Removing impurity formed in preparing 1,3-propanediol

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1,3-propanediol involving the following steps: (a) formation of aqueous solution of 3-hydroxypropanal; (b) hydrogenation of 3-hydroxypropanal to form crude mixture of 1,3-propanediol, water and cyclic acetal of molecular mass 132 Da (MW 132 cyclic acetal) and/or cyclic acetal of molecular mass 176 Da (MW 176 cyclic acetal); (c) distillation (drying) of indicated crude mixture of 1,3-propanediol for water removing and formation of the second crude mixture of 1,3-propanediol (the first flow of residues after distillation) containing 1,3-propanediol and MQ 132 cyclic acetal and/or MW 176 cyclic acetal; (d) contact of the flow containing MW 132 cyclic acetal and/or MW 176 cyclic acetal with acid-base cation-exchange resin or with acid zeolite, or with soluble acid, and (e) removal of MW 132 cyclic acetal. Method provides enhancing effectiveness for extraction and purification of 1,3-propanediol.

EFFECT: improved method of treatment.

10 cl, 9 tbl, 1 dwg, 6 ex

 

Description

The present invention relates to a method for producing 1,3-propane diol (PDO), in which is formed an aqueous solution of 3-hydroxypropane (HPA) and neutralized HPA is subjected to hydrogenation to obtain a mixture of PDO, which is subjected to distillation to obtain purified PDO.

Several companies have developed technology for PDO, based on ethylene oxide as the main raw materials. The ethylene oxide is reacted with synthesis gas (syngas), a mixture of carbon monoxide and hydrogen, which can be obtained by steam reforming of natural gas or partial oxidation of hydrocarbons. The reaction scheme of the interaction of ethylene oxide (EO) with syngas with obtaining PDO shown below:

EO+CO+2H2→PDO

In U.S. patent 4873378, 4873379 and 5053562 company Hoechst Celanese described one-step reaction using a 2:1 (molar) synthetic gas at a temperature of from 110 to 120°and about 1000 pounds per square inch man. (6900 kPa), which receive PDO with access from 65 to 78 molar percent and its original substances. Used catalytic system consisted of rhodium, various phosphines and various acids and water, as promoters.

In U.S. patent 5030766 and 5210318 company Union Carbide described the reaction of EO with syngas in the presence of catalysts containing rhodium. At 110°and 1000 pounds per square inch man. (6900 kPa) 2:1 oparnogo synthetic gas was achieved selectivity up to 47 mole percent, but the overall rate of formation of PDO and 3-hydroxypropane was very low: 0.05 to 0.07 moles per liter per hour. The best results were achieved by improving the relationship of promoter - phosphoric acid to rhodium catalyst.

In U.S. patent 5256827, 5304686 and 5304691 company Shell Oil described receive PDO from EO and synthetic gas using catalysts, complexes of tertiary phosphine with cobalt carbonyl. Under the reaction conditions, namely, from 90 to 105°and at a pressure of from 1400 to 1500 pounds per square inch man. (from 9650 to 10340 kPa) synthetic gas (molar ratio 1:1) within three hours of the selectivity of the process was in the range from 85 to 90 molar percent, and the conversion of EO was in the range from 21 to 34 percent. Later work showed an increase in the selectivity and conversion of EO.

In U.S. patent 5527973 described purification method PDO, which contains the carbonyl by-products, including acetals. An aqueous solution containing the carbonyl PDO is formed at pH less than 7 and then adding to the solution a sufficient amount of base to raise the pH above 7. The solution is then heated for the purpose of distillation from him most of the water followed by heating the remaining basic solution with the purpose of Stripping the most part PDO from the main solution, so that the composition of the PDO had a lower content of carbonyl than the original composition. This method is suitable for all kinds of what is multistage, and could be commercially viable to create a method that will produce the desired product containing lower amounts of carbonyl reducing the number of stages of the method.

MW 132 acetal in PDO is formed as an unwanted by-product of the reactions of hydroformylation and hydrogenation. MW 132 it is difficult to separate from the PDO by simple distillation because he has the same volatility as the PDO. His education reduces the total extraction of the PDO, as well as its purity. So much better to have a way in which MW 132 acetal may be subjected to chemical conversion into other products that are more easily separated from the PDO. The present invention provides a method of chemical conversion.

The invention

In one embodiment of the present invention is an improved method of obtaining 1,3-propane diol (PDO), including the formation of an aqueous solution of 3-hydroxypropane (HPA) and the hydrogenation of the hPa axis, which receive the crude PDO mixture containing PDO, water, MW 176 acetal (so-called because it represents an acetal and has a molecular weight of approximately 176) and high - and low-volatile products, drying the crude PDO mixture, usually by distillation, to obtain the first stream of the upper ring-containing water and some vysokoletuchie products, that is their as ethanol and/or solvents of the process, and dried the crude PDO mixture as the first wrap of the cubic residue containing PDO, MW 176 acetal and low-volatile products, is subjected to distillation to obtain a second stream of the upper shoulder strap, containing some vysokoletuchie products, mid-stream, containing PDO and MW 176 acetal, and the second shoulder strap VAT residue containing PDO and low-volatile products. The main part extracted PDO is in the middle of the stream and is up to 99.9% by weight of PDO. The second shoulder strap VAT residue may contain up to 50 weight percent of the PDO, but this PDO is difficult to separate from low-volatile products. In pursuit of still residue may contain traces of 176 MW acetal.

In this embodiment, the improvement comprises contacting 1) the crude PDO mixture before drying and/or 2) the dried crude PDO mixture before distillation, and/or 3) average flow (in this third embodiment will need to use a different distillation to remove the more volatile reaction products MW 176 acetal from PDO) with acid zeolite (for example, mordenite clay) at a temperature of from 40 to 150°to turn 176 MW cyclic acetal in other chemical products that can be more easily separated from the PDO through the distillation process, where the receiving other colored impurities or oligomers PDO is minimized. In another embodiment from which retene, 1) and/or 2), and/or 3) being in contact with the cation exchange resin-based acids, usually type sulfonic acid, at temperatures between ambient temperature and 150°C. In another embodiment the soluble acid, such as, for example, H2SO4use for processing streams, preferably in the column, which is corrosion resistant at a temperature of from 20 to 100°C.

The contacting of the crude PDO mixture with a solid acid cleaner is carried out in a continuous manner or intermittently, using standard methods and practices for contacting the fluid stream with a solid catalyst or adsorbent. Thus, the difficulties in the separation of impurities, such as MW 176 acetal, to a large extent eliminated, so that the PDO could be distilled to a high degree of purity with high recovery efficiency.

In another embodiment of the present invention provides a method of obtaining 1,3-propane diol containing stages:

a) formation of aqueous 3-hydroxypropyl,

b) hydrogenation of 3-hydroxypropane with the formation of the first crude mixture of 1,3-propane diol containing 1,3-propandiol, water and 132 MW cyclic acetal,

C) a first distillation of the crude mixture of 1,3-propane diol to remove water and low-boiling impurities and formation of the second neocidin the th mixture of 1,3-propane diol,

(d) contacting the second crude mixture of 1,3-propane diol with a cation exchange resin based on acid at a temperature of from 50 to 150°With the transformation of the 132 MW cyclic acetal in the more volatile cyclic acetals and/or other decomposition products, and

e) separation of the more volatile cyclic acetals and/or other decomposition products of 1,3-propane diol by distillation or Stripping gas.

In the preferred method embodiment, stage (d) and (e) perform together (for example, in the same vessel or column), so that the volatile cyclic acetals and/or other decomposition products are separated from 1,3-propane diol as they are formed. In another method of this embodiment may be used in acidic zeolite instead of the cation-exchange resin-based acids. In this case, the temperature is preferably from 80 to 200°C.

Brief description of drawing

Drawing is a very simple schematic representation of an example of a simplified diagram of distillation.

Detailed description of the invention

An aqueous solution of 3-hydroxypropane (HPA), which is the starting material of the present invention, can be obtained in various ways. In the above-mentioned U.S. patents 4873378, 4873379, 5053562, 5030766, 5210318, 5256827, 5304686 and 5304691, which are all included in the description as a reference, the op is Sana different ways of obtaining aqueous solutions of HPA. HPA can also be obtained by hydration of acrolein in the presence of acid catalysts. Methods for achieving this result is described in the U.S. patents 5426249, 5015789, 5171898, 5276201, 5334778 and 5364987, which are all included in the description by reference.

A preferred method for carrying out the entire process of the present invention are described in U.S. patent No. 5786524, which is included in the description by reference, and in General is as follows. The ethylene oxide (EO) is hydroformylating in the reactor, such as a bubble column or tank with agitator, at a pressure of from 200 to 5000 psig (1380 to 34500 kPa) synthetic gas having a ratio of hydrogen to carbon monoxide is from 1:5 to 25:1 at a temperature of from 50 to 110°in the presence of a catalyst of hydroformylation at a concentration of from 0.05 to 15 weight percent, more preferably from 0.05 to 1 percent.

The resulting stream from the reactor hydroformylation preferably extracted with a small amount of water at ratio of water to solvent in the range from 2:1 to 1:20 at a temperature of from 5 to 55°C, in an atmosphere of carbon monoxide greater than 50 psig (350 kPa). A layer of solvent containing more than 90 percent of the catalyst in the active form, is recycled back to the reactor hydroformylation. The NRA is extracted into the water layer at a concentration of about the 10 to 45 weight percent.

The catalyst may be removed from this aqueous solution NDA using any known means, including the first oxidation catalyst and subsequent removal using ion-exchange resin-based acids. The ion-exchange resin may be ion exchange resin based on a weak or strong acid. Examples of these include AMBERLYST 15, 35 and XN-1010, AMBERLITE IR-118, IRC76, A, DOWEX 50×2-100 and 5×8-100, XL-383 and -386, plus BIO RAD AG50W-X2 and AMBERSEP 252H resin or other resin based on a strong (sulfonic) acid or weak (carboxylic) acid (AMBERLYST, AMBERLITE, DOWEX, BIO RAD and AMBERSEP are trademarks). After neutralization with aqueous 3-hydroxypropyl he has been subjected to hydrogenation.

This can be accomplished by hydrogenation over a fixed bed of hydrogenation catalyst usually at a pressure of from 100 to 2000 psig (690 to 13800 kPa) of hydrogen. The hydrogenation catalyst may be one of those described in U.S. patent 5786524, which is included in the description by reference, including catalysts of group VIII metals such as Nickel, cobalt, ruthenium, platinum or palladium. The initial hydrogenation is preferably carried out at a temperature of from 40 to 80°and preferably the temperature is increased from 120 to 175°to obtain the interaction of reactive components, such as cyclic acetals that the s to reverse them back to the PDO. In the end, the water and gone mild (low-boiling) solvent and vysokoletuchie (low-boiling) impurities are subjected to distillation (stream top of a shoulder strap) from the crude PDO, and more low-volatile components are separated during distillation, as zipper bottoms.

MW 132 acetal

In order to realize the second embodiment of the present invention, the flow of the dried crude product (distillation)containing MW 132 acetal and PDO, is processed as described below, in order to extract PDO with high yield and high purity. The crude PDO, as described above, may contain significant quantities of impurities MW 132 cyclic acetal. This mixture is undesirable and limits the efficiency of extraction PDO during subsequent distillation. It can be formed by reaction with PDO HPA.

Reaction #1

It is known that 2-ethylene-1,3-dioxane is a cyclic acetal (EDCA), formed by acid catalytic decomposition MW 132 acetal, is more volatile than PDO. The following formula explains the dehydration MW 132 acetal with the formation of 2-ethylene-1,3-dioxane is a cyclic acetal (EDCA), which can be easily separated from the PDO by distillation. Acid zeolites, cation-exchange resin-based acids (such as used to remove cobalt) can the be used to clean PDO through reactions MW 132 acetal with education EDCA:

Reaction #2

Thus, the stream dried crude PDO containing unwanted MW 132 cyclic acetal, is in contact with the cation exchange resin based on the acid or acid zeolite under conditions that favor the reaction scheme shown above for the conversion of MW 132 acetal in EDCA. This stage is combined with the removal of EDCA through co-distillation or through the use of a desorption gas, such as nitrogen or steam.

Joint distillation and reaction, where the distillation and reaction are combined in the same process section for separating the reactants from the reaction products as they are formed, can use any of the well known methods for conducting "reactive distillation". Alternatively, an inert gas, such as nitrogen, can be used to remove reaction mixtures (co-distillation and reaction) is more volatile products of decomposition MW 132 acetal (EDCA) and thus prevent re-education 132 MW by chemical equilibrium. Usually in industry use of water vapor (steam) to provide process heat and inert agent to remove gas (light fractions). In this case, the distillation of light fractions is carried out again in the same process section that the reaction of the MW 132 acetal. N the FL of the reaction are removed as their education, to shift the chemical equilibrium to eliminate or reduce the content of MW 132 acetal. Thus, the Association reaction, catalyzed by acid, by distillation light ends in a single stage process provides a separation of the initial reagents from the reaction product as "reactive distillation" - a combination of reactions catalyzed by acid, and distillation.

In General, it was found that water suppresses handling and destruction of MW 132 acetal. However, a small amount of water normally present due to incomplete removal, sorption to the solid catalyst or as a result of the reaction of dehydration (#1 above) and may enable the removal portion 132 MW to continue through the return response #1. HPA, if it is formed in this way can then be further subjected to dehydration with getting vysokoletuchih of acrolein, which is easily desorbed or otherelse from the reaction mixture. Regardless of which mechanism dominates, the joint reaction catalyzed by the acid, with separation (distillation or desorption of volatile reaction products result in the reduction in the content of impurities 132 MW in the PDO product. Joint distillation or desorption of inert gas required to shift the chemical equilibrium from thermodynamically favorable for MW 132 of the loop is a mini-acetal. Can also be used acidic zeolite during the process described above, to catalyze the decomposition MW 132 acetal.

The use of cation-exchange resin on the basis of the acid with the joint Department provides virtually complete conversion of MW 132 acetal. The reaction preferably is carried out at a temperature of from 50 to 150°S, more preferably at a temperature of from 80 to 120°C. Contacting the catalyst resin is either a periodic manner, or in a column of continuous operation using well-known methods of constructing the reactor to provide virtually complete conversion of MW 132 acetal. Contacting a periodic manner at a temperature of from 80 to 120°may be conducted for from 1 to 5 hours with 10 percent by weight of the resin-based acids, for example, to achieve a complete transformation. Alternatively, the contacting may be carried out in the reactor of continuous operation, preferably a column, with the average hourly feed rate" (the weight of the source material PDO with impurities of the weight of the resin-based acids in an hour "WHSV") from 0.1 to 1 per hour.

When using zeolites activity reversion acetal below, therefore, require a higher temperature or increased time of contact with the zeolite. Reaction with acid zeolite preferably conducted the ri a temperature of from 70 to 250° S, more preferably from 90 to 170°through periodic or continuous contact. The same time contact duration or average hourly feed rate of the raw material can be used. For any system the combination of temperature and duration of contact with a solid acid cleaner (cation exchange resin based on the acid or acid zeolite) should be optimized to limit the unwanted coloring impurities and to minimize the formation of dimer and higher oligomers PDO.

The preferred catalysts are ion-exchange resin with a cationic exchange based on a strong acid cation exchange resin based on acid). They include ion-exchange resin gel type or macrostate (macroporous) resin with functional groups, sulfonic acid, in which the sulfonic acid is associated directly or indirectly with the main chain of the organic polymer. Examples include Rohm and Haas AMBERLITE or AMBERLYST a, A, IR-118, IR120, A15, A35, XN-1010 or having a uniform particle size A1200 resins; Dow MSC-1, M-31 or DOWEX 50-group resins, international sybron C-249, C-267, CFP-110 resin; PUROLITE C-100 or C-150 resin; RESINOTECH CG8; IWT C-211; SACMP; IWT C-381; or other comparable industrial cation exchange resin on the basis of a strong acid. Another example cationorm is the R resin is NAFION, acidified perfluorinated resin sulfonic acid (international sybron, PUROLITE, RESINTECH and NAFION are trademarks).

Suitable zeolite catalysts contain one or more modified zeolites, preferably in an acid form. These zeolites must contain pores sufficiently large size to permit the entrance or acyclic aliphatic compounds. Preferred zeolites include, for example, zeolites of structural type MFI (for example, ZSM-5), MEL (for example, ZSM-11), FER (for example, ferrierite and ZSM-35), FAU (for example, zeolite Y), BEA (e.g., beta), MFS (for example, ZSM-57), NES (for example, NU-87), MOR (e.g., mordenite), CHA (for example, chabazite), MTT (e.g., ZSM-23), MWW (e.g., MCM-22 and SSZ-25), EUO (e.g., EU-1, ZSM-50 and TPZ-3), OFF (for example, offretite), MTW (for example, ZSM-12), and zeolites ITQ-1, ITQ-2, MCM-56, MCM-49, ZSM-48, SSZ-35, SSZ-39, and zeolites mixed crystalline phases, such as zeolite PSH-3. Structural types and links on the synthesis of various zeolites can be found in "Atlas of Zeolite Structure Types" (published on behalf of the Structure Commission of the International Zeolite Association), W.M. Meier, D.H. Olson and Ch. Baerlocher, published by Butterworth-Heinemann, fourth revised edition, 1996. Structural types and links on the zeolites mentioned above, are listed in the World Wide Web www.iza-structure.org. Such zeolites are supplied on sale Zeolyst International Inc. and ExxonMobil Corporation. Additional examples of suitable zeolite catalysts could the t can be found in U.S. patent No. 5762777; 5808167; 5110995; 5874646; 4826667; 4439409; 4954325, 5236575; 5362697; 5827491; 5958370; 4016245; 4251499; 4795623; 4942027 and WO99/35087, which are included in the description by reference.

MW 176 acetal

As shown in the simplified illustrative diagram of distillation in the drawing, which is useful for describing the first embodiment of the present invention, water PDO containing 176 MW acetal, takes place in column 2 dry distillation. Water and some vysokoletuchie products are removed in stream 3 top shoulder straps and dried with PDO MW 176 acetal of the shoulder straps bottoms is fed to distillation column 5. More vysokoletuchie products are separated and go with the flow 6 of the upper shoulder strap, and shoulder straps 8 bottoms contains low-volatile products and some of the PDO, as well as traces of 176 MW acetal. Retrieved PDO goes in the middle stream. Vessels 1, 4 and 7 are optional vessels for processing acid (although at least one is required in the system shown in the drawing). Treatment of the acid catalyst may take place before drying in the vessel 1, or it may take place after the drying vessel 4, but before distillation, or it can occur after distillation in the vessel 7. When is the last embodiment, an additional distillation to separate the more volatile reaction products MW 176 acetal from PDO.

The crude PDO, as described above, sometimes contains Zn is a significant amount of impurities MW 176 cyclic acetal. It was found that this mixture only slightly less volatile than the PDO, which limits the efficiency of extraction PDO. When there are difficulties in separation from the PDO was conducted periodic laboratory distillation to estimate the relative leucuta impurities MW 176 and PDO. Approximately 85 g PDO contaminated with this substance and also diola5, was heated with refrigerator at a nominal pressure of 10 mm Hg (1.3 kPa) and the temperature of the cubic residue 143°C. Substances tags ethylene glycol (EG) and butanediol were added in an amount of about one weight percent in order to assist in establishing the relative leucuta. The results (table 1) show that as MW 176 acetal and diol With5are more severe than PDO. Good agreement of the results of retrieval between measured against reporting the relative volatility EG compared to PDO, which means that the equilibrium was indeed achieved in these measurements.

Table 1

Relative volatility1
DATA PERIODIC DISTILLATION
ProductsResidues from the distillation weight %Light fractions from the distillation of weight %Attitude

leucuta:

t/b
PDO97,8898,091,00
Ethylene glycol0,3690,8242,233
Diol With50,3260,2800,859
MW 176 acetal0,0550,0470,855
BDO1,3750,7620,554
1Reporting the relative volatility EG/PDO at 230°F (110°S)=2,16

2t="light fractions from the distillation or the product of the upper shoulder strap

b="the residues from distillation

It is known that MW 102 acetal formed by acid catalytic decomposition of 176 MW acetal, is much more volatile than PDO, and therefore can be easily separated from the PDO with high efficiency. This result was the basis of the expected absence of hydroxyl groups in MW 102 due to avoid condensation. Because the authors do not wish to be bound by a particular mechanism, the following reactions can explain the decomposition MW 176 acetal and education 102 MW acetal (which can be easily separated from the PDO by distillation) and education MW 132 acetal, as was observed in experiments.

It is known that "detektirovanie" produced what goes in acidic conditions. Aldehydes are easily condensed with PDO in acidic environments with the formation of thermodynamically favorable cyclic acetals, in this case MW 102 acetal.

Cation-exchange resin-based acids or acid zeolite also facilitates the removal of MW 132 acetal through transformations in 2-ethylene-1,3-dioxane is a cyclic acetal (EDCA), which is significantly more volatile product.

The flow of the crude PDO containing unwanted MW 176 acetal treated cation-exchange resin-based acids, or acidic zeolite, or soluble acid under conditions that are favorable for reactions, some of which were shown above. Periodic or continuous production process can be used in any way in which tightly contacting the fluid stream with a solid acidic cleaner or soluble acid. Usually continuous contacts in a fixed, fluidized or swollen layer is preferred in the industry when working either in a downward flow, either in the upstream or in the horizontal contact apparatus. While the optimal size of the bed depends on the particle size and properties used solid acid cleaner, a typical design would entail "an average hourly velocity of the supply of raw materials" (WHSV) of 0.1 to 10, moreover, the WHSV is expressed as the ratio of the mass flow of the crude PDO by weight of solid acid cleaner per hour. The optimal layer size and operating temperature are selected so that a high degree of conversion MW 176 acetal, at the same time minimizing the oligomerization PDO in other components of the heavy fractions.

When acidic zeolites are used as solid acid cleaner, typically requires temperatures in the range from 40 to 150°C, preferably from 60 to 120°C. a Temperature from ambient to 150°or lower temperatures (as low as ambient temperature up to 100° (C) can be used with cation-exchange resin-based acids, which are considered to be more active in removing impurities MW 176. When using soluble acid, the temperature may be from 20 to 100°C.

The preferred zeolite catalysts contain one or more modified zeolites, preferably in an acid form. These zeolites must contain pores sufficiently large size to permit the entrance or acyclic aliphatic compounds. Preferred zeolites include, for example, zeolites of structural type MFI (for example, ZSM-5), MEL (for example, ZSM-11), FER (for example, ferrierite and ZSM-35), FAU (for example, zeolite Y), BEA (e.g., beta), MFS (for example, ZSM57), NES (for example, NU-87), MOR (e.g., mordenite), CHA (for example, chabazite), MTT (e.g., ZSM-23), MWW (e.g., MCM-22, SSZ-25), EUO (e.g., EU-1, ZSM-50 and TPZ-3), OFF (for example, offretite), MTW (for example, ZSM-12), and zeolites ITQ-1, ITQ-2, MCM-56, MCM-49, ZSM-48, SSZ-35, SSZ-39, and zeolites mixed crystalline phases, such as zeolite PSH-3. Structural types and links on the synthesis of various zeolites can be found in "Atlas of Zeolite Structure Types" (published on behalf of the Structure Commission of the International Zeolite Association), W.M. Meier, D.H. Olson and Ch. Baerlocher, published by Butterworth-Heinemann, fourth revised edition, 1996. Structural types and links on the zeolites mentioned above, are listed in the World Wide Web www.iza-structure.org. Such zeolites are supplied on sale Zeolyst International Inc. and ExxonMobil Corporation. Additional examples of suitable catalysts zeolites can be found in U.S. patentsâ„–â„– 5762777; 5808167; 5110995; 5874646; 4826667; 4439409; 4954325; 5236575; 5362697; 5827491; 5958370; 4016245; 4251499; 4795623; 4942027 and WO99/35087, which are included in the description by reference.

Other suitable catalysts include cation-exchange resin-based acids. These include gel or macrostate (macroporous ion-exchange resin-based acids with functional groups, sulfonic acid, in which the sulfonic acid is associated directly or indirectly with the main chain of the organic polymer. Examples include Rohm and Haas AMBERLITE or AMBERLYST a, A, IR-118, IR120, A1, A35, XN-1010, or having a uniform particle size A1200 resins; Dow MSC-1 or DOWEX 50-group resins; international 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 comparable industrial resin. Another example of such cation exchange resins is NAFION, acidified perfluorinated polymer sulfonic acid.

Soluble acid, which can be used in the process include the H2SO4H3PO4,HCl and soluble sulfonic acids such as paratoluenesulfonyl acid, benzolsulfonat acid and methanesulfonamide acid, etc. H2SO4and soluble sulfonic acids are preferred. If you use these soluble acid, the most preferred corrosion resistant columns. The acid is removed together with the heavy components (heavy fraction). The concentration of the acid is preferably from 0.1 to 1.0 weight percent.

EXAMPLES

Examples MW 176

Example 176-1

The results in table 2 show that the processing of the samples PDO contaminated MW 176 acetal, at ambient temperature, type zeolite USY in acid form was ineffective in reversion MW 176 acetal. Was demonstrated reversion at room temperature using resin on the basis of a strong acid A15 (Rohm and Haas AMBERLYST 15). When vyskot mperatures processing a zeolite at 150° With over night were excluded MW 176 with the formation of 2-methyl-1,3-dioxane. However, at higher concentrations than the original MW 176 acetal was education PDO (di-1,3-propylene glycol and higher oligomers. The overall purity and yield were thus reduced, though much difficulty separating MW 176 acetal was removed.

Additional studies with exposure time were carried out at 100°using zeolite in the form USY H+. The results show the reaction conversion MW 176 acetal, especially the first peak of GC (gas chromatography) MW 176-1, which responds to the actual completion within 5 hours (MW 176 acetal has three peaks in the GC/mass spectral analysis; dominant peak MW 176-1 described in table 2, quickly disappears in the continuation of experiments on acid treatment, while the second "isomer" was directionspanel). Unlike earlier tests at 150°, 100°With the reversion of election was measured without the formation of di - or tri-1,3-propylene glycol by condensation of the PDO.

A sample of mordenite in its sodium form was first tested during a night out at a temperature of 150°that gave a significant number of new heavy fractions by-products, possibly due to the decomposition of PDO. As a result of heating of the sample of mordenite in acid form with t the m same PDO over night at 60° Since it was shown that essentially completely absent MW 176 acetal, but was formed 2-methyl-1,3-dioxane (MW 102 acetal) and impurities MW 132 acetal as observed in type zeolite USY. The reversion was selective, since it was not observed the formation of additional products. The effects of mordenite in acid form, was, therefore, comparable with the action of acid zeolite USY. These results show the optimum temperature required for the complete or partial removal of 176 MW acetal with minimal decomposition of PDO to other products.

Table 2

Purification of the solid acid from MW 176, polluting PDO

Example 176-2

The admixture MW 176 acetal with cation exchange resin based on a strong acid (Rohm and Haas AMBERLYST A35) at room temperature. The results in table 3 show the decomposition of 176 MW acetal with the formation of the MW 102 acetal, MW 18 (H2About) and MW 132 acetal.

Table 3

Pre-treatment PDO resin A35 at room temperature
Weight %
NameMWStartEnd
2-methyl cyclic is cetal 1020,000,10
Cyclic acetal1320,050,29
Cyclic acetal diol1760,240,01
Water180,021,02
PDO7699,4798,39
Other1620,020,00
Other1760,020,01
99,8199,83
The molar balance1,311,35

Treatment of solid acid PDO contaminated MW 176 acetal, may lead to the decomposition of this mixture into lighter components (102 MW dehydrosilybin acetal), which are easily separated by distillation. Cation exchange resins on the basis of a strong acid can reverse MW 176 acetal at room temperature. Acid zeolites can also reverse MW 176 acetal at a higher temperature. At even higher temperatures (as shown for 150° (C) PDO is condensed by acid zeolites in poly-1,3-is propylenglycol, that leads to loss of output and a lower purity.

Examples of 132 MW

Example 132-1 (comparative)

Treatment with resin-based acid prior to distillation

This experiment included the processing of 1500 grams of the crude PDO, with the subsequent removal of water by distillation, from 43.5 grams of dry A15 (Amberlyst A15 resin) cation-exchange resin on the basis of a strong acid in a nitrogen atmosphere for three hours at a temperature of 100°with a minimum separation (desorption). The processed material was bright yellow. The content of MW 132 acetal decreased only from 3.2 weight percent to 2.6 weight percent. The treated material was subjected to distillation, and subsequent fraction distillation showed a decrease in the content of MW 132 acetal from 11% to 2 weight percent, but the formation of acrylate up to 2700 ppm by final fractionation. Excessive formation of acrylate can be expected as a result of treatment in a strong acid, which chemically is not associated with the 3-hydroxypropionic acid, thus forming the maximum number of ester and eventually acrylate. This example shows that there was no significant removal of MW 132 acetal in the processing of the resin in the absence of joint separation (Stripping or distillation of volatile impurities.

Example 132-2

Processing the resin acid-based joint desorption to remove the acetal

The results of this experiment are shown in table 4. 1 gram dried in vacuum resin on the basis of a strong acid A15 was added to 10 grams of distillate PDO containing 1,38% by weight of 132 MW cyclic acetal, from which most of the water was removed by distillation. The sample was heated using a metal block heater to 100°With strong desorption of nitrogen (joint desorption), as evidenced by expansion of the fluid to about 10 volume percent. MW 132 acetal was easily removed with the formation of significant quantities of di - and tri-PDO by the immediate samarangense PDO.

Table 4
SampleTime

Watch
MW 132 Acetal weight %di-PCO weight %three-PDO

weight %
167-901,3800
194-110,3450,5481,356
194-230,0173,0091,934
194-350,0126,6671,997

This is the study were repeated with a different distillate. 1 gram of dry resin A15 was used for the treatment of 12 g of distillate PDO. MW 176 (more high-boiling cyclic acetal) and MW 132 acetals were excluded. Di - and tri-PDO were formed in significant amounts. The results are shown in table 5.

Table 5

Dry desorption resin
SampleTime ClockEG weight %rt1=21,69

Acrylate2< / br>
weight %
MW 132

Acetal

weight %
MW 176

rt=

26,18

weight %
rt1=

24,6

di-PDO

weight %
rt1=29,4

three-PDO

weight %
The source material with a high content of acetal
197-300,1420,4162,4090,42100
20b10,1260,1751,0320of 0.6152,559
20d20,1220,0780,28203,0043,938
20f 50,0840,0310,06705,9293,535
The source material with low content of acetal
192-5000,0230,30,05100
20A1000,07700,557was 0.138
20s2000,04402,0270,156
20E5000,02804,4860,206
1rt represents the time of exposure chromatography

23-hydroxypropylamino

Another similar experiment was conducted using 5 weight percent cation exchange resin on the basis of a strong acid M 31 (macroporous resin). As in the previous experiments, the number of MW 132 acetal decreased, and PDO dimer was obtained by contact with an acid catalyst and co-desorption of nitrogen. Result is you are given in table 6.

Table 6

Resin-based acid + N2 Stripping
5% resin 100°

catalyst
Time

Watch
MW 132

Acetal weight %
di-PDO weight %
No122,8650
A15121,50910,427
M31121,02410,316

Example 132-3

Dry desorption resin-based acids, followed by repeated distillation

Sample product PDO after a double distillation, having a visible light-yellow color when determining substances that lead to the chromaticity of the original substance, in contact with 5 weight percent of dry cation exchange resin on the basis of a strong acid A15 with desorption of nitrogen for 4 hours at 105°C. MW 132 acetal was actually removed at the same time formed to 1.7 weight percent di-PDO (table 7), giving GC (gas chromatographic) purity is 97.9 weight percent. The treated sample was subjected to repeated distillation at a pressure of 9 mm Hg (1.3 kPa) in a small 2-foot (0.6 m) a distillation column consisting of concentric tubes, the temperature of the cube from 121 to 123°s Paragons who showed easy separation of the di-PDO from PDO distillate. Fractions of the distillate is essentially not contained MW 132 acetal, GC frequency was 99.9 percent. The color definition now gave only a slight yellow tint, indicating the reduction of substances that cause the color in the original substances.

Table 7

Desorption of acid re-refining
GramsMW 132

parts per million
PDO weight %di-PDO weight %
Source material160,44No data97,9331,713
The fraction distilling#117,3450099,7660
243,1520099,9100
351,19099,8940
443,41099,8460
TOTAL155,09

Less pure sample containing 3 wt% of the MW 132 acetal, which had a certain color when the allocation of substances, determining the chromaticity of the original substances, was similarly treated with 5 weight percent resin based on a strong acid (A15) with the simultaneous desorption of nitrogen. The resulting PDO is not contained MW 132 acetal after 4 hours, but it contained a 2.9 weight percent di-PDO. Re-distillation at a pressure of 8 mm Hg (1.3 kPa) and the temperature of the cube from 122 to 129°With 2-foot (0.6 m) a distillation column consisting of concentric tubes,allows you to get a fraction distillation is shown in table 8. In addition, desorption of resin-based acid was removed a significant portion 132 MW acetal, therefore, could be derived products top product of the distillation, are free from this taint. Di-PDO formed during processing of the resin, was easily separated by distillation. The purity of the final fractions of the distillation must be very high, if not increasing education 102 MW acetal (2-methyl-1,3-dioxane), which is known as the more volatile than PDO, during distillation. Another distillation will release the product from this mixture.

Table 8

Desorption of acid re-refining
GramsMW 132

parts per million
PDO weight %di-PDO weight % 2-me-

dioxane

MW 102

Acetal

weight %
Source material192,66No data95,2042,9740
The fraction distilling #115,9646099,75600,304
250,45098,29200,308
345,87099,1060worn : 0.505
452,60099,32900,606
510,57098,57901,186
Total175,45

Example 132-4

Inorganic solid acids such as silica-alumina, or zeolites are more suitable for industrial use in the apparatus desorption of nitrogen or steam. However, their activity during dehydration of beta-hydroxycitricacid acetals, such as MW 132 is less than the activity of ion exchange is supposedly based on a strong acid under comparable conditions (table 9). Highly active resin, on the other hand, form a greater number of di - and tri-PDO, as by-products. However, these oligomers are not considered original coloring substances and faster separated by distillation than the original MW 132 acetal. Temperatures and reaction times (contact) preferably are optimally adjustable for cation-exchange resin on the basis of a strong acid in comparison with acidic zeolite, in order to maximize the reversion MW 132 acetal in PDO, at the same time minimizing the formation of other heavy impurities.

Table 9

Inorganic solid acid in comparison with ion exchange resin to acid Stripping
Solid acidTypePace-fever °Solid acid weight %Time ClockMW 132 source weight %MW 132 final-tion weight %di-PDO weeks-tion weight %
ASAAmorphous silica-alumina1002330,2960,2530
ASAAmorphous silica-alumina1552220,2960,209 0
YH+zeolite100the 5.710,2960,3230
ZSM5H+zeolite100432,41,50
ZSM5H+zeolite100430,30,070
A15The ion-exchange resin on the basis of strong acids105540,05801,73
A15The ion-exchange resin on the basis of strong acids1055,24302,97
A15The ion-exchange resin on the basis of strong acids1055122,91,510,3
A15The ion-exchange resin on the basis of strong acids1001031,380,0173

1. The way to obtain 1,3-propane diol, which includes stages:

a) formation of aqueous 3-hydroxypropyl,

b) hydrogenation of 3-hydroxypropane with obrazovanie.nauchno mixture of 1,3-propane diol, containing 1,3-propandiol, water and cyclic acetal with a molecular weight of 132 (132 MW cyclic acetal) and/or cyclic acetal molecular weight 176 (176 MW cyclic acetal),

c) distillation (drying) of the crude mixture of 1,3-propane diol removal of water and formation of the second crude mixture of 1,3-propane diol (first flux residue from distillation)containing 1,3-propandiol and 132 MW cyclic acetal and/or MW 176 cyclic acetal,

(d) contacting a stream containing 132 MW cyclic acetal and/or MW 176 cyclic acetal, with a cation exchange resin based on the acid or acid zeolite, or with soluble acid, and

e) removing MW 132 cyclic acetal and/or MW 176 cyclic acetal of 1,3-propane diol.

2. The method of obtaining 1,3-propane diol according to claim 1, in which is formed an aqueous solution of 3-hydroxypropane, and carry out the hydrogenation of 3-hydroxypropane with the formation of the crude mixture of 1,3-propane diol containing 1,3-propandiol, water, MW 176 cyclic acetal and high - and low-volatile products, the crude mixture of 1,3-propane diol dried to obtain the first stream of the upper ring-containing water, and the first flux residue from distillation, containing 1,3-propandiol, MW 176 cyclic acetal and high - and low-volatile products, and the first flux residue from the distillation is subjected PE is egance with obtaining the second thread of the upper shoulder strap, containing vysokoletuchie products, mid-stream containing 1,3-propandiol and MW 176 acetal, and the second flux residue from distillation, containing 1,3-propandiol and low-volatile products in which at least one of the crude mixture of 1,3-propane diol or the first stream distillation residues, or the average flow is introduced into the contact before drying with acid zeolite or cation exchange resin-based acids, or with soluble acid to convert MW 176 cyclic acetal in the more volatile products, which can be easily separated from 1,3-propane diol by distillation.

3. The method according to claim 2, in which the specified crude mixture of 1,3-propane diol is introduced into the contact before drying with acidic zeolite at a temperature of from 40 to 150°C, preferably from 60 to 120°whereby minimize the formation of coloring impurities and dimers, and higher oligomers of 1,3-propane diol, or with a cation exchange resin based on acid at a temperature from ambient temperature up to 150°C, preferably 100°With or soluble acid at a temperature of from 20 to 100°With turning MW176 cyclic acetal in the more volatile products, which can be easily separated from 1,3-propane diol by distillation.

4. The method according to claim 2, wherein said first flux residue from distillation before it is peregonkoj with acidic zeolite at a temperature of from 40 to 150° C, preferably from 60 to 120°whereby minimize the formation of coloring impurities and dimers, and higher oligomers of 1,3-propane diol, or with a cation exchange resin based on acid at a temperature from ambient temperature up to 150°C, preferably 100°With or soluble acid at a temperature of from 20 to 100°With conversion of MW 176 cyclic acetal in the more volatile products, which can be easily separated from 1,3-propane diol by distillation.

5. The method according to claim 2, wherein said secondary flow is injected into contact with the acidic zeolite at a temperature of from 40 to 150°C, preferably from 60 to 120°whereby minimize the formation of coloring impurities and dimers, and higher oligomers of 1,3-propane diol, or with a cation exchange resin based on acid at a temperature from ambient temperature up to 150°C, preferably 100°With or soluble acid at a temperature of from 20 to 100°with the transformation of 176 MW cyclic acetal in the more volatile materials, which can be easily separated from 1,3-propane diol by distillation.

6. The method according to claim 1 obtain 1,3-propane diol containing stages:

a) formation of aqueous 3-hydroxypropyl,

b) hydrogenation of 3-hydroxypropane with the formation of the first crude mixture of 1,3-p is bandiola, containing 1,3-propandiol, water and 132 MW cyclic acetal,

c) a first distillation of the crude mixture of 1,3-propane diol to remove water and low-boiling impurities and the formation of the second crude mixture of 1,3-propane diol,

(d) contacting the second crude mixture of 1,3-propane diol with a cation exchange resin based on acid at a temperature of from 50 to 150°C, preferably from 80 to 120°With or with acidic zeolite at a temperature of from about 70 to 250°C, preferably from 90 to 170°With conversion of 132 MW cyclic acetal in the more volatile cyclic acetals and/or other decomposition products, and

e) separation of the more volatile cyclic acetals and/or other decomposition products from 1,3-propane diol by distillation or Stripping gas.

7. The method according to claim 6, in which stage (d) and (e) perform together, so that the volatile cyclic acetals and/or other decomposition products are separated from 1,3-propane diol as they are formed.

8. The method according to claim 6, in which the second crude mixture of 1,3-propane diol is introduced into contact with a cation exchange resin or zeolite periodically for from about 1 to about 5 hours

9. The method according to claim 6, in which the second crude mixture of 1,3-propane diol is introduced into contact with a cation exchange resin or zeolite in the reactor of continuous operation at an average hourly SC who grow feed from about 0.1 to about 10.

10. The method according to claim 6, comprising the additional step of distillation of 1,3-propane diol to separate 1,3-propane diol from high-boiling impurities formed in stage (d).



 

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