the Structure Commission of the International Zeolite Association) by WM Meier, DH Olson and Ch. Baerlocher, published by Butterworth - Heinemann , revised fourth edition, 1996. The structural versions and references of the above zeolites are available on the World Wide Web at www.iza'structure.org. Such zeolites are commercially available from Zeolyst International, Inc. and ExxonMobil Corporation. Further examples of suitable fossil catalysts can be found in U.S. Patent Nos. 5,762,777; 5,808,167; 5,110,995; 5,874,646; 4,826,667; 4,439,409; 4,954,325; 5,236,575; 5,362,697 Nos. 5, 827, 491; 5, 958, 370; 4, 016, 245; 4, 251, 499; 4, 795, 623; 4, 942, 027 and 1 280 957 WO 99/35087, all of which are incorporated herein by reference. MW 176 acetal As shown in the example of Figure 1 to simplify the steaming scheme (which helps to illustrate the first embodiment of the invention), the aqueous solution of pd hydrazine containing MW 176 is introduced into the dehydration column 2 . The water and some highly volatile materials are removed in the overhead &<3> and the dehydrated pD(R) containing the Mwm acid is passed from the distillate bottoms stream to the distillation column 5. The higher volatility material is separated and exits via column (out) (4), while (iv) liquid bottom: #积流8 contains low volatility and some pD 〇 and a small amount of 76 acetal. The recoverable PD0 system exits in the middle distillate stream. Containers 4 and 7 are optional (although it is shown in the drawings that at least one is required in the system). The acid catalyst treatment can be carried out before dehydration in the vessel 1, or after the dehydration in the Gujie 4 but before the distillation, or after the vessel 7 is steamed. When the last specific example is performed, an additional steaming plant is required to separate the more volatile Mwi76 shrink disk reaction product from PD0. · The crude PD〇 as described above sometimes exhibits a high content of MW176 smear-like acid impurities. This impurity was found to be only slightly lower than the slightly lower ones. This limits the efficiency of PDO. Laboratory batch distillation was performed to assess the relative volatility of MW176 impurities and =〇 due to the difficulty in separating from pD〇. At a nominal 1 () mm Hg (u kPa) pressure and I43 c bottom sediment temperature, about 85 grams of PDO contaminated with such impurities and 5-alcohol were refluxed. About J wt% of ethylene glycol (EG) and butyl 19 1280957 diol markers were added to aid in the determination of relative volatility. The results (Table 1) show that both MW176 acetal and C5 diol are heavier than PDO. There is good agreement between the EG's measurement of PDO and the relative volatility of the report, indicating that the equilibrium does approach these measurements. Table 1: Relative Volatile Batch Distillation Data: Species Distillate Bottom Sediment Tit Distillate, Volatile Ratio: wt% wt% t/b2 PDO 97.88 98.09 1.00 Ethylene Glycol 0.369 0.824 2.233 c5 Glycol 0.326 0.280 0.859 MW176 acetal 0.055 0.047 0.855 butanediol 1.375 0.762 0.554 Reported relative volatility of EG/PDO at 230 °F (110 °C) = 2.16 t = distillation "tower" or " overhead" Product "b = distillation" 'bottom deposit'

The MW102 acetal formed under the acid-catalyzed decomposition of MW176 acetal is known to have a much higher volatility than PDO and thus can be easily separated from PDO with high efficiency. This result is based on the expectation that MW1 02 does not contain a hydroxyl group due to condensation elimination. Although we do not wish to be bound by a particular mechanism, the following reactions may explain the degradation of MW176 acetal and the formation of MW102 acetal (which can be easily separated from PDO via distillation) and the formation of MW132 acetal, as in the experiment. Observed. 20 1280957

"Deethoxylation" is known to occur under acidic conditions. The aldehydes and PDO will readily condense under acidic conditions to form a thermodynamically preferred cyclic acetal, in this case MW102 acetal. The acid form of the cation exchange resin or acid zeolite also contributes to the conversion of the MW132 acetal to the 2-extended ethyl-1,3-dioxane cyclic acetal (EDC A) (a substantially higher volatility) Removal of the substance). _

The crude PDO stream comprising the undesired MW176 acetal is treated with an acid form of a cation exchange resin or an acidic zeolite or a soluble acid under conditions conducive to the reaction shown in the reaction 21 1280957 /. The batch or continuous flow sequence can be used in any manner to provide a close connection between the liquid stream and the solid acid purifier or soluble acid, typically commercially in a fixed line, fluidized bed or expanded bed. Continuous contact, downward flow or upward flow operation can be either transparent or good. Although, the optimal size of the bed depends on the solid acid used, 'the particle size and nature of the agent', but the typical design will be accompanied by the 重量i to w" weight hourly space velocity, (WHSV), where whsv The table is not the crude PDQ f flow rate per hour of the (tetra) body acid purifying agent. The optimal bed size and operating temperature are selected to achieve a high level of mwi76 shrinkage conversion rate 'at the same time. The low polymerization of the ingredients is minimized. "When wood is used as a solid acid purifying agent, it is typically required to be in the range of 40 to 15 generations, preferably in the range of 6 to 12 inches. The ambient temperature is 15 〇. The temperature of the water or the lower temperature (low to ambient temperature to traces can be used with the acid form of the cation exchange resin, which has been shown to be more active in the removal of Mwm impurities. When using soluble acids, the temperature is 100oC. Preferably, the zeolite catalyst comprises one or more modified zeolites, preferably in the form of a green form. Such zeolites should comprise pores of a size large enough to allow acyclic or fat to enter. Zeolites include, for example, zeolites of the following structural types (e.g., 'ZSM-5), MEL (e.g., s-n), with (e.g., zeolite and ZSM_35), (10) (e.g., zeolite Y) ^ BEA ( >fe,f μ u ,,βΕΑ (eg 'beta), MFS (eg ZSM_57), deleted (eg, purchase 7), for example, rayon buddha 22 1280957 stone), CHA (eg, chabazite) , MTT (eg, ZSM-23), MWW (eg, MCM-22 and SSZ-25), EUO (eg, EU-1

, ZSM-50, and TPZ-3), OFF (for example, bismuthite), MTW (for example, ZSM-12) and zeolites ITQ-1, ITQ-2, MCM-56, MCM-49, ZSM-48 , SSZ-35, SSZ-39 Shoukou has a crystalline phase of zeolite, such as PSH-3 zeolite. References for the type and synthesis of various zeolites can be found in "Atlas of Zeolite Structure Types" (represented by the Structure Commission of the International Zeolite Association) by WM Meier, DH Olson and Ch. Baerlocher, Butterworth - Heinemann, revised Fourth edition, 1996. The structural types and references of the zeolites mentioned above are available on the World Wide Web at www.iza-structure.org. Such zeolites are commercially available from Zeolyst International, Inc. and ExxonMobil Corporation. Further examples of suitable zeolite catalysts can be found in U.S. Patent Nos. 5,762,777; 5,808,167; 5,1,10,995; 5,874,646; 4,826,667; 4,439,409; 4,954,325; 5,236,575; , No. 5, 827, No. 4, No. 5, 958, 370, No. 4, 016, 245, No. 4, 251, 499, No. 4, 795, 623, No. 4, 942, 027, and WO 99/35087, all of which are incorporated herein by reference.

Other suitable catalysts include acid-type cation exchange resins. These include gel-type or macroreticular (macroporous) ion exchange resins with acid sulfonic acid functional groups, wherein the sulfonic acid functional groups are bonded directly or indirectly to the organic polymer backbone. Examples include: Rohm and Haas AMBERLITE 23 1280957 or AMBERLYST A200, A252, IR-118, IR120, A15, A35, XN-1010, or A1200 resin of uniform particle size; Dow MSC-1 or DOWEX 50-series SYBRON C-249, C-267, CFP-110 resin; PUROLITE C-100 or C-150 resin; RESINTECH CG8; IWT C-211, SACMP; IWT C-381; and other commensurate commercial resins. Another example of such cation exchange resins is a perfluorinated sulfonic acid polymer acidified with NAFION. Soluble acids which can be used include: H2S04, H3P04, HCl and soluble sulfonic acids such as p-sulfonic acid, benzenesulfonic acid and methanesulfonic acid. H2S04 and soluble sulfonic acid are preferred. If such a soluble acid is used, the height is preferably a corrosion resistant tower. The acid is removed with the heaviest component (heavy fraction). The concentration of the acid is preferably from 0.1 to 1.0% by weight. EXAMPLES MW176 EXAMPLES Example 176-1 The results in Table 2 show that treatment with an acid USY zeolite at ambient temperature PDO samples contaminated with MW176 acetal do not effectively reverse the MW176 acetal. Illustrated is room temperature inversion using Rohm and Haas AMBERLYST 15 . High temperature treatment with zeolite at 150 °C overnight resulted in the elimination of MW1 76 to form 2-methyl-1,3-dioxane. However, the formation of poly PDO (di-1,3-propanediol) and higher oligomers occurs at a higher concentration than the original MW176 acetal. Although the problem of more difficult to separate MW 176 acetal is eliminated, the overall purity of 24 1280957 degrees and the yield are thus reduced. The zeolite in the form of USY H+ was used at 1 Torr. (1: Additional timing studies were performed. The results show the reaction conversion of M W17 6 acetal, especially the first gc (gas chromatograph) peak MW176-1, which reacts to almost complete within 5 hours. Degree (MW176 acetal showed 3 peaks in gc/mass spectrometry; the main MW176_i main peak described in Table 2 easily disappeared during acid treatment, while the second, isomer, did not seem to react Different from the earlier test at 150 °C, the conversion at 1 〇〇〇c is selective, and there is no measurable di- or tri-anthracene, and the propylene glycol is condensed by pD〇 to form a shinny silk buddha. The stone sample was accidentally first produced in the form of sodium in the 丨5〇(>c test- 4» instrument to the Dali new heavy-tailed by-product, which may be produced by degradation of pd〇. However, the acid form The mordenite sample was heated overnight at 60 C with the same PDO, showing substantially complete elimination of the MW 丨 76 acetal, which formed the same 2-methyl-1,3 as generally observed with the USY zeolite. - impurities such as dioxane (Mwl 2 acetal) and Mwi32 acetal. This reversal is Selective, because no additional Lutian J product was observed. The acid form of mordenite is therefore comparable to the usy acid form of zeolite. These results indicate that MW176 shrinks when PDO degrades to other by-products to a minimum. Optimum temperature for complete or partial removal of aldehydes 25 1280957 Table 2: Solid acid purification time of PDO contaminated with MW176 Catalyst temperature °c Catalyst wt% MW176 wt% MW132 wt% MW102 wt% RT26.8 MW176 -1 wt% di-PDO wt% tri- PDO wt% Other new HE wt% 0 none (feed) 25 0.0 0.240 0.050 0.000 0.168 0.000 0.000 0.0 24 Acid resin A35 25 4.0 0.010 0.290 0.100 0 0.000 0.000 0.0 24 USYH+ Zeolite 25 4.0 0.240 0.050 0.000 na 0.000 0.000 0.0 24 USYH+ zeolite 15 4.0 0.010 0.041 0.124 0.002 0.545 0.514 0.0 0 No (feed) 25 0.0 0.237 0.093 0.000 0.161 0.000 0.000 0.0 18 Acid resin A15 25 10.0 0.005 0.402 0.161 0.002 0.000 0.000 0.0 18 Acid A15H5% h2o 25 10.0 0.01 0.111 0.048 0.005 0.000 0.000 0.0 27 Na-Silk Buddha 15 10.0 0.016 0.0 84 0.018 0.013 0.000 0.000 20.5 22 H+ mordenite 60 3.6 0.017 0.431 0.143 0.005 0.000 0.000 0.0 0 No (feed) 10 0.0 0.237 0.093 0.000 0.161 0.000 0.000 0.0 1 USY H+ zeolite 10 10.0 0.136 0.209 0.075 0.082 0.000 0.000 0.0 3 USY H+ Zeolite 10 10.0 0.048 0.330 0.127 0.018 0.000 0.000 0.0 5 USY H+ zeolite 10 10.0 0.033 0.371 0.142 0.004 0.000 0.000 0.0 27 USYH+ zeolite 10 10.0 0.030 0.351 0.147 0.003 0.000 0.000 0.0 USY H+ zeolite = CBV-500-X16 LR22765 (4/2/ 2000) H-mordenite = LR23768-128 (1/28/2000) Example 176_2 MW176 acetal impurities were treated at room temperature using a strong cation acid ion exchange resin (Rohm and Haas AMBERLYST A35). The results shown in Table 3 indicate the degradation of MW176 acetal to form MW102 acetal, MW18 (H20) and MW132 acetal. 26 1280957 Table 3: PDO treatment with A35 resin at room temperature Weight % Name MW Start of 2-mercapto cyclic acid 102 0.00 0.10 Cyclic acetal 132 0.05 0.29 Cyclic acetal diol 0.25 0.24 0.01 Water 18 0.02 1.02 PDO 76 99.47 98.39 Other 162 0.02 0.00 Other 176 0.02 0.01 99.81 99.83 Moule balance 1.31 1.35 Treatment of PDO contaminated with MW176 acetal by solid acid treatment can degrade this impurity into a lighter component that can be easily separated by distillation (MW102 Without acidification of the base). The strong cationic acid ion exchange resin reverses the MW176 acetal at room temperature. Acidic zeolites also reverse the MW176 acetal at higher temperatures. At higher temperatures (such as 15 〇〇c used in the experiments), PDO is condensed into polyfluorene, 3-propanediol, by acidic zeolites, resulting in yield loss and lower purity. MW 132 EXAMPLES Example 1 3 2 -1 (Comparative Example) Acid Resin Treatment Prior to Distillation This experiment requires the use of 43.5 g of dry A15 (Amberlyst A15 resin) strong acid form cation after 1500 g of crude pd〇 is removed by distillation to remove moisture. Exchange resin at 100. (: Nitrogen was treated with minimum separation (extraction) for 3 hours. The treated material was bright yellow. The MW132 acetal was only reduced from 3·2 weight 27 1280957% to 2.6% by weight. The treated material was distilled. And the continuous distillation fraction shows that the MW132 acetal is reduced from 11 wt%/❶ to 2 wt%, but the final fraction has up to 2700 ppm of acrylate formation. Because it can release the strong fee treatment of 3-technical K, It is expected that the propionate will be over-formed, thus producing the greatest amount of ester and the final acrylate formation. This example illustrates the treatment of the resin under the absence of synergistic separation (extraction or distillation) of volatile impurities, and no observation To significant MW132 acetal removal. Paste Example 132-2 • Removal of acid-reducing acid resin by synergistic extraction The results of this experiment are listed in Table 4. Add 1 gram of vacuum dried A15 strong acid resin Up to 1 gram of PDO distillate containing 5% by weight of MW132 cyclic acetal (most of which has been distilled off). Heat the sample to 丨〇〇〇c with a metal block heater, while applying Intense nitrogen extraction (collaboration Taken from the liquid expansion of about 1% by volume. The MW132 shrinkage is easily eliminated, and a significant amount of di- or tri-PDO is formed by condensation of the direct PD〇 itself. φ Table 4 Sample time hours 132 Aldehyde weight % di-PDO wt% tri-PDO wt% 167-9 0 1.38 0 0 194-1 1 0.345 0.548 1.356 194-2 3 0.017 3.009 1.934 194-3 5 0.012 6. 667 1.997 28 1280957 Different distillates Repeat this study. 12 grams of PDO distillate was treated with gram dry A15 resin. MW176 acetal (a higher boiling cyclic acetal) and MW132 acetal were eliminated. Two- and three _pd lanthanides The results are shown in Table 5. The results are shown in Table 5. Sample time EG 1^=21.69 MW132 MW176 rt1==24.6 rt'=29.4 hour weight % acrylate 2 acetal rt=26.18 di-PDO tri-PDO weight % wt% wt% wt% wt% N fine feed 197-3 0 0.142 0.416 2.409 0.421 0 〇20b 1 0.126 0.175 1.032 0 0. 615 2.559 20d 2 0.122 0.078 0.282 0 3.004 3.938 20f 5 0.084 0.031 0.067 0 5.929 3.535 Low shrinkage feed 192-5 0 0 0.023 0.3 0.051 0 0 20a -—---- 1 0 0 0.077 0 0.557 0.138 20c 2 0 0 0.044 0 2.027 0.156 20e 5 0 0 0.028 0 4.486 0.206 for gas chromatography retention time 2 hydroxypropyl 3-hydroxypropyl ester used 5% by weight Another similar experiment was carried out with a M3 1 strong acid form cation exchange resin (macroreticular resin). As in previous experiments, the amount of MWl 32 acetal was reduced and PDO dimer was produced via contact with an acid catalyst and synergistic nitrogen extraction. The results are shown in Table 6. 29 1280957 Table 6: Acid Resin + N2 Extraction 5% Resin 100 ° C Catalyst Time Hours MW132 Acetal Weight % Di-PDO Weight % None 12 2.865 0 A15 12 1.509 10.427 M31 12 1.024 10.316 Example 132-3 Distilled dry extract of the resin will show the visible light yellowish secondary distilled PDO product sample in contact with the 5% by weight dry A15 strong acid form cation exchange resin while testing the chromophoric precursor, while nitrogen extraction at l〇5 °C 4 hours. The MW132 shrinkage was substantially removed while forming 1.7 wt% of the bis-PDO (Table 7), yielding a purity of 97.9 wt% gc (gas chromatography). The treated sample was placed in a small 2-inch (〇·6 m) concentric tube column at a bottom temperature of 121 to 123 ° C and re-steamed at 9 mm Hg (丨.3 kPa). Pavilion. Distillation showed that the di-PDO could be easily separated from the PD hydrazine distillate. The MW132 acetal in the distillation was substantially reduced and the gc purity was close to 99 〇/. . The color test produced only a pale yellow color, indicating a decrease in the amount of the chromophoric precursor. Grams MW 132 ppm PDO Weight % Di-PDO Weight % Feed ^160.44 Γ η η. d. 97.933 1.713^ Distillate fraction # 1 ^734 500 99.766 0 2 ^43J5 200 99.910 0 — 3 0 99.894 0 ~' 4 ^ 4341 0 99.846 0 Total 155.09 30 1280957 A less pure sample containing 3% by weight of MW132 acetal which exhibits a pronounced color when analyzing its chromophoric precursor, also as a 5% by weight strong acid resin at the time of nitrogen extraction @ (A15) processing. The resulting PDO did not contain MW132 acetal after four hours, but it did contain 2.9 wt% of di-PDO. Re-distillation was carried out in a 2 inch (0.6 m) concentric tube column at 8 mm Hg (1.3 kPa) and a bottom temperature of 122 to 129 ° C to produce a distillation fraction shown in Table 8. Again, the acid resin eliminates the significant portion of the M W1 3 2 shrink disk, allowing the overhead product without such impurities to be prepared. The di-PDO formed during the resin treatment can be easily separated by distillation. If the MW102 carboxylic acid (2-methyl-1,3-dioxane), which is known to be more volatile than PDO, is not gradually formed during the distillation, the purity of the final distillation fraction becomes very high. However, another distillation will remove this impurity product from the product. Table 8: Acids with re-steaming 1 credits MW132 ppm PDO wt% di-PDO wt% 2-methyl-dioxane MW102 acetal wt% _ feed 192.66 nd 95.204 2.974 0 _^ Therapeutic fraction # 1 15.96 460 99.756 0 0.304 2 50.45 0 98.292 0 0.308 a 3 45.87 0 99.106 0 0.505 a 4 52.60 0 99.329 0 0.606 a 5 10.57 0 98.579 0 1.186 Total 175.45 31 1280957 Example 132-4 such as yttrium oxide Inorganic solid acids such as alumina or zeolite are more suitable for commercial use in nitrogen or steam extractors. However, under comparable conditions, their activity in dehydrating beta-hydroxy cyclic acetals such as MW132 was inferior to that of strong acid ion exchange resins (Table 9). On the other hand, highly reactive resins produce more di- or tri-PDO by-products. However, such oligomers are not considered to be color precursors and are easier to separate by distillation than the original MW132 acetal. For acid-base cation exchange resins and acid zeolites, the temperature and reaction (contact) time are preferably optimally adjusted to maximize the inversion of MW132 acetal to PDO while minimizing the formation of other heavy impurities. . Table 9: Inorganic Solid Acid and Ion Exchange Resin for Acid Extraction Solid Acid Type Temperature °C Solid Acid Weight % Time Hour MW132 Initial Weight % MW132 End Weight % Di-PDO End Weight % ASA Amorphous Oxidation Dream - Oxidation铭100 23 3 0.296 0.253 0 ASA Amorphous cerium oxide-alumina 155 22 2 0.296 0.209 0 Y Η+ zeolite 100 5.7 1 0.296 0.323 0 ZSM5 Η+ zeolite 100 4 3 2.4 1.5 0 ZSM5 Η+ zeolite 100 4 3 0.3 0.07 0 Α15 Strong acid ion exchange resin 105 5 4 0.058 0 1.73 Α15 Strong acid ion exchange resin 105 5.2 4 3 0 2. 97 Α15 Strong acid ion exchange resin 105 5 12 2.9 1.5 10.3 Α15 Strong acid ion exchange resin 100 10 3 1.38 0.017 3 32 1280957 [Simplified Schematic] (1) Figure 1 is a very simple schematic diagram of an embodiment of a simplified distillation process. (2) Component symbol 1 container . 2 dehydration distillation tower 3 overhead distillation stream 4 vessel 5 5 distillation column 6 overhead stream 7 vessel 8 distillate bottom sedimentation stream

33

Claims (1)

1280957 Pickup, patent application scope: 1. A method for preparing 1,3-propanediol, comprising the steps of: a) forming an aqueous solution of 3-hydroxypropanal, b) hydrogenating the 3-hydroxypropanal to form ι,3 a crude 1,3-propanediol mixture of propylene glycol, water and MW132 cyclic acetal and/or MW176 cyclic acetal, c) distillation (dehydration) of the crude 1,3-propanediol mixture to remove water and form 1 a second crude 1,3-propanediol mixture of 3-propanediol and MW132 cyclic acetal and/or MW176 cyclic acetal (first distillate bottoms stream), d) a MW132 cyclic acetal comprising / or MW176 cyclic acetal stream is contacted with a monoacid form cation exchange resin or acid zeolite or soluble acid, and e) removal of the MW132 cyclic acetal and / or MW176 cyclic acetal from 1,3-propanediol . 2. The method for preparing hydrazine, 3-propylene glycol according to claim 1, wherein an aqueous solution of 3-hydroxypropanal is formed, and the hydroxypropanal is hydrogenated to form a 1,3-propanediol, water, MW176 ring. Crude aldehyde and a mixture of high and low volatile materials, a mixture of 3-propanediol, the crude hydrazine, 3-propylene glycol mixture is dehydrated to produce a first overhead stream comprising water and highly volatile materials and comprising hydrazine a 3-dipropylene glycol, a MW176 cyclic acetal with a low volatility I product, a distillate bottoms stream, and a distillation of the first distillate bottoms stream to produce a second overhead stream comprising a high volatility material a stream, an intermediate stream comprising 1,3-propanediol and MW176 acetal, and a second distillate bottoms stream comprising propylene glycol and 34 1280957 low volatility, wherein the crude hydrazine, 3 propylene glycol mixture or first stream At least one of the liquid bottoms deposition stream or intermediate stream is contacted with an acidic zeolite or acid form cationic parent resin or a soluble acid prior to dehydration to convert the MW176 cyclic acetal to a k 1,3 -propanol via A more volatile material that is easily separated by distillation. 3. The method of claim 2, wherein the crude i,3, propylene glycol mixture is contacted with an acidic zeolite at 4 to 150 C prior to dehydration, whereby the color-producing impurities are combined with hydrazine, 3-propanediol. The formation of a more ruthenium oligomer of the water 14 is minimized, or it is contacted with the acid form cation exchange resin at ambient temperature to the temperature, or contacted with a soluble acid at a temperature of 2 Torr to 100 ° C. The MW176 ring is converted into a more volatile material which can be easily separated by distillation of (9) 1,3-propanediol. It is very similar to A. The patent range propylene glycol mixture is in contact with acidic zeolite under 6G to 12 generations. The method of claim 3, wherein the crude "propane:alcohol mixture is contacted with the acid form cation exchange resin at ambient temperature. Liquid bottom: The method of deleting two items, the first, 15th. . . Under the C ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ 15. . . Bottom: Ge, in contact with the acid form or with a soluble acid at a temperature of 2 (35 1280957 to i〇〇°c to convert the MW176 cyclic acetal to a soluble, and -2 by a retorting from 1, A more volatile material which is easily separated from 3-propanediol. The method of claim 2, wherein the intermediate stream is contacted with the acidic zeolite at 40 to 15 〇〇c, thereby producing a color = The production of the dimer and the higher oligomer of the pure substance and the 1,3-propanediol is minimized, or is contacted with the acid form cation exchange resin at a peripheral temperature of 15 ° C or with a soluble acid at 20 to Contact at a temperature of 1 〇〇〇c to convert the MW176 cyclic secret into a more volatile material which can be easily separated from the propylene glycol by distillation. 8. According to the method of claim 6 or 7, #中的物流系与酸硫酸为6〇至丨2〇.〇下 Contact. ...9. According to the method of claim 6 or 7 of the patent scope, ############################################################## Weekly temperature to 1〇〇. Contact with your arm. 10. According to the system of patent application scope i A method of 3: propylene glycol, wherein the method comprises the following steps: a) forming an aqueous solution of 3-hydroxypropanal, b) hydrogenating the 3-hydroxypropanal to form a propylene glycol-containing "MWi32 cyclic acetal" a crude hydrazine, a mixture of 3-propylene glycol, 0 distillation of the first-crude U·propylene glycol mixture to remove moisture and small boiling impurities, and a second crude propylene glycol mixture, d) a second crude propylene glycol mixture and an acid form Contact with resin at a temperature of 50 to 15 generations, or contact with acidic zeolite at 7 Torr; 250Y & temperature to convert _32 ring-down to more: 36 1280957 Volatile cyclic acetal and / Or other degradation products, and b = fine separation of more volatile cyclic acid and/or other degradation products from u propanediol by distillation or gas extraction. γ: The method according to the scope of the application, wherein the second crude 1,3-propanediol mixture is contacted with the acid form cation exchange resin at a temperature of (9) to 120 ° C. The method of item 10, wherein the second coarse: touch, the mixture of the enzyme and the acidic zeolite is at a temperature of 9 ° to 17 ° ° C = according to the method of claim 1G of the patent scope, the step t (7) and The product 仃i is such that the more volatile ring is reduced and/or otherwise reduced, and is separated from the 1,3-propanediol when it is formed, according to the method of claim 1, wherein The second coarse contact...two: the method of the cation exchange resin or the zeolite is prepared by the batch 1,3-, and the method of the 祀 贞 祀 祀 第 第 ' ' ' ' ' ' ' ' ' The chelating system is in contact with the cation exchange resin or the phoenix in a continuous reverse, at a space velocity of up to 10 per hour. - Step by:: The method of claim 10, which includes the following height , point is not pure pick up, circle: 37