CN102936632B - Method for improving hydrolytic efficiency of cellulose - Google Patents
Method for improving hydrolytic efficiency of cellulose Download PDFInfo
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- CN102936632B CN102936632B CN201210438249.1A CN201210438249A CN102936632B CN 102936632 B CN102936632 B CN 102936632B CN 201210438249 A CN201210438249 A CN 201210438249A CN 102936632 B CN102936632 B CN 102936632B
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Abstract
The invention relates to a preparation method and an application of a cellulose modifier, particularly to a method for improving the hydrolytic efficiency of cellulose. The cellulose modifier of a triazine derivative is synthesized with cyanuric chloride serving as an active component and phenol, phenol-4-sulfonic acid or H acid monosodium salt serving as a functional component, and the structure of the modifier is presented through infrared spectrum and mass spectrum; and then the synthesized triazine derivative is used for modifying the cellulose and the modified microcrystalline cellulose is hydrolyzed in 8% of H2SO4 at a temperature of 130 DEG C for 5h. The result proves that when the relative mole content (by glucose ring) of the modifier is 16.67%, the yield of reducing sugar through hydrolysis of the cellulose is 23.54% maximally. Modification enables the crystalline structure of the microcrystalline cellulose to change through analysis of a wide angle X-ray diffraction pattern, amorphous regions are added, the crystallographic index is declined, and the grain size is reduced. The method has wide application prospect in hydrolysis of the cellulose.
Description
Technical field
The present invention relates to a kind of method that improves cellulose hydrolysis efficiency, especially a kind of method of utilizing cellulosic chemical modification to improve cellulose hydrolysis efficiency.
Background technology
Ethanol (being commonly called as alcohol) is a kind of important industrial raw material, be widely used in the fields such as chemical industry, food, drink industry, military project, daily-use chemical industry and medical and health, can also be as the basic material of energy industry, fuel (fuel value is 26900KJ/Kg).Mierocrystalline cellulose is occurring in nature content one of the most much higher sugared resource, utilize cellulose conversion to become ethanol to replace research field to receive much attention as biomass energy in fossil energy, but cellulose conversion is the key of clean fuel and chemical ethanol, be to find effective way by the cellulose hydrolysis fermentation soluble sugar such as be glucose.Mierocrystalline cellulose is the long chain molecule that β-D-Glucose residue is linked into Isosorbide-5-Nitrae-glycoside bond each other, and long chain molecule further forms a kind of supramolecule rock steady structure with highly crystalline district, and this makes Mierocrystalline cellulose be difficult to hydrolysis.
Scientific research is found, Mierocrystalline cellulose is carried out to certain pre-treatment, can improve the yield that its hydrolysis produces reducing sugar, the pretreated method of Mierocrystalline cellulose mainly contains physical method (mechanical disintegration, steam explosion, supercritical water treatment etc.), chemical process (alkaline purification, acid treatment, oxidizer treatment etc.), biological method at present.But these methods have dual character, as steam explosion can produce the material of inhibitory enzyme hydrolysis and fermentation, alkaline purification can also be taken away part hemicellulose in removing a part of xylogen, affects the yield of total reducing sugar etc.And do not change its chain structure for most of pretreatment process of cellulosic material, and very little on the impact of crystalline texture, cause enzymatic hydrolysis to occur in Mierocrystalline cellulose pars amorpha, acid catalyst is also very little to the accessibility of Mierocrystalline cellulose crystallizing field.Therefore, find the pretreatment process that significantly improves Mierocrystalline cellulose accessibility and remain the emphasis of current Mierocrystalline cellulose-ethanol conversion research.
The carboxymethyl cellulose hydrolysis efficiency that the people such as pool Sa have reported low degree of substitution is than the high (J.Borsa of Mierocrystalline cellulose, I.Tanczos, I.Rusznak.Acid hydrolysis of carboxymethylcellulsoe of low degree of substitution[J] .Collold Polymer Science, 1990,268 (7): 649-657); Dai Wei, the people such as karst apply molecule simulation method and have studied the group modified Mierocrystalline cellulose of different volumes, dope substituting group that volume is larger to improving favourable (the David T.Karst of cellulose hydrolysis efficiency, Yiqi Yang.Effect of structure of large aromatic molecules grafted onto cellulsoe on hydrolysis of the glycosidic linkages[J] .Macromolecular Chemistry and Physics, 2007,208:784-791); The hydrolysis sugar yield that Jiang Xue etc. have disclosed the cyanuric chloride modified-cellulose that amino, the sulfonic phenyl of band replaces obtained remarkable increase (Jiang Xue, Tian Xiuzhi, Gu Jian, yellow lead, Wang Shugen. application number: 201110154930.9).
Therefore, the present invention is taking cyanuric chloride base as active constituent, taking the compound phenol that contains hydroxyl, p-hydroxybenzenyl sulfonate, 1-amino-8-naphthol-3,6-sodium disulfonate as function component, utilize hydroxyl to synthesize properties-correcting agent with reacting of cyanuric chloride, and Mierocrystalline cellulose is carried out to modification, change cellulosic chain structure by the reaction of properties-correcting agent, reduce cellulosic degree of crystallinity and then improve cellulose hydrolysis efficiency.
Summary of the invention
The object of the invention is to overcome the deficiency existing in existing cellulose fuel ethanol technology of preparing, a kind of method that improves cellulose hydrolysis efficiency is provided, its feature comprises the following steps:
1) in the reactor of being furnished with stirring, add active constituent solution and reductive agent, function component solution is placed in to constant voltage dropping liquid and leaks and slowly splash into reactor, last 1 ~ 2h and drip completely, then react 1 ~ 3h at 0～5 DEG C; After precipitation, filter, and use organic solvent recrystallization, solid is in 50 DEG C of vacuum-dryings, properties-correcting agent productive rate 60%～80%.
2) 2 parts of Mierocrystalline celluloses, 10 ~ 40 parts of solvents, 4 parts of alkaline solutions are placed in to reactor, relatively molar content (taking glucose ring) is placed in constant pressure funnel as the modifier solution of 1/40～1 part, slowly drip alkaline solution to entering in reactor, react 3h at 40 DEG C; Reaction finishes after product suction filtration, extremely neutral with clear water washing leaching cake pH, dry 24h in 50 DEG C of vacuum drying ovens; 1 ~ 0.5 part of modified-cellulose is placed in to the reactor of being furnished with stirring, and adding concentration is 8% sulfuric acid 10ml, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate.
Described active ingredient is 1:1～2 with the molar mass ratio of function ingredients.。
Described active constituent is cyanuric chloride,
The solvent of described active constituent solution is methylene dichloride or acetone.
Described reductive agent is sodium sulphite anhydrous 99.3.
Described function component is the mixing of any one or more arbitrary proportions in phenol, p-hydroxybenzenyl sulfonate, 1-amino-8-naphthol-3,6-sodium disulfonate.
The solvent of described function component solution is the aqueous solution of anhydrous sodium carbonate.
Described recrystallization solvent is the mixing of tetrahydrofuran (THF) and water.
Described alkaline solution is 10% sodium hydroxide solution.
The present invention is taking the compound phenol that contains hydroxyl, p-hydroxybenzenyl sulfonate, 1-amino-8-naphthol-3,6-sodium disulfonate as function component, in active constituent cyanuric chloride, only introduce phenyl ring and the naphthalene nucleus of hydroxyl, cellulose modified dose of synthetic pyrrolotriazine derivatives, then with the single phenoxy group that contains different ratios synthesizing and the pyrrolotriazine derivatives modified-cellulose of naphthalene epoxy group(ing) triazine ring, the s-triazine group of the phenyl ring that contains hydroxyl and naphthalene nucleus carries out modification to Mierocrystalline cellulose.Experiment shows, the Reducing sugar after the cellulose hydrolysis of pyrrolotriazine derivatives modification has improved, and as when the relative molar content (in glucose ring) of properties-correcting agent is 16.67% time, cellulose hydrolysis becomes Reducing sugar to be 23.54% to the maximum; Find that by analyzing wide-angle x-ray diffractogram modification changes the crystalline texture of Microcrystalline Cellulose, pars amorpha increases, crystalline indice declines, grain-size reduces.By changing cellulosic chain structure, reduce cellulosic degree of crystallinity and then improve cellulose hydrolysis the transformation efficiency that becomes fermentable sugars, the method has broad application prospects in cellulose hydrolysis.
Figure of description
The mass spectrum of Fig. 1 properties-correcting agent
The infrared spectra of Fig. 2 properties-correcting agent
The infrared spectra of Fig. 3 modified-cellulose
The X-ray diffractogram of Fig. 4 modified-cellulose, (A) Mierocrystalline cellulose; (B) ~ and (F): embodiment 1～5
Embodiment
The present invention mainly comprises three partial contents:
(1) the synthetic properties-correcting agent that contains active constituent and function component;
(2) utilize properties-correcting agent and fibrin reaction to prepare modified-cellulose;
(3) hydrolysis of the modified-cellulose of different ratios.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
(1) take 4 parts of cyanuric chlorides in reactor, add 40 parts of methylene dichloride, be then placed in ice-water bath and stir; 2 parts of phenol and 2 parts of anhydrous sodium carbonates and 0.1 part of sodium sulphite anhydrous 99.3 are with slowly splashing into above-mentioned system after 30 parts of water dissolution, lasting 1h drips complete, continue reaction 2h, stopped reaction, pours in separating funnel, leave standstill 1h, after the abundant layering of system, separate the transparent liquid of lower floor, steam methylene dichloride and obtain thick product, slightly for product, tetrahydrofuran (THF)-water recrystallization obtains white solid, productive rate 65.5%.
(2) take 2 parts of Mierocrystalline celluloses in reactor, add 10 parts of acetone; Take relative molar content (taking glucose ring) as 1/40 part of properties-correcting agent, and add 30 parts of acetone to make it to dissolve under stirring, and splash at leisure in above-mentioned system; Taking 10wt%NaOH as catalyzer, be to react 3h at 40 DEG C in temperature, product is through suction filtration, deionized water wash to neutral, and gained solid is drying 24h under reduced pressure;
(3) 0.5 part of modified-cellulose is placed in to reactor, adding concentration is 10 parts, 8% sulfuric acid, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate to be detected.
Embodiment 2:
(1) take 2 parts of cyanuric chlorides in reactor, add 20 parts of methylene dichloride, be then placed in ice-water bath and stir; 1 part of phenol and 1 part of anhydrous sodium carbonate and 0.1 part of sodium sulphite anhydrous 99.3 are with slowly splashing into above-mentioned system after 30 parts of water dissolution, lasting 1h drips complete, continue reaction 2h, stopped reaction, pours in separating funnel, leave standstill 1h, after the abundant layering of system, separate the transparent liquid of lower floor, steam methylene dichloride and obtain thick product, slightly for product, tetrahydrofuran (THF)-water recrystallization obtains white solid, productive rate 75.5%.
(2) take 2 parts of Mierocrystalline celluloses in reactor, add 10 parts of acetone; Taking relative molar content (taking glucose ring) is 1/20 properties-correcting agent, and adds 30 parts of acetone to make it to dissolve under stirring, and splashes at leisure in above-mentioned system; Taking 10wt%NaOH as catalyzer, be to react 3h at 40 DEG C in temperature, product is through suction filtration, deionized water wash to neutral, and gained solid is drying 24h under reduced pressure;
(3) 0.5 part of modified-cellulose is placed in to reactor, adding concentration is 10 parts, 8% sulfuric acid, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate to be detected.
Embodiment 3:
(1) take 1 part of cyanuric chloride in reactor, add 10 parts of methylene dichloride, be then placed in ice-water bath and stir; 1 part of phenol and 1 part of anhydrous sodium carbonate and 0.1 part of sodium sulphite anhydrous 99.3 are with slowly splashing into above-mentioned system after 30 parts of water dissolution, lasting 1h drips complete, continue reaction 2h, stopped reaction, pours in separating funnel, leave standstill 1h, after the abundant layering of system, separate the transparent liquid of lower floor, steam methylene dichloride and obtain thick product, slightly for product, tetrahydrofuran (THF)-water recrystallization obtains white solid, productive rate 60.5%.
(2) take 2 parts of Mierocrystalline celluloses in reactor, add 10 parts of acetone; Take relative molar content (taking glucose ring) as 1/5 part of properties-correcting agent, and add 30 parts of acetone to make it to dissolve under stirring, and splash at leisure in above-mentioned system; Taking 10wt%NaOH as catalyzer, be to react 3h at 40 DEG C in temperature, product is through suction filtration, deionized water wash to neutral, and gained solid is drying 24h under reduced pressure;
(3) 0.5 part of modified-cellulose is placed in to reactor, adding concentration is 10 parts, 8% sulfuric acid, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate to be detected.
Embodiment 4:
(1) take 4 parts of cyanuric chlorides in reactor, add 40 parts of acetone, be then placed in ice-water bath and stir; 2 parts of p-hydroxybenzenyl sulfonates and 2 parts of anhydrous sodium carbonates and 0.1 part of sodium sulphite anhydrous 99.3 are with slowly splashing into above-mentioned system after 30 parts of water dissolution, lasting 1h drips complete, continue reaction 2h, stopped reaction, pours in separating funnel, leave standstill 1h, after the abundant layering of system, separate the transparent liquid of lower floor, steam methylene dichloride and obtain thick product, slightly for product, tetrahydrofuran (THF)-water recrystallization obtains white solid, productive rate 65.5%.
(2) take 2 parts of Mierocrystalline celluloses in reactor, add 10mL acetone; Take relative molar content (taking glucose ring) as 1/3 part of properties-correcting agent, and add 30 parts of acetone to make it to dissolve under stirring, and splash at leisure in above-mentioned system; Taking 10wt%NaOH as catalyzer, be to react 3h at 40 DEG C in temperature, product is through suction filtration, deionized water wash to neutral, and gained solid is drying 24h under reduced pressure;
(3) 0.5 part of modified-cellulose is placed in to reactor, adding concentration is 10 parts, 8% sulfuric acid, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate to be detected.
Embodiment 5:
(1) take 4 parts of cyanuric chlorides in reactor, add 40 parts of methylene dichloride, be then placed in ice-water bath and stir; 2 parts of 1-amino-8-naphthol-3,6-sodium disulfonate and 2 parts of anhydrous sodium carbonates and 0.1 part of sodium sulphite anhydrous 99.3 are with slowly splashing into above-mentioned system after 30 parts of water dissolution, lasting 1h drips complete, continue reaction 2h, stopped reaction, pours in separating funnel, leave standstill 1h, after the abundant layering of system, separate the transparent liquid of lower floor, steam methylene dichloride and obtain thick product, slightly for product, tetrahydrofuran (THF)-water recrystallization obtains white solid, productive rate 65.5%.
(2) take 2 parts of Mierocrystalline celluloses in reactor, add 10 parts of acetone; Take relative molar content (taking glucose ring) as 1/2 part of properties-correcting agent, and add 30 parts of acetone to make it to dissolve under stirring, and splash at leisure in above-mentioned system; Taking 10wt%NaOH as catalyzer, be to react 3h at 40 DEG C in temperature, product is through suction filtration, deionized water wash to neutral, and gained solid is drying 24h under reduced pressure;
(3) 0.5 part of modified-cellulose is placed in to reactor, adding concentration is 10 parts, 8% sulfuric acid, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate to be detected.
The properties such as structure and hydrolysis property of the modified-cellulose that method of modifying of the present invention obtains can adopt following index to detect:
(1) reducing sugar content: adopt 3,5-dinitrosalicylic Acid Colorimetry (DNS) to measure reducing sugar content in hydrolyzed solution.The glucose typical curve that 494nm place records is Y=0.91412X-0.10154 (R
2=0.9985).Method of calculation as shown in the formula:
(2) structural analysis is measured: FTIR analyzes and uses NICOLET NEXUS 470 infrared spectrometers, and sample preparation adopts KBr pressed disc method.Spectrograph resolving power is 4cm
-1, scanning times is 30.The X-ray diffraction analysis of sample is carried out on the D8Advance type x-ray diffractometer of German BrukerAXS company, adopt copper target Cu K α (λ=0.15406nm), power is 1600W (40kV × 40mA), adopt NaI crystal scintillation counter to measure the intensity of X-ray, sweep limit is 3 °-60 °, 4 °/min of sweep velocity, 0.02 ° of step-length.
(3) grain-size is calculated: grain-size is according to Scherrer formula
calculate, wherein D is grain-size; K is Scherrer constant, gets k=0.89; λ is X ray wavelength, to copper target λ=0.15406nm; B is the maximum halfwidth of characteristic diffraction peak, represents with radian; θ is Bragg angle, calculates the grain-size of 002 in literary composition.Adopt formula CrI=(I
002-I
am)/I
002calculate the crystalline indice of product, I in formula
002be the maximum value of 002 crystal face diffracted intensity, I
amrefer to the diffracted intensity that 2 θ=18.3 ° are located.
Table 1 modified-cellulose detected result
Claims (4)
1. improve a method for cellulose hydrolysis efficiency, its feature comprises the following steps:
1) in the reactor of being furnished with stirring, add active constituent solution and reductive agent, function component solution is placed in to constant voltage dropping liquid and leaks and slowly splash into reactor, last 1～2h and drip completely, then react 1～3h at 0～5 DEG C; After precipitation, filter, and use organic solvent recrystallization, solid is in 50 DEG C of vacuum-dryings, properties-correcting agent productive rate 60%～80%; 2) 2 parts of Mierocrystalline celluloses, 10～40 parts of solvents, 4 parts of alkaline solutions are placed in to reactor, be placed in constant pressure funnel taking the relative molar content of glucose ring as the modifier solution of 1/40～1 part, slowly drip alkaline solution to entering in reactor, react 3h at 40 DEG C; Reaction finishes after product suction filtration, extremely neutral with clear water washing leaching cake pH, dry 24h in 50 DEG C of vacuum drying ovens; 1～0.5 part of modified-cellulose is placed in to the reactor of being furnished with stirring, and adding concentration is 8% sulfuric acid 10ml, is hydrolyzed 5h at 130 DEG C, and centrifugation, obtains hydrolysate; Described active ingredient is 1:1～2 with the molar mass ratio of function ingredients; Described active constituent is cyanuric chloride; The solvent of described active constituent solution is methylene dichloride or acetone; Described reductive agent is sodium sulphite anhydrous 99.3; Described function component is the mixing of any one or more arbitrary proportions in phenol, p-hydroxybenzenyl sulfonate, 1-amino-8-naphthol-3,6-sodium disulfonate.
2. method according to claim 1, the aqueous solution that the solvent that it is characterized in that described function component solution is anhydrous sodium carbonate.
3. method according to claim 1, is characterized in that described recrystallization solvent is the mixing of tetrahydrofuran (THF) and water.
4. method according to claim 1, is characterized in that described alkaline solution is 10% sodium hydroxide solution.
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| WO2006086861A2 (en) * | 2005-02-15 | 2006-08-24 | Oxiteno S.A. Indústria E Comércio | Acid hydrolysis process of cellulosic and lignocellulosic materials, digestion vessel and hydrolysis reactor |
| CN102218306A (en) * | 2011-04-27 | 2011-10-19 | 中国科学院西双版纳热带植物园 | Solid nanometer catalyst and applications thereof in cellulose hydrolysis |
| CN102409113A (en) * | 2011-06-07 | 2012-04-11 | 江南大学 | Method for improving cellulose hydrolysis efficiency |
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| WO2006086861A2 (en) * | 2005-02-15 | 2006-08-24 | Oxiteno S.A. Indústria E Comércio | Acid hydrolysis process of cellulosic and lignocellulosic materials, digestion vessel and hydrolysis reactor |
| CN102218306A (en) * | 2011-04-27 | 2011-10-19 | 中国科学院西双版纳热带植物园 | Solid nanometer catalyst and applications thereof in cellulose hydrolysis |
| CN102409113A (en) * | 2011-06-07 | 2012-04-11 | 江南大学 | Method for improving cellulose hydrolysis efficiency |
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| 顾坚，等.2-氯-4,6-二苯氨基-1,3,5-三嗪改性纤维素的制备、结晶结构与水解性能.《化学学报》.2011,第69卷(第24期),第2975-2980页. * |
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