CN1246275C - Reaction extraction process for extracting lower polybasic alcohol from thin aqueous solution - Google Patents
Reaction extraction process for extracting lower polybasic alcohol from thin aqueous solution Download PDFInfo
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- CN1246275C CN1246275C CN 200410038300 CN200410038300A CN1246275C CN 1246275 C CN1246275 C CN 1246275C CN 200410038300 CN200410038300 CN 200410038300 CN 200410038300 A CN200410038300 A CN 200410038300A CN 1246275 C CN1246275 C CN 1246275C
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- 238000000605 extraction Methods 0.000 title claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000007864 aqueous solution Substances 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 239000000284 extract Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims description 39
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 36
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 30
- 150000001299 aldehydes Chemical class 0.000 claims description 30
- 229920005862 polyol Polymers 0.000 claims description 30
- 150000003077 polyols Chemical class 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclic acetal Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000000855 fermentation Methods 0.000 abstract description 7
- 230000004151 fermentation Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 5
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 235000011187 glycerol Nutrition 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000001577 simple distillation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000588747 Klebsiella pneumoniae Species 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a novel reactive extraction process for extracting low-grade polyhydric alcohol from a thin aqueous solution, which belongs to the technical field of chemical extraction. The reactive extraction technology is a novel reacting extraction method for taking a reaction agent and an extracting agent as the same material. Polyatomic alcohol and aldehyde are carried out with aldolisation to generate annular acetal. Aldehyde which is partially mixed with water is selected as the reaction agent and the extracting agent. In this way, a new organic solvent does not need to be added. Technology is simple. A boiling point of selected aldehyde is lower than that of water. In this way, when a distillation or rectification method is used for recovering the aldehyde from an extract phase, the aldehyde can be obtained from distillate. Energy consumption is low. Impurities in a water phase can be simultaneously stored in the water phase and be separated. The present invention is important to a complex system containing a large amount of impurities, such as fermentation liquid, etc.
Description
Technical field
The invention belongs to the chemical separation technology field, particularly a kind of novel reaction extraction process that from dilute aqueous soln, extracts lower polyol.
Background technology
1, ammediol (1,3-Propandiol is called for short Pdo) is the monomer of production Poly(Trimethylene Terephthalate) (PTT).At document " J, Makromol Chem Phys, 1994, " the Witt U of 195:793～802; Muller RJ; Augusta J, et al, Synthesis properties and biodegradability of polyesters based on1,3-propanediol " " and " Appl Microbiol Biotechol, 1999,52, " the Biebl H of 289-297; Menzel; K, Zeng A-P, et al, Microbial production of 1,3-propanediol " " in report; PTT is a kind of polyester material of excellent performance; existing Pdo production method mainly contains propenal method and epoxyethane method; but problems such as these two kinds of methods exist that side reaction is many, severe reaction conditions and environmental pollution; and output is less; greatly restricted production and the application of PTT, and it is advantages such as renewable resources, environmental pollution be little that fermentation method has mild condition, raw materials for production, is subjected to increasing attention.
Qi Wentao, repair " the glycerine disproportionation produces 1; metabolism of ammediol process and gene regulating mechanism progress " and Zhang Jian that the will dragon is delivered in " Chinese biological engineering magazine; 2003; 23; 64-68 ", Zhao Hongying, " glucose is as cosubstrate fermentative production 1; research of ammediol " that Liu Hongjuan etc. deliver on " modern chemical industry; 2002; 22; 32-35 " show, is raw material with glycerine or glycerol fermented broth and glucose, when utilizing Cray Bai Shi pneumobacillus bacterial classifications such as (Klebsiella pneumoniae) to ferment, during fermentation ends 1, the concentration of ammediol in fermented liquid is about 5%.Also contain a lot of by-product acetic acid salt, lactic acid salt, succinate, glycerine, ethanol, 2 in the fermented liquid simultaneously, 3-butyleneglycol and thalline and remaining components such as substratum.Want to extract 1 from fermented liquid, ammediol, glycerine, 2,3-butyleneglycol just must separate with water these materials with impurity.
Existing from dilute aqueous soln or fermented liquid separation and Extraction 1, the method for lower polyols such as ammediol mainly contains:
1. concentrate distillation method, at first germ-carrying fermented liquid straight run distillation is concentrated; After the cooling, add ethanol or methyl alcohol, n-propyl alcohol, Virahol, acetone, butanone etc. by a certain percentage, by sedimentation or filtration or centrifugation precipitation, get supernatant liquor then; Use same alcohol or ketone washing precipitation again, by sedimentation or filtration or centrifugation precipitation, get supernatant liquor then; The gained supernatant liquor is reclaimed alcohol by distillation or rectifying or ketone (is repaiied the will dragon; Zhang Daijia; Gao Sujun etc., extraction separation 1 in the microbial fermentation solution, the method CN14606712003.12.10 of ammediol).
2. use ion exchange method by Zeo-karb, again by solvent elution, collects 1, ammediol component (Hilaly with fermented liquid; Ahmad K; Binder; Thomas P., Method of recovering1,3-propanediol from fermentation broth, US 6,479,716, and November 12,2002; Roturier; Jean-Michel; Fouache; Catherine; Berghmans; Elie, Process for thepurification of 1,3-propanediol from a fermentation medium, US 6,428,992, August 6,2002).
3. alkali is regulated fermented liquid pH, separates by additive method again, comprises distillation, rectifying, operation such as filtration, extraction and crystallization (Ames; Tyler T., Process for the isolation of 1,3-propanediol fromfermentation broth US 6,361,983, March 26,2002).
4. use the simple liquid-liquid extraction of alcohols from fermented liquid, to extract 1, ammediol (Janusz J.Malinowski, Evaluation of liquid extraction potentials for downstream separationof 1,3-propanediol, Biotechnology Techniques 13:127-130,1999.).
5. use the ion-pair extraction method from fermented liquid, to extract 1, ammediol (Robert R.Broekhuis, ScottLynn, and C.Judson King, Recovery of Propylene Glycol from Dilute AqueousSolutions by Complexation with Organoboronates in Ion-Pair Extractants, Ind.Eng.Chem.Res.1996,35,1206-1214).
6. use formaldehyde, acetaldehyde and 1, ammediol or other lower polyols react, product restores (Robert R.Broekhuis with organic solvent extraction, Scott Lynn, and C.Judson King, Recovery ofPropylene Glycol from Dilute Aqueous Solutions viaReversible Reaction withAldehydes, Ind.Eng.Chem, Res.1994,33,3230-3237; Janusz J.Malinowski, ReactiveExtraction for Downstream Separation of 1,3-Propanediol, Biotechnol.Prog.2000,16,76-79; Janusz J.Malinowskil, and Andrew J.Daugulis, The effective approach forrecovery of methyl-substituted 1,3-dioxane from aqueous media, separation scienceand technology, 37 (11), 2659-2667 (2002); To great waves, Chen Shufeng, Liu Dehua, in the fermented liquid 1, the extracting and separating of ammediol, Tsing-Hua University's journal (natural science edition) 2001,41 (12) 53-55).
From dilute aqueous soln, extract 1 for listed above, the method for ammediol or other lower polyols, 1,3 methods exist energy consumption big, consume the shortcoming of a large amount of organic solvents; 2, the method commercial viability in 4 is relatively poor; The extraction agent price height that method in 5 is used, and extractant regeneration complexity; Method formaldehyde, acetaldehyde boiling point in 6 are low, and easily form polymer and reclaim difficulty, and use organic solvent extraction toxicity such as benzene bigger.
Summary of the invention
The purpose of this invention is to provide a kind of novel reaction extraction process that from dilute aqueous soln, extracts lower polyol.It is characterized in that: described reaction, extraction technology is that reagent and extraction agent are the novel reaction extraction process method of same substance, and the technological process of the described lower polyol that extracts from dilute aqueous soln is:
1. regulate the pH of the dilute aqueous soln that contains lower polyol less than 3 with acid; Or use the catalyzing cation exchange resin aldolization.
2. in dilute aqueous soln, add 5wt%～100wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or the isovaleric aldehyde of solution, make aldehydes can form a phase separately, as extraction agent.
3. the aldehydes and the lower polyol that are dissolved in the dilute aqueous soln, form cyclic acetal and are extracted into the aldehyde phase after 0.2～24 hour-10～60 ℃ of reactions, and separating aldehyde phase and water make acetal and aqueous phase separation.
4. the water that adds 5wt%～10wt% in the extraction phase at acidic conditions or have under the condition of catalyzer and distill, makes acetal decomposition produce lower polyol and aldehydes.Make decomposition reaction be able to forward after aldehydes distills out and carry out, obtain the lower polyol product, reclaim aldehydes simultaneously.
5. dissolved aldehydes in the dilute aqueous soln extracting phase, by distillation or rectifying with its Separation and Recovery.
Described lower polyol comprises: ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerol, 2,3-butyleneglycol, 1,3 butylene glycol or 1,4-butyleneglycol and or its two or more mixture.
Beneficial effect of the present invention is 0.5h reaction end under optimum conditions, speed of reaction is fast, be suitable for serialization production, reagent and extraction agent are same substance, and operational path is simple, and the lower polyol yield can reach more than 95%, save concentration process, energy consumption is lower, does not use extraction agents such as benzene, pollutes characteristics such as lower.
Description of drawings
Fig. 1 extracts the novel reaction extraction process flow synoptic diagram of lower polyol from dilute aqueous soln.
Embodiment
The invention provides a kind of from the novel reaction extraction process of mass concentration less than extraction lower polyol the dilute aqueous soln of 30wt%.Described reaction, extraction technology is that reagent and extraction agent are the novel reaction extraction process method of same substance, to have and contain two or more hydroxyls, carbonatoms is smaller or equal to 4 lower polyol (ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerol, 2,3-butyleneglycol, 1,4-butyleneglycol and 1,3 butylene glycol or its two or more mixture.) carry out aldolization with aldehydes, generate the cyclic acetal, its hydrophobicity is increased, select for use boiling point lower than water, with the miscible aldehydes (propionic aldehyde, butyraldehyde-n, isobutyric aldehyde and isovaleric aldehyde) of water section as the reagent extraction agent of holding concurrently, need not introduce new solvent in addition, technology is simple, the boiling point of selected aldehydes is lower than water, when using distillation or rectificating method like this from extracting phase recovery aldehyde, aldehydes obtains from fraction, make the impurity of aqueous phase can be stored in water and separated going simultaneously, this is even more important for the complex system that fermented liquid etc. contains a large amount of impurity.The technological process of the lower polyol that extracts from dilute aqueous soln is (as shown in Figure 1):
1. the pH that regulates the dilute aqueous soln contain lower polyol with acid is less than 3, or uses Zeo-karb, or with catalyst aldolizations such as solid acids;
2. in dilute aqueous soln, add 5wt%～100wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or the isovaleric aldehyde of solution, make aldehydes can form a phase separately, as extraction agent;
3. after being dissolved in aldehydes in the dilute aqueous soln and lower polyol and reacting in the reaction, extraction tower in Fig. 1, form cyclic acetal and be extracted into the aldehyde phase, separating aldehyde mutually and water makes acetal and aqueous phase separation;
4. the water that adds 5wt%～10wt% in extraction phase at acidic conditions or have under the condition of catalyzer and distill, makes acetal decomposition produce lower polyol and aldehydes.Make decomposition reaction be able to forward after aldehydes distills out and carry out, in lower polyol reduction tower, obtain the lower polyol product.
5. dissolved aldehydes in the dilute aqueous soln extracting phase is incited somebody to action wherein impurity Separation and Recovery in the aldehydes recovery tower by distillation or rectifying.Lifting specific examples is below again illustrated the inventive method.
Example 1
(1) 1 of lower alcohol dilute aqueous soln: 5wt%, ammediol aqueous solution 30mL,
(2) extraction agent: propionic aldehyde 10mL
(3) reaction conditions: transferring pH with hydrochloric acid is 1
(4) temperature of reaction: 15 ℃
(5) extractive reaction time: 1h
(6) extractive reaction result: after intermittently stirring, obtain propionic aldehyde phase 4mL, wherein contain most of acetal that generates.
(7) decomposition of acetal: extraction phase is separated, put into water distilling apparatus, add 0.4mL water, the 0.1mL concentrated hydrochloric acid, overhead product is collected in 50～100 ℃ of heating.After testing, overhead product is the 95wt% propionic aldehyde, and the distillation bottom product is 98wt%1, ammediol.
(8) the extracting phase propionic aldehyde reclaims: by detecting, in the extracting phase 1, the concentration of ammediol is lower than 0.01%,
Extracting phase by 50～80 ℃ of simple distillations, can be obtained the propionic aldehyde of 95wt%.
Example 2
(1) 1 of lower alcohol dilute aqueous soln: 5wt%, ammediol aqueous solution 30mL;
(2) extraction agent: propionic aldehyde 10mL;
(3) reaction conditions: H type Zeo-karb 0.1～3g;
(4) temperature of reaction: 15 ℃;
(5) extractive reaction time: 0.5h;
(6) extractive reaction result: after intermittently stirring, obtain propionic aldehyde phase 4mL, wherein contain most of acetal that generates.
(7) decomposition of acetal: extraction phase is separated, put into water distilling apparatus, add 0.4mL water, H type Zeo-karb 0.5g, overhead product is collected in 50～100 ℃ of heating.After testing, overhead product is the 95wt% propionic aldehyde, and the distillation bottom product is 98wt%l, ammediol.
(8) the extracting phase propionic aldehyde reclaims: extracting phase by 50～80 ℃ of simple distillations, can be obtained the propionic aldehyde of 95wt%.
Example 3
(1) 1 of lower alcohol dilute aqueous soln: 5wt%, ammediol aqueous solution 30mL;
(2) extraction agent: butyraldehyde-n 10mL;
(3) reaction conditions: H type Zeo-karb 0.1～3g;
(4) temperature of reaction: 15 ℃;
(5) extractive reaction time: 0.5h;
(6) extractive reaction result: after intermittently stirring, obtain butyraldehyde-n phase 6mL, wherein contain most of acetal that generates.
(7) decomposition of acetal: extraction phase is separated, put into water distilling apparatus, add 0.5mL water, H type Zeo-karb 0.5g, overhead product is collected in 50～100 ℃ of heating.After testing, overhead product is the 95wt% butyraldehyde-n, and the distillation bottom product is 98wt%l, ammediol.
(8) the extracting phase butyraldehyde-n reclaims: by detecting, in the extracting phase 1, the concentration of ammediol is lower than 0.01%, and extracting phase by 50～80 ℃ of simple distillations, can be obtained 95% butyraldehyde-n.
Example 4
(1) 1 of lower alcohol dilute aqueous soln: 5wt%, ammediol aqueous solution 30mL;
(2) extraction agent: isobutyric aldehyde 10mL;
(3) reaction conditions: H type Zeo-karb 0.1～3g;
(4) temperature of reaction: 15 ℃;
(5) extractive reaction time: 0.5h;
(6) extractive reaction result: after intermittently stirring, obtain isobutyric aldehyde phase 6mL, wherein contain most of acetal that generates.
(7) decomposition of acetal: extraction phase is separated, put into water distilling apparatus, add 0.5mL water, H type Zeo-karb 0.5g, overhead product is collected in 50～100 ℃ of heating.After testing, overhead product is the 95wt% isobutyric aldehyde, and the distillation bottom product is 98%1, ammediol.
(8) the extracting phase isobutyric aldehyde reclaims: by detecting, in the extracting phase 1, the concentration of ammediol is lower than 0.01%, and extracting phase by 50～80 ℃ of simple distillations, can be obtained the isobutyric aldehyde of 95wt%.
Example 5
(1) 1 of lower alcohol dilute aqueous soln: 5wt%, ammediol+2wt%2,3-butyleneglycol+3wt% glycerine mixed fermentation liquid 30mL;
(2) extraction agent: propionic aldehyde 20mL;
(3) reaction conditions: H type Zeo-karb 0.1～3g;
(4) temperature of reaction: 15 ℃;
(5) extractive reaction time: 1h;
(6) extractive reaction result: after intermittently stirring, obtain aldehyde phase 10mL, wherein contain most of acetal that generates.
(7) decomposition of acetal: extraction phase is separated, put into water distilling apparatus, add 1mL water, H type Zeo-karb 0.5g, overhead product is collected in 50～100 ℃ of heating.After testing, overhead product is the 95wt% propionic aldehyde, and the distillation bottom product is 1, ammediol, 2,3-butyleneglycol, glycerol mixture.
(8) the extracting phase propionic aldehyde reclaims: by detecting, and in the extracting phase 1, ammediol, 2, the concentration of 3-butyleneglycol, glycerine all is lower than 0.01wt%, and extracting phase by 50～80 ℃ of simple distillations, can be reclaimed the propionic aldehyde that obtains 95wt%.
Claims (2)
1. novel reaction extraction process that from dilute aqueous soln, extracts lower polyol, it is characterized in that: described reaction, extraction technology is that reagent and extraction agent are the novel reaction extraction process method of same substance, the described extraction from dilute aqueous soln contained two or more hydroxyls, and carbonatoms smaller or equal to the technological process of 4 lower polyol is:
1) pH that regulates the dilute aqueous soln contain lower polyol with acid is less than 3, or uses the catalyzing cation exchange resin aldolization;
2) 5wt%～100wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or the isovaleric aldehyde of adding solution in dilute aqueous soln make aldehydes can form a phase separately, as extraction agent;
3) aldehydes and the lower polyol that is dissolved in the dilute aqueous soln, forms cyclic acetal and is extracted into the aldehyde phase after 0.2～24 hour-10～60 ℃ of reactions, and separating aldehyde phase and water make acetal and aqueous phase separation;
4) add the water of 5wt%～10wt% in the extraction phase, at acidic conditions or have under the condition of catalyzer and distill, make acetal decomposition produce lower polyol and aldehydes, make decomposition reaction be able to forward after aldehydes distills out and carry out, obtain the lower polyol product, reclaim aldehydes simultaneously;
5) dissolved aldehydes in the dilute aqueous soln extracting phase, by the distillation or rectifying with its Separation and Recovery.
2. according to the described novel reaction extraction process that from dilute aqueous soln, extracts lower polyol of claim 1, it is characterized in that: described lower polyol comprises: ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerol, 2,3-butyleneglycol, 1,4-butyleneglycol or 1,3 butylene glycol or its two or more mixture.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102004059334A1 (en) * | 2004-12-09 | 2006-06-22 | Ticona Gmbh | Process for the preparation of acetals |
| CN103664517A (en) * | 2013-12-02 | 2014-03-26 | 天津大学 | Method for recovering polyol from wastewater |
| CN105712841B (en) * | 2014-12-05 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of method of the propane diols of the separation and Extraction from zymotic fluid 1,3 |
| CN105712842B (en) * | 2014-12-05 | 2018-06-19 | 中国石油化工股份有限公司 | The separating and extracting process of 1,3- propylene glycol in a kind of zymotic fluid |
| CN104628711B (en) * | 2015-02-05 | 2017-02-22 | 太原理工大学 | Preparation method of diglycerol diacetal |
| CN110746270B (en) * | 2019-11-04 | 2023-06-06 | 江苏扬农化工集团有限公司 | Method for recycling epichlorohydrin wastewater |
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