CN110790636B - Refining method for removing trace aldehyde group in 1, 3-propylene glycol - Google Patents
Refining method for removing trace aldehyde group in 1, 3-propylene glycol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
The invention relates to a method for removing residual trace aldehyde group-containing impurities in 1, 3-propylene glycol (1, 3-PDO). The hydrogenation reaction product of 3-hydroxypropionaldehyde is dehydrated and concentrated to obtain 1,3-PDO solution containing a trace amount of aldehyde group impurities, sulfonic acid ionic liquid is added into the solution, dealdehyding treatment is carried out at a certain temperature, the 1,3-PDO solution after dealdehyding is rectified under reduced pressure, and distillate is condensed to obtain a high-purity 1,3-PDO product. The 1,3-PDO produced by the acrolein hydration route can reduce the content of residual aldehyde group impurities to below 10ppm after the method is adopted, obtain products with the purity higher than 99.7 percent, and meet the requirements of synthesizing low-chroma polyester PTT on the quality of raw materials. The treatment method is simple to operate, green and efficient, and the acidic ionic liquid can be recycled.
Description
Technical Field
The invention belongs to the field of refining and purification of chemical synthesis, and particularly relates to a refining method for removing trace aldehyde groups in 1, 3-propylene glycol.
Background
1, 3-propanediol (1,3-PDO) is an important organic chemical raw material, and is widely applied to the fields of organic solvents, lubricants, antifreeze agents, medical intermediates, cosmetics, heterocyclic compound synthesis and the like, and in addition, 1,3-PDO also has wide application prospects in the aspects of thermoplastic polyurethane, copolyester and engineering plastics. At present, the most important application is to synthesize a novel polyester material, polytrimethylene terephthalate (PTT), as a polymerization monomer.
The development trend of synthetic fibers is always led since the advent of polyethylene terephthalate (PET) fibers, PTT has the high-strength stability of PET and the excellent molding processability of PBT (polybutylene terephthalate), related textiles are non-wrinkled, high in rebound resilience, firm, wear-resistant, good in dirt resistance, soft in texture, quick-drying, easy to dye and good in color fastness, and the PTT and PBT composite fiber has the advantages of terylene, chinlon and even spandex, can be used for manufacturing high-fluffy BCF yarns, composite fibers, carpets, elastic fabrics and non-woven fabrics, is suitable for clothing and various potential applications, is a hotspot for developing synthetic fibers internationally and has great market potential. With the continuous development of new technologies, the Degussa company, the Shell company and the DuPont company realize the low-cost large-scale industrial production of 1, 3-propanediol, and the good development prospect of PTT gradually attracts people's extensive attention. Because of lower technical difficulty, mild process conditions and mature process scheme, the acrolein hydration hydrogenation route is one of the routes which are developed earlier and are successfully realized in industrialization at present.
When the acrolein hydration route is adopted to synthesize the 1, 3-propanediol, the acrolein is firstly hydrated to generate the 3-hydroxypropionaldehyde (3-HPA), and then the 3-propanediol is obtained by hydrogenation. Since both acrolein and 3-HPA are extremely unstable, polymerization is very likely to occur under the conditions of an acidic catalyst and high temperature, and a small amount of aldehyde by-products are produced. The 3-HPA and the aldehyde by-products are respectively converted into 1, 3-propylene glycol and other alcohol substances after being hydrogenated, but because the hydrogenation is not thorough, partial aldehyde impurities still remain in the hydrogenated products, so that the separated and purified 1, 3-propylene glycol products contain 200-300 ppm of the aldehyde impurities (calculated as formaldehyde), which directly influences the purity of the 1,3-PDO products and the quality of the synthesized PTT fibers, and particularly has more obvious influence on the dyeing effect and the dyeing stability of fiber dyeing. Therefore, a certain method is needed to remove aldehyde impurities in the synthesis process of the 1, 3-propylene glycol, and the aldehyde group content in the 1,3-PDO product is reduced.
At present, the method reported by related patents at home and abroad mainly utilizes the aldol condensation reaction of aldehyde groups under the condition of acid catalysis or alkali catalysis to achieve the aim of reducing the aldehyde content. U.S. Pat. No. 6,9918709 uses perfluorinated ion exchange resin with sulfonic acid side groups as catalyst for the dealdehydization treatment, and the aldehyde content in the 1, 3-propanediol of the product can be reduced to 20 ppm. US 5527973 discloses a process for purifying PDO comprising forming a solution of PDO in an acidic aqueous medium, adding a sufficient amount of base to the aqueous medium to form a basic solution having a pH greater than 7, heating the basic solution to effect distillation of a substantial portion of the water and PDO under different conditions to obtain a PDO composition having a reduced content of carbonyl compounds.
Chinese patent CN1345710 discloses that 1, 3-propanediol containing residual aldehyde impurities is treated with granular clayThe content of residual aldehyde group impurities is reduced to below 50 ppm; CN1417184 discloses that 1, 3-propanediol containing residual aldehyde impurities is treated with sulfonic acid type cation exchange resin, so that the content of residual aldehyde impurities can be reduced to below 20 ppm; CN1417185 discloses the use of 1, 3-propanediol containing residual aldehyde group impurities with a compound having-N+(CH3) The content of residual aldehyde group impurities can be reduced to below 10ppm by treating the strongly basic anion exchange resin with OH-surface functional groups; CN1708467 discloses a process for treating a crude PDO mixture with an acidic zeolite, an acidic cation exchange resin or a soluble acid, converting the cyclic acetal into a more volatile material which can be easily separated from PDO by distillation, and separating the more volatile cyclic acetal from 1, 3-propanediol by distillation or gas stripping; CN1803744A discloses the use of a solid super acidic catalyst SO4 2-/MxOyPerforming dealdehyding treatment at a certain temperature to prepare a 1,3-PDO product which has the 1, 3-propanediol content of more than 99.7 percent and the aldehyde content of less than 10ppm and meets the requirement of synthesizing low-chroma polyester PTT; CN1810750 discloses that a heteropoly acid, a heteropoly acid salt or an immobilized heteropoly acid catalyst is added into a 1, 3-propylene glycol solution containing aldehyde groups after a hydrogenation reaction product of 3-hydroxypropanal is dehydrated to obtain a 1,3-PDO product with the purity higher than 99.6 percent and the aldehyde group content lower than 10ppm, and the quality requirement of polyester PTT on raw materials is met; CN1413971A discloses that a small amount of NH is added into 1,3-PDO aqueous solution containing a small amount of aldehyde groups by utilizing the chemical property that aldehyde can perform addition reaction with ammonia derivatives2The compound of (e) -Y can reduce the residual carbonyl content to 50 μ g/g or less (based on C ═ 0).
In the method, the effect is poor when the carclazyte and the ammonia derivative are adopted for dealdehyding, and the dealdehyding effect is good when the acid-base ion exchange resin is used as the catalyst, but the resin has the defects of high cost, slow reaction rate, poor thermal stability, incapability of regeneration and the like.
Therefore, aiming at the problem of higher aldehyde group impurities in the 1,3-PDO product in the acrolein hydration hydrogenation process, a more effective method is needed to be found to solve the defects in the prior art.
Disclosure of Invention
The invention aims to overcome the defects in the existing aldehyde removal technology and provides a method for catalytically removing trace aldehyde group impurities in 1, 3-propanediol, which has the advantages of high catalytic efficiency, good aldehyde removal effect, easiness in separation, reusability of a catalyst and the like.
From the structure of aldehyde group impurities in 1,3-PDO, the aldehyde group impurities all have active hydrogen on alpha position, and can generate condensation reaction under the action of acid or alkali to form molecules with complex structures or be converted into more volatile substances, and the boiling points of the molecules are greatly different from that of 1,3-PDO, so that the molecules can be easily separated by distillation. Experiments show that the acidic ionic liquid is a feasible aldehyde group removal catalyst, and the sulfonic acid functionalized acidic ionic liquid has the advantages of designability of structure, adjustable acidity, extremely low saturated vapor pressure and the like, and has the advantages of high catalytic efficiency, good recycling performance and the like.
In order to achieve the above objects and achieve the above technical effects, the technical solution of the present invention is as follows:
a refining method for removing the trace aldehyde group from 1, 3-propanediol includes such steps as adding the ionic liquid of sulfonic acid to the dewatered 1, 3-propanediol concentrate containing trace aldehyde group impurities, catalytic reaction of aldehyde group by ionic liquid for removing aldehyde, and vacuum rectification.
The 1, 3-propanediol dehydrated concentrate is obtained by removing low-boiling alcohol and partial dehydration from 3-HPA hydrogenated liquid, and the water content is 10-30%.
In the invention, the structural formula of the sulfonic acid ionic liquid is shown in the specification
Wherein the anion is
Selected from Cl-、BF4 -、HSO4 -、CF3SO3 -Is preferably HSO4 -Or CF3SO3 -；
m is 0 to 4, preferably 0 to 3; a is 0 or 1; n is 1 to 12, preferably 1 to 5.
In the invention, at least one ion in the anion or cation of the used sulfonic acid ionic liquid carries a sulfonic acid group, and when two sulfonic acid groups are carried, the two groups can be the same or different. The sulfonic acid functionality greatly increases its acidity and water solubility.
The ionic liquid is prepared by a one-step method or a two-step method, and the preparation method is referred to in the literature "
The acidic ionic liquid catalyzes the acetalization reaction to synthesize polymethoxy dialkyl ether (the journal of catalysis, 2017, 38(5): 853-. The preparation process of the two methods is as follows:
a one-step method: adding a certain amount of N-alkyl imidazole into a reaction container, slowly dropwise adding 98% concentrated sulfuric acid into the reaction container at the temperature of 0 ℃ in a molar ratio of 1:1, stirring the mixture for 1h, heating the mixture to reflux, keeping the reflux for 6h, cooling the mixture to room temperature, washing the mixture for 3 to 5 times by using diethyl ether or ethyl acetate, rotationally evaporating a small amount of water in the mixture, and then putting the mixture into a vacuum drying oven for drying to obtain the corresponding ionic liquid.
A two-step method: firstly synthesizing corresponding ionic liquid precursor, and then adding corresponding acid for acidification to obtain ionic liquid with different anions. The specific method comprises the following steps: weighing a certain amount of corresponding N-alkyl imidazole, and uniformly mixing with organic solvents such as toluene or dichloromethane and the like at 0-25 ℃. Equimolar amounts of sultone or chloroalkylsulfonic acid are weighed and added dropwise to a solution of imidazole in toluene or dichloromethane. After 30-90min, the temperature is raised to 70-90 ℃, and the reflux reaction is carried out for 6-24 h. After the reaction is finished, cooling the reaction solution to room temperature, and filtering the organic solvent through a Buchner funnel to obtain a crude product of the zwitterionic liquid precursor. Washing and drying to obtain a corresponding zwitterionic liquid precursor, and drying in vacuum at a certain temperature for later use; and adding corresponding acid into a container containing the ionic liquid precursor dropwise according to an equimolar amount, reacting at room temperature for 30-90min, raising the temperature to 80 ℃, and reacting for 12-48h or reacting at room temperature for about 30 days. And after the reaction is finished, cooling to room temperature, dissolving the obtained crude product of the ionic liquid in dry acetonitrile to form an acetonitrile solution of the ionic liquid, adding activated carbon, stirring, filtering to remove the activated carbon, and performing rotary evaporation to remove the acetonitrile solution to obtain the crude product of the ionic liquid, or directly performing rotary evaporation to remove most of water or HCl in the reaction system to obtain the crude product of the ionic liquid. The crude product is washed 3-5 times with dry organic solvents, diethyl ether or ethyl acetate. And (3) drying the obtained ionic liquid in a vacuum drying oven at 40-80 ℃ for 24-48h to obtain the target ionic liquid.
The structure of the N-alkyl imidazole is
n is 0 to 12, preferably 1 to 5.
Preferably, the structure of the sulfonic acid ionic liquid used in the present invention is as follows:
in the present invention, the sulfonic acid ionic liquid is added to the 1, 3-propanediol dehydrated concentrate in a proportion of 0.1 to 10% by weight, preferably 0.5 to 2% by weight.
In the present invention, the reactor for the dealdehyding reaction is selected from a packed fixed bed reactor, a stirred tank reactor, a fluidized bed reactor or a multitubular fixed bed reactor, and preferably a tank reactor.
In the present invention, the temperature of the dealdehyding reaction is 60 to 140 ℃ and preferably 80 to 100 ℃. During the aldehyde removal operation, the treatment temperature has great influence on the content of aldehyde group substances in the product, and the aldehyde group is removed more completely at higher temperature. However, since 1, 3-propanediol is also subject to intermolecular or intramolecular dehydration in an acidic environment, a suitable temperature range is required.
In the present invention, the time for the dealdehyding reaction is 0.5 to 6 hours, preferably 1 to 3 hours.
In the invention, the theoretical plate number during vacuum rectification is 16-40, the reflux ratio is 2:1-15:1, the temperature of the tower kettle is 138-.
The pressures are absolute pressures.
The refining method can obtain the 1, 3-propylene glycol product with residual aldehyde impurity content less than 10ppm and purity more than 99.7 percent.
The method for removing aldehyde and refining in the invention is used for separating and refining products in the production of 1, 3-propylene glycol in an acrolein hydration route, or is used as a method for removing trace aldehyde impurities in general 1, 3-propylene glycol, and is suitable for removing aldehyde and refining 1, 3-propylene glycol of various commodities.
The invention has the positive effects that:
(1) the aldehyde-removing refining method can obtain the product with residual aldehyde group impurity content less than 10ppm and purity more than 99.7%.
(2) Simple operation, easy separation, reusable ionic liquid and obvious cost advantage.
(3) Can be used as a method for removing micro aldehyde in general 1, 3-propylene glycol, and is suitable for the aldehyde-removing refining of various commercial 1, 3-propylene glycols.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to these examples.
Main raw material table
Nuclear magnetic characterization (NMR): the instrument was a Bruker ASCEND spectrometer,1H，600MHz；13C{1H}，150MHz；11B{1H}，192MHz；19F{1H}，564MHz；31P{1h, 243MHz spectrum. The ionic liquid was qualitatively characterized.
Preparing ionic liquid BIL-1-8:
preparing BIL-1: adding 2.5g of N-methylimidazole into a 100mL three-neck flask, slowly dropwise adding 98% concentrated sulfuric acid into the mixture at the temperature of 0 ℃ in a molar ratio of 1:1, stirring the mixture for 1h, heating the mixture to reflux, keeping the reflux for 6h, cooling the mixture to room temperature, washing the mixture for 3 to 5 times by using diethyl ether, rotationally evaporating a small amount of water in the mixture, and then putting the mixture into a vacuum drying oven at the temperature of 60 ℃ for drying for 12h to obtain yellow liquid, namely BIL-1.
In the invention, except that the ionic liquid BIL-1 is directly synthesized by a one-step method, other ionic liquids are obtained by a two-step method, namely, the corresponding zwitter-ion precursor is firstly synthesized, and then the corresponding acid is added for acidification to obtain the ionic liquids with different anions.
Synthesizing a BIL-2-5 zwitterionic liquid precursor: methylimidazole (10g, 0.12mol) and toluene (50mL) were placed in a 100mL three-necked flask and mixed well at 0 ℃. Equimolar amounts of 1, 3-propanesultone were weighed and added dropwise to the methylimidazotoluene solution. After 30min, the oil bath temperature was raised to 80 ℃ and the reaction was refluxed for 24 h. After the reaction is finished, cooling the reaction solution to room temperature, and filtering the toluene solvent through a Buchner funnel to obtain a crude product of the zwitterionic liquid precursor. Washing with ethyl acetate for 3-5 times, filtering, and drying the white solid in a vacuum drying oven at 80 deg.C for 48h to obtain white powdery zwitterionic liquid precursor.
Preparing BIL-2: 2.0g (10X 10) are weighed out-3mol) the ionic liquid precursor prepared above was placed in a 50mL round-bottom flask, an equimolar amount of 36 wt% hydrochloric acid was added dropwise to the flask, and after reacting for 30min at room temperature, the temperature was raised to 80 ℃ and reacted for 24 h. And after the reaction is finished, removing most of water in the reaction system by rotary evaporation to obtain a BIL-2 crude product. The crude product was washed 3-5 times with dry ether, ethyl acetate. And (3) drying the obtained BIL-2 in a vacuum drying oven at 80 ℃ for 24h to obtain the BIL-2.
Preparing BIL-3: weighing 2.0g (10X 10)-3mol) the ionic liquid precursor prepared above was placed in a 50mL round-bottom flask, an equimolar amount of 60 wt% tetrafluoroboric acid was added dropwise to the flask, and after 30 days of reaction at room temperature, most of water in the reaction system was removed by rotary evaporation at 40 ℃. With dried diethyl ether, ethyl etherWashing the crude product with ethyl acetate for 3-5 times, and drying under high vacuum (0-10Pa) at 40 deg.C for 48h to obtain BIL-3.
Preparing BIL-4 and BIL-5: weighing 4.0g (0.048mol) of ionic liquid precursor, placing the ionic liquid precursor into a 50mL round-bottom flask, dropwise adding equimolar sulfuric acid (for synthesizing BIL-4) or trifluoromethanesulfonic acid (for synthesizing BIL-5) into the flask, reacting at room temperature for 60min, raising the temperature of a high oil bath to 80 ℃, and reacting for 24 h. And after the reaction is finished and cooled to room temperature, dissolving the obtained crude ionic liquid product in 20mL of dried acetonitrile to form an ionic liquid acetonitrile solution, adding 5g of activated carbon, stirring for 30min, filtering to remove the activated carbon, and performing rotary evaporation to remove the acetonitrile solution to obtain a light yellow oily liquid. The crude product was washed 3-5 times with diethyl ether, ethyl acetate. Drying the obtained ionic liquid at 80 deg.C under high vacuum (0-10Pa) for 24 hr to obtain BIL-4 and BIL-5, respectively.
Qualitative characterization of BIL-4:1H NMR(600MHz,D2O-d2,298K):δ(ppm)8.65(s,1H),7.42(t,J＝1.2Hz,1H),7.34(t,J＝1.2Hz,1H),4.20(t,J＝7.2Hz,2H),3.83(s,3H),2.82(t,J＝7.2Hz,2H),2.23(t,J＝7.2Hz,2H)；13C{1H}NMR(150MHz,D2O-d2,298K):δ(ppm)136.4,123.8,122.2,47.8,47.3,35.9,25.2。
qualitative characterization of BIL-5:1H NMR(600MHz,D2O-d2,298K):δ(ppm)8.66(s,1H),7.43(s,1H),4.28(t,J＝7.2Hz,2H),3.80(s,3H),2.85(t,J＝7.8Hz,2H),2.23(p,J＝7.2Hz,2H)；1H NMR(600MHz,CD3CN-d3,298K):δ(ppm)10.92(s,1H),8.51(s,1H),7.42(s,1H),7.35(s,1H),4.32(t,J＝7.2Hz,2H),3.84(s,3H),3.10(t,J＝7.2Hz,2H),2.33(p,J＝7.2Hz,2H)；19F{1H}NMR(564MHz,CD3CN-d3,298K):δ(ppm)-79.27；13C{1H}NMR(150MHz,D2O-d2,298K):δ(ppm)136.4,123.8,122.4,47.8,47.5,35.9,25.0。
preparing BIL-6: methylimidazole (5.0g, 0.6mol) was first dissolved in 100mL of dry dichloromethane and equimolar chlorosulfonic acid was added dropwise. The reaction solution was stirred at 25 ℃ for 30min to give a white flocculent solid, which was allowed to stand for 5min, and the dichloromethane supernatant was poured out of the reaction flask. The remaining white solid product was washed 3-5 times with dry dichloromethane, and the remaining organic solvent (0-10Pa) was pumped out with a vacuum oil pump. Then adding equimolar trifluoromethanesulfonic acid, continuously stirring under a reduced pressure condition, and extracting a byproduct HCl to obtain a BIL-6 crude product. Washing the crude product with dry ether for 3-5 times, and vacuum drying to obtain BIL-6.
Preparing BIL-7: the synthesis method is the same as that of BIL-4, except that 1, 3-propanesultone is replaced by equimolar 1, 4-butanesultone when synthesizing the precursor.
Preparing BIL-8: the synthesis method is the same as that of BIL-4, except that the precursor is synthesized by using N-butylimidazole in an equimolar amount instead of N-methylimidazole.
Preparing BIL-9: imidazole (15.0g, 0.220mol) was directly mixed with an equimolar amount of NaOH, reacted at 95 ℃ for 8h, and vacuum dried at 110 ℃ for 4h to give imidazole sodium salt. The resulting imidazole sodium salt was mixed with 100mL of tetrahydrofuran at room temperature and 0.9 equivalent of 1-bromododecane was added rapidly. The mixture was stirred at 65 ℃ for reaction overnight. After the reaction was completed, the reaction solution was cooled to room temperature and filtered to obtain a pale yellow filtrate. The solvent was removed by rotary evaporation to give a crude 1-dodecaneimidazole. The crude product was dissolved in 250mL of dichloromethane and 10g of activated carbon and 5g of MgSO were added4Stirring for 15min, and filtering. The filtrate was freed of the solvent by rotary evaporation to give a pale yellow product.
0.030mol of light yellow 1-dodecyl imidazole product and toluene (10mL) are placed in a 50mL three-neck flask and are mixed uniformly at 0 ℃. Equimolar amounts of 1, 3-propanesultone were weighed and added dropwise to the solution. After 1h, the oil bath temperature was raised to 90 ℃ and the reaction was refluxed for 24 h. After the reaction is finished, cooling the reaction solution to room temperature, and filtering the toluene solvent through a Buchner funnel to obtain a crude product of the zwitterionic liquid precursor. Washing with ethyl acetate for 3-5 times, filtering, placing the milky solid in a high-temperature vacuum drying oven, and drying at 80 ℃ for 48h to obtain a milky waxy zwitterionic liquid precursor.
And (3) placing the obtained ionic liquid precursor into a 50mL round-bottom flask, dropwise adding 0.025mol of 98 wt% trifluoromethanesulfonic acid, reacting at room temperature for 60min, and raising the oil bath temperature to 80 ℃ to react for 48 h. And after the reaction is finished and cooled to room temperature, dissolving the obtained crude ionic liquid product in 20mL of dried acetonitrile to form an ionic liquid acetonitrile solution, adding 5g of activated carbon, stirring for 30min, filtering to remove the activated carbon, and performing rotary evaporation to remove the acetonitrile solution to obtain a light yellow oily liquid. The crude product was washed 3-5 times with dry ether, ethyl acetate. And respectively drying the obtained ionic liquid in a high-vacuum (0-10Pa) drying oven at 80 ℃ for 24h to obtain BIL-9.
Examples 1 to 16
Preheating 1, 3-propylene glycol solution containing aldehyde impurities to 60-140 ℃, pumping into 250mL of a stirring tank type reactor by using a pump, adding sulfonic acid ionic liquid to the concentration of 0.1-10 wt%, and carrying out dealdehyding reaction for 0.5-6 h. Distilling the treated 1, 3-propylene glycol, wherein the number of the tower plates is 16-40, the temperature of the tower bottom is 138-155 ℃, the reflux ratio is 2:1-15:1, and the pressure at the tower top is 1-10 kPa. The specific operating conditions and treatment effects are shown in the following table, and the aldehyde group content in the raw material before the aldehyde removal treatment is 792 ppm.
TABLE 1 Dealdehyde Process and Effect of different sulfonic acid Ionic liquids
Claims (15)
1. A refining method for removing trace aldehyde group in 1, 3-propanediol is characterized in that sulfonic acid ionic liquid is added into 1, 3-propanediol dehydrated concentrated solution containing trace aldehyde group impurities, aldehyde group is catalyzed by the ionic liquid to carry out aldehyde removal reaction, and then products with low aldehyde content and high 1, 3-propanediol purity are obtained through reduced pressure rectification;
wherein the structural formula of the sulfonic acid ionic liquid is shown in the specification
Wherein the anion is
Selected from Cl-、BF4 -、HSO4 -、CF3SO3 -M is 0-4, a is 0 or 1, and n is 1-12.
2. The method as claimed in claim 1, wherein the sulfonic acid ionic liquid used has an anion of the formula
Selected from HSO4 -Or CF3SO3 -M is 0-3, n is 1-5.
3. The method according to claim 1 or 2, wherein at least one of the anion and the cation of the sulfonic acid ionic liquid used carries a sulfonic acid group, and when two sulfonic acid groups are carried at the same time, the two groups may be the same or different.
4. The method according to claim 1 or 2, wherein the sulfonic acid ionic liquid is added to the 1, 3-propanediol dehydrated concentrate in a proportion of 0.1 to 10 wt%.
5. The method according to claim 4, wherein the sulfonic acid ionic liquid is added to the 1, 3-propanediol dehydrated concentrate in a proportion of 0.5 to 2 wt.%.
6. The method according to claim 1 or 2, wherein the reactor for the dealdehydizing reaction is selected from a packed fixed bed reactor, a stirred tank reactor, a fluidized bed reactor and a multi-tube fixed bed reactor.
7. The method of claim 6, wherein the reactor for the dealdehyding reaction is a stirred tank reactor.
8. The method according to claim 1 or 2, wherein the temperature of the dealdehyding reaction is 60 to 140 ℃.
9. The method according to claim 8, wherein the temperature of the dealdehyding reaction is 80 to 100 ℃.
10. The process according to claim 1 or 2, wherein the time for the dealdehydizing reaction is 0.5 to 6 hours.
11. The method according to claim 10, wherein the time for the dealdehydizing reaction is 1 to 3 hours.
12. The method as claimed in claim 1 or 2, wherein the theoretical plate number during vacuum distillation is 16-40, the reflux ratio is 2:1-15:1, the temperature in the column bottom is 138-155 ℃, and the operating pressure is 1-10 kPa.
13. The process of claim 1 or 2, wherein the purification process results in a 1, 3-propanediol product having a residual aldehyde impurity level of less than 10ppm and a purity of greater than 99.7%.
14. The method as claimed in claim 1 or 2, wherein the method is suitable for the aldehyde-removing purification of various commercial 1, 3-propanediol as a method for removing the trace aldehyde impurities in the general 1, 3-propanediol.
15. The method as claimed in claim 14, wherein the method is used for separation and purification of the product in the production of 1, 3-propanediol by the acrolein hydration route.
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| CN113248441A (en) * | 2021-04-30 | 2021-08-13 | 大连理工大学 | Dual-functional ionic liquid, preparation method thereof and application thereof in catalytic synthesis of bisphenol compound |
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