CN1796552A - Method for preparing porous material in lumpy in use for biological zymophore - Google Patents
Method for preparing porous material in lumpy in use for biological zymophore Download PDFInfo
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- CN1796552A CN1796552A CN 200410099206 CN200410099206A CN1796552A CN 1796552 A CN1796552 A CN 1796552A CN 200410099206 CN200410099206 CN 200410099206 CN 200410099206 A CN200410099206 A CN 200410099206A CN 1796552 A CN1796552 A CN 1796552A
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Abstract
This invention describes a process for producing block porous materials used as a carrier for bio-enzymes. The process uses metal alkoxides and organic polymers as raw materials, and adopts the sol-gel method to produce SiO2 and SiO2-TiO2 block porous materials as a carrier for immobilized bio-enzymes. The carrier for immobilized bio-enzymes produced by this invention has a diameter of 10-50mm, a length of 2-10mm, and a density of 0.3-1.2g/cu cm, and is suitable for reactor operation. The process has a high success rate, a short production cycle, and is suitable for mass production. The products have good chemical stability and a narrow distribution of pore diameters.
Description
Technical field
The present invention relates to a kind of is main raw material with metal alkoxide and organic polymer etc., and the utilization sol-gel processing prepares SiO
2And SiO
2-TiO
2Block porous material is as the method for biological fixnig enzyme carrier.
Background technology
Enzyme is by organism institute synthetic protein, and it has almost become chemical catalyst for reaction in all organisms.The reaction of enzyme in the past can only be carried out in the aqueous solution, again and again enzyme and substrate is mixed with batch mode, and question response finishes, from product, enzyme is separated, and be very difficult but will when reclaiming, keep its activity to avoid losing.In fact, in each separating reaction process, all to slattern a part of enzyme.Enzyme is made the insoluble in water type and become immobilized enzyme, can make enzyme reaction be replaced with successive processes, enzyme just can use and realize the continuous and automatic of reaction process repeatedly, and process also can precision have been controlled.Early sixties, people such as katchallski-Katzir at first are fixed in some proteolytic ferments on the insoluble carrier or are wrapped in artificial rust, make immobilized enzyme, as document 1:Annu.Rev.Biochem.35,773-908,1966.People such as the Japanese Tanake Seiyaku Chibata of company successfully were used for enzyme immobilization technology industrial production first in 1967, and as document 2:Biotechnol.Bioeng.9,603-615 describes in 1967.Utilize immobilized enzyme to carry out industrial production, enzyme can be reclaimed, reuse, reduced the catalyzer cost, also improved the stability of enzyme, avoided the pollution of zymoprotein to product, simplified aftertreatment, researchdevelopment in this respect is rapid.Prepare effective porous support is a research emphasis in this field always.
The porous support of present widely used immobilized enzyme has Mierocrystalline cellulose, other polymer substance and sintered glass.The organic porous material of poor chemical stability and nonideal enzyme carrier.Compare with organic porous material, the inanimate matter porous material has following advantage: 1. thermostability height, and use temperature generally can reach more than 400 ℃; 2. chemical stability is good, acid and alkali-resistance; 3. ultimate compression strength is big, is suitable for condition of high voltage; 4. the composition of inorganics is generally nontoxic, can not produce secondary pollution, and cleaning and regeneration are easily; 5. generally with microorganism biochemical reaction, the Degradation of anti-microorganism, the solvency action of organic solvent-resistant do not take place; 6. the fatigue aging of material is extremely slow, long service life; 7. pore distribution is narrow.Long-time running under higher temperature will reach several months as bio-reactor, and this just provides possibility to bacterial multiplication.But in the stable micropore of inorganics, in all can not going into greater than the bacterium of 100nm, thereby can keep the aperture stable, organic porous insert then can be corroded by bacterium.
Utilize fusion again the method for phase-splitting can produce porous silica glass, as document 3: silicate journal, 1984,12 (2), 193-202.But split-phase method need be passed through 1500 ℃ of high temperature melting glass, need again also will carry out long acid treatment then at 500 ℃～600 ℃ following reheat, and the complicated difficult control of manufacturing process, and also goods cost an arm and a leg.In addition, this method will be carried out the acid treatment pore-forming with the HF or the vitriol oil can have pollution to environment; Yield rate is low.
In ceramic batch, introduce pore-forming material, make the pore-forming material volatilization by burning till, thereby the method for making porous ceramics is the method for a quasi-tradition.Pore-forming material has inorganic and organic two classes, and inorganic pore-forming material has: volatile salt, bicarbonate of ammonia, ammonium chloride and coal dust, carbon dust etc.; Organic pore-forming agents mainly contains: natural fiber, high molecular polymer, organic acid etc., the forming method of porous ceramics is identical with the conventional ceramic forming method.This technology can be made into the ceramic of complex-shaped and various air hole structures, but that shortcoming is a gas cell distribution is poor, void content is low and air vent aperture is big, as document 4: powder metallurgy technology, 2002,20 (6), 365-368.
The synthesizing ordered porous material of sol-gel method is the novel method that a kind of development in recent years is got up.This method primary process is: metal alkoxide is dissolved in the lower alcohol, splashes into the water reaction that is hydrolyzed lentamente, obtain the colloidal sol of respective metal oxide compound, and the pH value of regulating this colloidal sol, the metal oxide microparticle of nanoscale will be assembled, and forms gel.With gel drying, thermal treatment, just can obtain metal oxide materials (generally being pottery).Because organism decomposes or the inorganics dissolving in preparation process, the aperture of different steps product is different.It is the method for the high regularity of preparation, submicron-scale porous material that sol-gel method and other means combine, as document 5: Journal of Inorganic Materials, 2002,17 (3), 407-414.Nearest report from " SCIENCE " and " NATURE ", the fresh approach of porous material preparation mainly contains: be template and in conjunction with sol-gel method with the particle of homogeneous radius 1., 2. with the tensio-active agent template and in conjunction with sol-gel method, 3. be template and with the compound of special construction in conjunction with sol-gel method, as document 6: New Chemical Materials, 2001,29 (1), 22-25.The report for preparing porous-film and powder body material with these methods is in the majority, relevant synthetic be suitable for as the research of the block porous material of enzyme carrier less.And can collapse in the medium-term and long-term words of using of hot solution system as the voluminous powder of this class of MSM-41, the aperture is not suitable for this type of commercial use also less than 10nm.
Summary of the invention
In order to overcome the shortcoming of said fixing enzyme carrier, the invention provides the method that a kind of preparation is used for the block porous material of biological enzyme carrier, be difficult to the synthetic problem to solve the porous bulk, improve the chemical stability of carrier, and improved enzymic activity.
The object of the present invention is achieved like this:
The method that preparation provided by the invention is used for the block porous material of biological enzyme carrier comprises the following steps:
(1) colloidal sol, gel is synthetic:
Proportion scale is as follows:
A: tetraethoxy 0-80 weight part;
B: tetrabutyl titanate 0-50 weight part;
C: organic polymer 0.5-50 weight part;
D chemical additive 0.5-20 weight part
E: chemical seasoning control agent 0.5-20 weight part;
F: catalyzer 0.1-10 weight part;
Wherein the umber of composition A and B can not be 0 simultaneously; Organic polymer is one or more in polyoxyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethyl acrylic acid, the polyoxy ethane; Chemical additive is a γ-An Bingjisanyiyangjiguiwan; The chemical seasoning control agent is methyl ethyl diketone, N, one or more in dinethylformamide and the dimethyl formamide; Catalyzer is one or more in acetic acid, hydrochloric acid, nitric acid and the ammoniacal liquor;
A, B, C, D, E, F thorough mixing are carried out, be hydrolyzed in containing water and alcoholic acid system, polycondensation, temperature of reaction is 20-80 ℃, and polyase 13 0 minute-5 hours solidified 0.5-10 hour again, obtained wet gel.
(2) become piece and thermal treatment:
Wet gel is dried in 50-250 ℃ of following vacuum drying oven, then xerogel is smashed, grinds, crossed to pieces the 40-500 mesh sieve in agate mortar, compression moulding in mould again, and forming pressure is 5-50MPa.By drying, the block of moulding is removed organism after being warming up to 400-1000 ℃ of following thermal treatment 1-5 hour again, promptly obtains white light-weight porous bulk.
Beneficial effect: the fixed enzyme vector diameter of the present invention's preparation is 10-50mm, the high 2-10mm of being, density is 0.3-1.2g/cm
3, be suitable for the reactor operation; Preparation method's yield rate height, preparation cycle are shorter, are suitable for mass production; The chemical stability of goods is good, and pore size distribution is narrow.
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
(1) under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 5ml thorough mixing, add ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react.Be warming up to 80 ℃ of following polyase 13s 0 minute, 50 ℃ solidified 7 hours down, obtain xerogel.
(2) xerogel is dried in 250 ℃ of following vacuum drying ovens, sieves then, and with powder compression moulding in mould again, forming pressure is 5MPa.The block of moulding is warming up to 800 ℃ of following thermal treatments after 2 hours with the speed of 4 ℃/min, removes organism, promptly obtains white light-weight porous bulk.
Embodiment 2:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyvinyl alcohol 30g, ethanol 100ml and water 20ml thorough mixing, add ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, be warming up to 20 ℃ of following polymerizations 5 hours, 50 ℃ solidified 0.5 hour down, obtain xerogel.
(2) xerogel is dried in 80 ℃ of following vacuum drying ovens, sieves then, and with powder compression moulding in mould again, forming pressure is 30MPa.The block of moulding was warming up to 400 ℃ of following thermal treatments after 1 hour, removed organism, promptly obtained white light-weight porous bulk.
Embodiment 3:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyacrylamide 30g, ethanol 100ml and water 15ml thorough mixing, add ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, be warming up to 50 ℃ of following polyase 13s hour, 50 ℃ solidified 10 hours down, obtain xerogel.
(2) xerogel is dried in 165 ℃ of following vacuum drying ovens, sieves then, and with powder compression moulding in mould again, forming pressure is 25MPa.The block of moulding is warming up to 700 ℃ of following thermal treatments after 5 hours with the speed of 4 ℃/min, removes organism, promptly obtains white light-weight porous bulk.
Embodiment 4:
Preparation process with tetraethoxy 50g, polyacrylic acid 30g, ethanol 100ml and water 15ml thorough mixing, adds ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml with embodiment 1 under the room temperature again, stirs, reacts, and other is constant.
Embodiment 5:
Preparation process is with embodiment 2, under the room temperature with tetrabutyl titanate 40g, polymethyl acrylic acid 30g, ethanol 100ml and water 15ml thorough mixing, add ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 6:
Preparation process is with embodiment 3, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxy ethane 30g, ethanol 100ml and water 15ml thorough mixing, add ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 7:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 15ml thorough mixing, add ammoniacal liquor 5ml, N again, dinethylformamide 20ml, γ-An Bingjisanyiyangjiguiwan 5ml, stir, react, other is constant.
Embodiment 8:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 15ml thorough mixing, add ammoniacal liquor 5ml, dimethyl formamide 25ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 9:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 15ml thorough mixing, add acetic acid 10ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 10:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 15ml thorough mixing, add hydrochloric acid 6ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 11:
Preparation process is with embodiment 1, under the room temperature with tetraethoxy 50g, tetrabutyl titanate 20g, polyoxyethylene glycol 30g, ethanol 100ml and water 15ml thorough mixing, add nitric acid 8ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml again, stir, react, other is constant.
Embodiment 12:
Preparation process with tetraethoxy 60g, polyoxyethylene glycol 30g, ethanol 80ml and water 15ml thorough mixing, adds ammoniacal liquor 5ml, methyl ethyl diketone 10ml, γ-An Bingjisanyiyangjiguiwan 5ml with embodiment 1 under the room temperature again, stirs, reacts, and other is constant.
Embodiment 13:
(1) food ingredient is with embodiment 1, obtain xerogel after, in 50 ℃ of following vacuum drying ovens, dry, sieve then, other is constant.
Embodiment 14:
(1) food ingredient is with embodiment 1, obtain xerogel after, in 250 ℃ of following vacuum drying ovens, dry, sieve then, with powder compression moulding in mould again, forming pressure is 50MPa.The block of moulding is warming up to 1000 ℃ of following thermal treatments after 1 hour with the speed of 4 ℃/min, removes organism, promptly obtains white light-weight porous bulk.
Claims (4)
1, is used for the preparation method of the block porous material of biological enzyme carrier, it is characterized in that, comprise the following steps:
(1) colloidal sol, gel is synthetic:
Proportion scale is as follows:
A: tetraethoxy 0-80 weight part;
B: tetrabutyl titanate 0-50 weight part;
C: organic polymer 0.5-50 weight part;
D chemical additive 0.5-20 weight part
E: chemical seasoning control agent 0.5-20 weight part;
F: catalyzer 0.1-10 weight part;
Wherein the umber of composition A and B can not be 0 simultaneously; Organic polymer is one or more in polyoxyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethyl acrylic acid, the polyoxy ethane; Chemical additive is a γ-An Bingjisanyiyangjiguiwan; The chemical seasoning control agent is methyl ethyl diketone, N, one or more in dinethylformamide and the dimethyl formamide; Catalyzer is one or more in acetic acid, hydrochloric acid, nitric acid and the ammoniacal liquor;
A, B, C, D, E, F thorough mixing are carried out, be hydrolyzed in containing water and alcoholic acid system, polycondensation, temperature of reaction is 20-80 ℃, and polyase 13 0 minute-5 hours solidified 0.5-10 hour again, obtained wet gel;
(2) become piece and thermal treatment:
Wet gel is dried in 50-250 ℃ of following vacuum drying oven, then xerogel smashed, grind, crossed to pieces the 40-500 mesh sieve in agate mortar, compression moulding in mould again, forming pressure is 5-50MPa, by drying, the block of moulding is removed organism after being warming up to 400-1000 ℃ of following thermal treatment 1-5 hour again, promptly obtains white light-weight porous bulk.
2, require 1 described preparation method as getting profit, it is characterized in that the solidification value in the step (1) is 50 ℃.
3, require 1 described preparation method as getting profit, it is characterized in that, the heat treated temperature rise rate of formed blocks is 4 ℃/min in the step (2).
4, require 1 described preparation method as getting profit, it is characterized in that, xerogel is smashed, is ground the back to pieces and crosses the 60-300 mesh sieve in step (2).
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| CN102137900A (en) * | 2007-11-12 | 2011-07-27 | 拜奥洛卡斯股份公司 | Anti-fouling composition comprising an aerogel |
| CN102676494A (en) * | 2012-05-03 | 2012-09-19 | 天津大学 | Core-shell structure immobilized enzyme particle and preparation method thereof |
| CN105565509A (en) * | 2015-12-23 | 2016-05-11 | 南昌航空大学 | Method for degrading methyl orange by means of photo-catalytic oxidation by aid of CYP119 enzymes loaded with TiO2-phenanthroline |
| CN105621627A (en) * | 2015-12-23 | 2016-06-01 | 南昌航空大学 | Method for performing photocatalytic reduction on Cr6+ by utilizing TiO2-CeO2 loaded CYP119 enzyme |
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| CN105967721A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of Bi2SiO5 porous material |
| CN105967746A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of porous Bi2SiO5 block |
| CN105967748A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of BaTiO3 porous material |
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2004
- 2004-12-29 CN CN 200410099206 patent/CN1796552A/en active Pending
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| CN102137900A (en) * | 2007-11-12 | 2011-07-27 | 拜奥洛卡斯股份公司 | Anti-fouling composition comprising an aerogel |
| CN102676494A (en) * | 2012-05-03 | 2012-09-19 | 天津大学 | Core-shell structure immobilized enzyme particle and preparation method thereof |
| CN102676494B (en) * | 2012-05-03 | 2013-10-30 | 天津大学 | Core-shell structure immobilized enzyme particle and preparation method thereof |
| CN105565509A (en) * | 2015-12-23 | 2016-05-11 | 南昌航空大学 | Method for degrading methyl orange by means of photo-catalytic oxidation by aid of CYP119 enzymes loaded with TiO2-phenanthroline |
| CN105621627A (en) * | 2015-12-23 | 2016-06-01 | 南昌航空大学 | Method for performing photocatalytic reduction on Cr6+ by utilizing TiO2-CeO2 loaded CYP119 enzyme |
| CN105621627B (en) * | 2015-12-23 | 2017-12-05 | 南昌航空大学 | One kind utilizes TiO2‑CeO2Load C YP119 enzyme photo catalytic reductions Cr6+Method |
| CN105967723A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of silica porous material |
| CN105967745A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of porous stable state Bi12SiO20 block |
| CN105948805A (en) * | 2016-05-05 | 2016-09-21 | 陕西科技大学 | Preparation method of titanium dioxide porous material |
| CN105948808A (en) * | 2016-05-05 | 2016-09-21 | 陕西科技大学 | Preparation method of stable Bi12SiO20 nano-porous material |
| CN105924144A (en) * | 2016-05-05 | 2016-09-07 | 陕西科技大学 | Preparing method for porous metastable stable Bi2SiO5 block |
| CN105967722A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of Bi4Si3O12 porous material |
| CN105967724A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of zinc oxide porous material |
| CN105948806A (en) * | 2016-05-05 | 2016-09-21 | 陕西科技大学 | Preparation method of porous steady-state Bi4Si3O12 bulk |
| CN105967747A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Stable-state Bi4Si3O12 porous material preparation method |
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| CN105967721A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of Bi2SiO5 porous material |
| CN105967746A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of porous Bi2SiO5 block |
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| CN105967720A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of BaTiO3 porous material |
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