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    US patent

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    4 просмотров9 страниц

    US8766019B2

    Загружено:

    Erpin Febrian
    US patent

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    © All Rights Reserved
    Скачайте в формате PDF или читайте онлайн в Scribd
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    (2) oy 0s) my an @ (66) (7) ws) G0) Aug. 6, 2010 United States Patent Ying et al. METHOD FOR SEPARATING BUTANOL Inventors: Hanjie Ving, Nanjing (CN): Xtaoging ‘Nanjing (CN): Yong Chen, Nanjing (CN); Niaoetan Chen, Nanjing (CN), Bai, Nanjing (CN); Jian Niong, Nanjing (CN); Wenbin Qian, Nanjing (Ci) Jingling Nie, Nanjing (CN); ‘inglan Wu, Nanjing (CN) Assignee: Nanjing University of Technology, Fiangsu (CN) Notice: Subject to any disclaimer, the team ofthis pateat is extended of adjusted under 35 USC. 1340) by O days, Appl.No: 1378144400 PCT Filed: Ape 18,2011 PCTNo $371 (ot), (2), (4) Date PCTICN201 072890 Feb. 26, 2013 PCT Pub, Nos WO2012/016480 PCT Pubs, Date: Feb, 9, 2012 Prior P US 20130158308 AI ication Duta Jun. 20, 2013 Forcign Application Priority Data «cy 2010 1 0250835 'US008766019B2 (10) Patent No. 4s) Date of Patent: US 8,766,019 B2 Jul. 1, 2014 G1) Ine core 2974 (2006.01) (2) USs.cI usec 5680917 (58) Fleld of Classification Search usec 568/917 ce application file for complete search history. 66) References Cited FOREIGN PATENT DOCUMENTS WO — Wo2008005906 AL * K2008 * cited by examiner Elvis 0 Price ‘Christie, Parker & Hale, Primary Examiner (74) Attorney TP Agent, or Firm 6 ABSTRACT Disclosed is « method for separating butanol. The method ‘uses hydrophobic macroporous polymer sxlsorbent to sepa rate butanol in # mixed solution, and the process comprises the following steps 1) using macroporous polymer adsorbent to adsorb butanol in a mixed solution; 2) desorbing butanol from macroporous polymer adsorbent. The method is simple the separation ime is shor theeffcieneyof butanol recovery is high and the separating cost slow. 21 Claims, 3 Drawing Sheets U.S. Patent Jul. 1, 2014 Sheet 1 of 3 US 8,766,019 B2 Adsorption Capacity othe soa 8s U.S. Patent Jul. 1, 2014 Sheet 2 of 3 US 8,766,019 B2 3 T = * Concentration (mg/L) Fig. 4 U.S, Patent Macroporous Polymer Adsorbent) Jul. 1, 2014 Sheet 3 of 3 US 8,766,019 B2 PS butanal |S etnanol Concentration (g/L) Fig. 5 US 8,766,019 B2 1 METHOD FOR SEPARATING BUTANOL, (CROSS-REPERENCE TO RELATED APPLICATION(S) ‘This applications a National Phase Patent Appliationand claims priority to and benefit of Intemational Application ‘Number PCT/CN2011/072890, filed on Ape. 15,2011, which claims priority to and henefit of Chinese Patent Application Numer 201010250435,3, fled on Avg, 6, 2010, the entire disclosure of which are incorporated hercin by reference. TECHNICAL FIELD ‘The present invention belongs to the technical feld of biochemical separation, and relates toamethxd for separating butanol BACKGROUND ART Biobutanl is mainly used in producing plasticizers, such ‘as dibutyl phthalate and aliphatic dicarboxylic acid butyl ‘esters, and is therefore widely used in the protuction of 2 variety of plastic and rubber products. Butanol ean also be used fo produce butyraldenyde, butyric acd, butylamine and butyl acetate, which ean be used as the slveats of the res paints and adhesives, and also can be used as extractants of nvases, drugs and perfumes, and as additives for alk resin ‘coatings. Meanwhile, butane is also a now Biofuel of great potential ‘Biobutanol is prodaced through the method of mirobial {ermentation, in the method, renewable biomasses, such as starchiness, pulp waste, molasses and wild plants are used as the raw material, and Clostridium acetobutylicum oF Clostridium beijerinki is inoculated thereino, and thea ‘acetone, butanol and ethanol and other prods are produced through complicated biochemical changes. Therefore, the above fermentation process for producing biobutana is also called ABE (acetone-hutanol-cthanol) fermentation, Due to toxie effects of butanol on the bacteria, severe pret inhi bition occurs doring the entite fermentation process, and ‘when the concentration of butanol reaches acertan vale, the microorganism stops growing, therefore, the concentration of butaao! in the fermentation broth is very’ Tow, and th eost of recovering butanol by the conventional distillation method is ‘extremely high, TInorder to solve this key problem, itis necessary to adopt an effective method to remove the products of ABE from the ‘Fermentation broth, reduce the inhibition effect ofthe prod- ucts, thereby improving the yield of fermentation and rede- fing the industrial cost ‘Currently, major technologies for separating the fermentae tion products of ABE include pas stripping (GS), liquid-liquid ‘extncton, pervaporation (PV Jand adsorption, Meagher etal (US. Pat, No, $.785,967) adopt the method of pervaporation to separateacetone and butanol by developing zeolite mem- brane filed with silicone rubber, andthe zeolite membrane has excelent selective adsorption on acetone and butanol ‘compared with adsorption on the ethanol, acetic acid and butytic acid. Qureshi, N. et sl. (Qureshi, Nu et al 2005, Bioprocess and Biosystems Engineering, 27(4); 215-222) recover biobutanal by the method of adsorption-desorption, Jn terms of energy consumption, the methwx! of adsorption- _desonption isthe best recovery process, which mainly studies the adsomption performances of some adsorption media ‘inchiding sctivated carbon, bone char, siliceous rock, poly= mer resin XAD4 and XAD-, and polyvinyl pyridine resin. 0 o 2 However, the total recovery cate of butanol is Jow de to the following 1wo reasons: on the one hand, the adsorption capac- ty ofthe adsorption moda is low, such a Hess than 100 mg ‘butanol adsorbent; on the other hand, butanol cannot be desorbed from the adsorbent effectively: DUK et al. (WO 20081008896 A1) separate biobutanot by using a hyper ‘rossinked mieroporous resin, bute resin adsorbs. certain mount of acetone and ethanol, which increases the cost for later separation processes. Arjan Oudshoom ea. (Biochem cal Engineering Joural 2009, 48:99-103) adopt the eolite to adsorb and separate biobutanol, ae investigate adsorption performances of thrce zeolites including CBV28014, CBVS1, CBV901 on biobutano, but the problems of this smthod are tht the adsomption capacity of the zeolite on the Diobutanol is not high, and aeetone and ethanol are aso adsorbed while butanol is adsorbed, resulting inthe increase of cost lor late separation, David R, Nielsen e al. (Biotech- nology and Bioengineering 2009, 102(3): 811-821) recover biobutanol in situ by utilizing a polymer resin, ad invest- gles the adsorption perfomance of the polymer resin on biobutanol, but there are problems on this method, for ‘example the resin contacts with the fermentation broth relly, causing contamination to the resin, some resins have poor biocompatibility. andcan adsorb the substrateof glucose ‘and intermediates ofthe Fermentation reation, some resins [have relcvely low adsorption eapacity, and the resins adsorb Jarge amounts of acetone and ethanol although they have higher adsorption capacity on butanol. SUMMARY OF THE INVENTION The object ofthe present invention isto provide a novel smthod for separating butanol, ta recover butanal economi- cally and effectively, Te above object ofthe present invention is implements by the following technical solution. ‘The present invention provides a method for separating ‘butanol, which ineludes the following steps: 1) adsorbing ‘anol ia a mixed solution by a hydrophobie macroporos polymer adsorbent to each saturation; 2) desorbing butanol from the hydrophobic macroporous polymer adsorbent ‘through @ method of thermal desorption. Preferably, the adsorption temperature in the step 1) is 30-37°C, Preferably he step 1) further includes the sep of shaking ‘the mixed solution ata rate of 20-250 rpm during slsorption. Preferably; the weight volume ratio (gimL.) ofthe hydeo- phobie macroporous polymer adsorbent to the mixed solution ‘used inthe step 1) is 1:50. Preferably, the desorption temperature in the step 2) is hove 120°C. Preferably, the inital concentration ofthe butanol in the nixed solution is $-380 gL. referably, the mixed softion farther includes ethanol snd acetone, preferably from fermentation bro; Preferably, the butanol i n-butanol Preferably the method further inches the step of regen- erating the hydrophobic macroporous polymer adsorbent; nore preferably, the regeneration of the hydrophobi ‘macroporous polymer adsorbent and desorption of the butanol are completed simultaneously Preferably, the step 1) farther includes the stp of shaking ‘the mixed solution ata rate of 20-250 rpm during slsorption, Preferably, the hyrophobie macroporous polymer adsor- bent is selected from one oF more of the group consisting oF styrene-diethyl benzene, polyacrylamide, amide group eyann aroup and phenolic hydroxy US 8,766,019 B2 3 Preferably, the inner surface area of the hydophobic sacroporovs polymer adsorbent ix 10-2000 Preferably, the particle sizeof the hydophobic scroporois polymer adsorbent is 20-60 mesh Preferably, the pore diameter of the hydrophobic smacroporos polymer adsorbent is I~180 ns: ad the pore ‘lume of the hydrophobic macroporous polymer adsorbent 04-3 Preferably, the wet apparent density of the hydrophobic snacroparos polymer adsorbent is 590-750 g/L: Preferably, the water content of the. hykophobic sacroporois polymer adsorbent is 40-80" ‘na peefood embodiment of the prseot invention, the followingtwo hydrophobic mscroporots polymer adsorbents ane selected to senate butanol: one adsorbent isa non-polar resi, which as skeleton strctie of styrenedithy bene ‘ene without any functional roup, and mainly relies onthe talks side chin of Batol an the benzene ring in the skeleton structure of styene-dety] benzene to generate Iyrophobic interac Taree, thats w sy, a hydrophobic interaction fore; and another adsorbent is polar resi Which his skeleton stnctre of polyacrylamide, and i Thtional groups ae generally poet fanctonal groups con- tuning nitrogen oxygen oul sochs amie roupeyano soup and phenol hydroxy, and the adsorbent mainly relies ‘nthe aleahole hydroxyls of butanol and hydroxyls of poe Tanetional groups in te polar adsorbent resin to generate hydrogen bonding fore. After they dophobic mscroporous polymer adsorbent adsorbs te sokition containing acetone, bhutan and ethanol to reach saturation, water is used to Wash the resin! soltion which is not adsorbed fit. and then butanol desorbed fom the adsorbent trough the method of thermal desorption wile the adsorbent is epencrted Butanol is hydrophobic and volatile substance, and snail relics onthe adsorption force catmed by van der Waals Foreesadhdrogen bonds to combine withthe adsorbent the present invention ins tha the adsorption free between the “nkovbent and bao! can be destroyed by heating butno}, for example, heating upto near boiling pont, therefore ts ceasior to. dosorb and rover bitanol withthe method of thermal desomplion, and there are sgnicant differences oa desorption and recovery of butanol at iflerent thermal des- ‘rpion temperatures. Moreover the skelt sruturs and Tunetinal soups of the diferent adsorbens are cilereat, resilling in illeeat hydrophobic interaction forces hetea the resins and butanol, which wl fet the adsomtion and ‘desorption of the resins. The desomption rate of the used Iydrophobie) macroporous polymer adsorbents through sercening in the present invention can reach above 95%, ‘while the highest desorption rate of the resins reported can only reach 85%, in summary the present invention is mainly advantage in that using the met of them desorption, butanol can be ‘desorbed fom the adsorbent more elfctively while the ‘nkorbent also canbe regenerate, and based on the difer ‘ence between the afnty of the macroporous polymer adsor- bet with the tet substance of butanol an that with the impurities such as acetone and ethanol, ficient separation of bua! fromacetone and ethanol further achieved by using the hydrophobie macroporous polymer adsorbent which only ‘adsorbs butanol but does not adsorb of adsorbs smaller amount of fanetional groups of seetone and ethanol Ths i ‘ean be soon that the method of th peeset invention has vantages of novel conception, simple proces, shor sepa ration time, high recovery eficiney af hutanal,aw eos of 68 Production, and hot good prospect of promotion. Exper ents sow that, using the method ofthe preset invention, 0 o 4 early 70% of butanol ean be adsorbed within 30 min, and sorption of butanol can reach 95% after 9 hous, wherein purity of butanol ean reach above 99% BRIBE DESCRIPTION OF THE DRAWINGS. Hereinafter, the embodiments ofthe present invention wil beillustrated in detail in combination with the accompanying awings, wherein: FIG. 1 shows results of adsorption capacities of various macroporous polymer adsorbents measured in Example | of the present invention FIG. 2s a chromatogram of « mixed solution of acetone, butanol and ethanol (ABE) messured in Example 2 of the present invention; FIG. 3 isan adsorption kinetic pseudo second-order equa tion fiting diagram of « macroporous polymer adsorbent measured in Example 3 ofthe present invention; FIG. 4 shows adsorption isotherms of a macroporss poly mer adsorbent at diferent temperatures measured in Example ‘FoF the present invention: and FIG. § shows effects of different initial concentrations of ‘butanol on a macroporous polymer adiorbent which aremea- sured in Example 4 ofthe present invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS ‘The present invention will be illustrated with reference to specific examples hereinafter. Those persons skied in the at ill appreciate that these examples are merely used to ilus- trate the present invention rather than limit the scope of the present invention ia any way. Tncach of the following examples the concentration ofthe mixed solution of acetone, butanol and etlanol (ABE) is {tected through the high performance liquid cheomatogr- ‘hy; the used instruments and conditions for detection ar as follows: Agilent 1200 high performance liguid chromato- raph (DAD diode array detector), andl Aminex HPX-87H chromatographic column (@300x75 mm) are used, the ‘mobile phaseis 0.5 mmol/L sulfuric acid soution, with Nowe rate of 0.500 mL/min, the column temperature is 15°C. the injetion volume of sample s 20 a, anda differential refrae- tive index detctor is used for detection, TIneach ofthe following examples, the adsorption capacity ‘of the macroporous polymer adsorbent is calculated by the following formu wherein C, represents the initial solubility (g/.) of butane: CC represents the equilibrium solubility (@/L) of butanol; V represen the volume (L) of a butanol solution: and W rep- resents the mass (a) of macroporous polymer adsorbent, Example 1 In this example, the adsorption eapacities of different hydrophobic macroporous polymer adsorbents on acetone, ‘butanol and ethanol in the mixed solution are measured, whieh is described specifically as follows. ‘An ABE solution ofa corain concentration was prepared, and |g different dry macroporous polymer adsorbents (L..¢ fare respectively resins of Amberlite series, Diaion series and series) aflerairpump filtration were respectively added into US 8,766,019 B2 5 the ABE solution after the adsorbent reaches adsorption satu- ration, the adsorption capacity of the macroporous polymer ‘adsorbent on the ABE and the separation factor were ealeu- lated through the high performance liquid chromatography method (HPLC). “The experimental results areshown in FIG. 1 Thean be soon fiom FIG. 1 thatthe adsorption capacities of resins of Dision series (L-2, 3, Lod, L-13, L-17) on butanol are relatively low, and the L217 resin also adsorbs a small amount of bbypreducts such as. acetone while adsorbing butanol: resins of Deseries (Ll, L-S, 6, 17, L8, L9, E10, L-l1, L-2, L-14, L-16, L-18) have slighty higher sorption capacities ‘on butanol, but these resins also adsorb byproducts such as ‘acetone and ethanol at the same time; resins of Ambeie series (L-15,1.-19)have extremely high adsorption capacities ‘on butanol, and does not aclsorb bypreduets such as acetone ‘and ethane ‘Methods for measuring various parameters of resins areas {ollows: the Water content ofthe resins is measured according to the method described in the literature (GBS757-86S); the ‘content of ative groups of he resins and the apparent density (f,)of the resins are measured with reference to the method «disclosed inthe literature (Binglin He, Wengiang Huang, Jon ‘exchange and adsorption resins (M]. Shanghai: Shanghai ‘ence and Technology Fdveation Press, 1995); special surface fares ofthe resins is mensured with reference tothe literatore (Qiming Tan, Zoosing Shi. Measuring specific surface of resins with simple nitrogen adsorption method (J). lon Exchange and Adsorption, 1987, (1): 30) by using a simple [BET instrament; pore volume is calculated according to the orm! yume Vel: and theaverage pore diameter js calculated according tothe forma M2 Vy yorum! Example 2 i example, butanol is Separated from the mixed solu ing. the LIS macroporous polymer adsorbent of Example I, which specifically includes the following steps 1) 30 mL. mixed solution containing acetone, butanol and ethanol (ABE) (ts chromatogram is shown in FIG. 2) ‘was placed in the 37° C. thermostatic waterbath with Sirving speed of 200 rpm, and 1 g macroporous polymer adsorbent was used o adsorb the mixed solution o reach saturation (over 24 hours): 2) the water in at least doubled amount of resin (V/V) was used to Wash the fesidval solution which was not adsorbed: 3) the adsorbent was heated to 120° C., and butanol was desorbed from the adsorbent while the regenerated adsorbent was obvained. Example 3 Inthis example, adsorption kintis of butanol was studied by using the L1S macroporous polymer adsorbeat of Example 1 1 L butanol solution of 16.196 g/L was prepared, and 20 2 ‘wet macroporous polymer adsorbent was added therein, ‘and placed in 37°C, thermostatie water bath with sizing speedo! 20pm, the solution was samplod at different times, ‘and the concentation of butanol was detected through the high performance liquid chromatography method, the spe- cilie results ae shown in Table 1, wherein adsorption rate of butanol iscalculted throughdlviing the adsomption capacity at each time point by the adsorption capacity at 1,440 min, ‘Thedata were fitted witha pseudo second-order equation, and 0 o 6 TARL ‘Consonant inte bios ian on iam 8 sae a ss sh 12800 Example 4 In this example, butanol adsorption isotherms at different ‘emperaturesare tested, the specie process isa follows '50 ml. ABE solutions of different concentrations were prepared, 1 g wet L15 macroporous polymer adsorbent Was ‘added thereinto and respectively place in shaking tables of 10° C., 20° C., 30°C. and 37° C. with string speed of the shaking table Bing 200 rpm, and the equilibrium concentra- tiomaf the solution was detect when the maeroporots poly met adsorbent adsorbed the mixed solution to reach Satur “The adsorption isotherms were drawn, as shown in FIG. 4. I can be seen from FIG. 4 that, dhe adsorption capacity of butanol increases as temperature rises, and the adsomption capacity reaches the maximum at 37°C. fects of butanol solutions of different inital concentra tions on the LS macroporous polymer adsorbent are tested inthe following, 13 bottles of $0 mL. ABE solutions of different concent sons were prepared, I g wet macroporous polymer adsorbent was added therein respectively, and placed in 37°C. sbak- ing table with stirring speed of the shaking table being 200 pm, and the equilibrium concentration of the solution was dtected when the macroporous polymer adsorbent adsorbed ‘the solution to reach saturation, FIG. 5 showsa curve representing te elation between the concentrations of butanol in to phases when butanol mol- ecules reseh equilibrium during process of adsomption at the interlace of two phases at a certain temperature (37°C. fan be scen from FIG, § that the adsorption of the :maeroporous polymer adsorbent on butanol is accorded with the Langmvir adsorption model. It can be Known fom the calculation of adsorption isotherms at different temperatures the adsorption of the resin on butanol is a favorable process. US 8,766,019 B2 1 Specifically, experimental data were fitted through the Langmuir adsorption isothenn model linar formula by measuring adsorption isotherms at diferent temperatures, sothat differen K, caa be obtained, then R, ateorresponding ‘temperature was calculated seconding tothe formu are indicates that the adsomption process is disadvantageous (un- favorable); Ry=1 indicates that the adsorption isotherm is linear; 0

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