CN102285664B - Special molecular sieve for separating L-lactic acid and D-lactic acid with simulated moving bed and preparation method thereof - Google Patents
Special molecular sieve for separating L-lactic acid and D-lactic acid with simulated moving bed and preparation method thereof Download PDFInfo
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- CN102285664B CN102285664B CN 201110139266 CN201110139266A CN102285664B CN 102285664 B CN102285664 B CN 102285664B CN 201110139266 CN201110139266 CN 201110139266 CN 201110139266 A CN201110139266 A CN 201110139266A CN 102285664 B CN102285664 B CN 102285664B
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Abstract
The invention discloses a special molecular sieve for separating L-lactic acid and D-lactic acid with a simulated moving bed and a preparation method thereof. The preparation method comprises the working procedures of sol preparation, calcining, cooling, polishing, primary reaction, filtering, secondary reaction, filtering, third reaction, filtering and airing and comprises the following steps: adopting a sol-gel method to form porous solid particles which are used as the carrier, performing a chemical reaction to ensure that chemical bonds are formed between the surfaces of particles and 3-aminopropropyltriethoxysilane, between the surfaces of particles and glutaraldehyde, and between the surfaces of particles and bovine serum albumin in turn under the set conditions, and finally obtaining the molecular sieve with good adsorption property and high acid resistance. By adopting the molecular sieve prepared by the method, L-lactic acid and D-lactic acid can be effectively separated; and the molecular sieve has long service life, high separation factor and good production effect and is suitable for scale simulated moving bed separation of L-lactic acid and D-lactic acid.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, particularly the dedicated molecular sieve used preparation method of simulation moving-bed separating L-lactic acid and D-ALPHA-Hydroxypropionic acid.
Technical background
Lactic acid has unsymmetrical carbon as a kind of important organic acid in its molecule, and therefore, lactic acid has L-and two kinds of optically active isomers of D-and DL-racemic modification.Because human body can only carry out metabolism to Pfansteihl, thus World Health Organization's clear, the amount of the D-ALPHA-Hydroxypropionic acid of taking in for each person every day should be limited in the 100mg/kg body weight, and Pfansteihl does not have similar restriction.Worldwide, the Pfansteihl of high-optical-purity has been widely used in industries such as grocery trade, pharmaceutical sector, beauty and health care industries.
At present the comparision of production of Pfansteihl is commonly used is to utilize rhizopus to the ferment method of direct production Pfansteihl of the materials such as starch.The bacterial strain that the method is utilized requires high to living environment, lower to the utilization ratio of fermentation substrate, the by product kind that produces in fermenting process is many, and is strict to follow-up separating technology; Under comparing, utilize milk-acid bacteria to material direct fermentations such as starch, although produce simultaneously Pfansteihl and D-ALPHA-Hydroxypropionic acid, fermentation strain is low to environmental requirement, survival rate is high, and is high to substrate utilization ratio, and the by product that produces in fermenting process is few.So, how to take full advantage of lactobacillus-fermented, the separation of produced Pfansteihl becomes more popular problem.
But the method for mass-producing separating L-lactic acid and D-ALPHA-Hydroxypropionic acid does not also occur at present; and the simulation moving-bed separating L-lactic acid that arrives involved in the present invention and the dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid can well solve the problem of mass-producing separating L-lactic acid and D-ALPHA-Hydroxypropionic acid.
Summary of the invention
The purpose of this invention is to provide a kind of can separating L-lactic acid and the simulation moving-bed dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid, by the molecular sieve that present method is made, its surface coverage has one deck adsorption layer, the thickness of layer is the 15-50 nanometer.
The present invention is achieved in that
simulation moving-bed separating L-lactic acid and D-ALPHA-Hydroxypropionic acid are dedicated molecular sieve used and preparation method thereof, it is characterized in that: comprise colloidal sol, calcining, third-order reaction and filter progress, first adopt sol-gel method and calcining preparation honeycombed grain carrier, by chemical reaction for the first time, the honeycombed grain carrier surface is combined with the 3-aminopropyl triethoxysilane, adding glutaraldehyde to carry out chemical reaction for the second time in chemical reactant for the first time, chemical reactant and bovine serum albumin carry out chemical reaction for the third time for the second time, obtain the dedicated molecular sieve used product of simulation moving-bed separating L-lactic acid and D-ALPHA-Hydroxypropionic acid.
The preparation of described honeycombed grain carrier is first will contain the kaolin of aqueous solution of urea that massfraction is 3.5-8.5% and water content≤10% with 1: the ratio of 1-2 is mixed with colloidal sol, again 300-500 ℃ temperature lower calcination 2-4 hour, cooling, polishing is shaped, and obtains the honeycombed grain carrier of diameter 5-10mm.
Described primary first-order equation is that prepared honeycombed grain carrier is added massfraction is to soak in the dry toluene mixed solution of 3-aminopropyl triethoxysilane of 3-5%, then be filled with nitrogen, heat up, chemical reaction is carried out in stirring one time, obtain the reactant that concrete dynamic modulus solid particles surface and 3-aminopropyl triethoxysilane form chemical bond, filter reaction mother liquor and reclaim standby.
Described primary first-order equation is controlled 150-300 ℃ of temperature of reaction, reaction times 8-10 hour.
Described secondary reaction is the reactant with concrete dynamic modulus solid particles surface and 3-aminopropyl triethoxysilane formation chemical bond, add that more than 3 times, massfraction is the glutaraldehyde of 6-10%, control the pH=6.5-8.0 of reaction soln, stirred 4-7 hour under room temperature, after reaction finishes, filter reaction mother liquor and reclaim standby.
Described third-order reaction is after the concrete dynamic modulus solid particulate finishes with this and 3-aminopropyl triethoxysilane and glutaraldehyde reaction, filter, again it is added and contain the bovine serum albumin that massfraction is 2.5-5.5% more than 3 times, control the pH=6.5-8.0 of reaction soln, stirring reaction takes out particle after finishing, and it is dried naturally, namely obtain molecular sieve, filter reaction mother liquor and reclaim standby.
Described third-order reaction is controlled 3-6 ℃ of temperature of reaction, reaction times 8-10 hour.
Advantage of the present invention and positively effect:
1, the present invention first adopts sol-gel method to form the concrete dynamic modulus solid particulate as carrier, make successively the reaction under the condition of setting of particle surface and 3-aminopropyl triethoxysilane, glutaraldehyde and bovine serum albumin form chemical bond by chemical reaction again, finally obtain the molecular sieve that absorption property is good, acid resistance is strong.
2, with the molecular sieve of the inventive method preparation, effectively separating L-lactic acid and D-ALPHA-Hydroxypropionic acid, long service life, separation factor is high and production effect good, is applicable to the simulation moving-bed separating L-lactic acid of mass-producing and D-ALPHA-Hydroxypropionic acid.
3, respectively go on foot all recyclable recyclings of reaction mother liquor, reduce consuming, save cost, have economic benefit preferably.
Description of drawings
Fig. 1: process flow diagram of the present invention.
Simulation moving-bed separating L-lactic acid and D-ALPHA-Hydroxypropionic acid are dedicated molecular sieve used and preparation method thereof, comprise colloidal sol, calcining, cooling, polishing, primary first-order equation, filtration, secondary reaction, filtration, third-order reaction, filter and dry and obtain dedicated molecular sieve used product.
Embodiment
Embodiment 1
At first will contain massfraction and be 3.5% aqueous solution of urea and water content and be 9.8% kaolin mixes according to the mass ratio of 1: 1 and forms lyosol; Lyosol is put into 500 ℃ of calcinations of retort furnace 2 hours, take out and be cooled to room temperature; The concrete dynamic modulus solid polishing that obtains is formed the particle that several diameters are about 10mm; These particles are immersed to contain in the anhydrous toluene solution that massfraction is 3% 3-aminopropyl triethoxysilane soak, then this solidliquid mixture is placed in the 150 ℃ of heating of blind roaster 10 hours that are filled with nitrogen; Take out honeycombed grain after heating finishes, the massfraction that contains that joins 3 times is 6% glutaraldehyde, controls the pH=7.0 of reaction soln, stirs 4 hours under 23 ℃ of conditions; Take out honeycombed grain, it is added the massfraction that contains of 3 times again is 2.5% bovine serum albumin, controls the pH=7.0 of reaction soln, stirs 8 hours under 3 ℃; Take out particulate matter, and it is dried naturally, obtain target product.The reaction mother liquor in each stage reclaims respectively standby.
The molecular sieve that aforesaid method is obtained be placed in laboratory scale simulation moving-bed in, adopting racemic lactic acid solution is raw material, carries out 5 circulations and separates, separating effect sees Table 1:
Table 1: the dedicated molecular sieve used application result of laboratory simulation moving-bed (unit: Bx)
Embodiment 2
At first will contain massfraction and be 3.5% aqueous solution of urea and water content and be 9.6% kaolin mixes according to the mass ratio of 1: 1.5 and forms lyosol; Lyosol is put into 400 ℃ of calcinations of retort furnace 3 hours, take out and be cooled to room temperature; The concrete dynamic modulus solid polishing that obtains is formed the particle that several diameters are about 7mm; These particles are immersed to contain in the anhydrous toluene solution that massfraction is 4% 3-aminopropyl triethoxysilane soak, this solidliquid mixture is placed in the 250 ℃ of heating of blind roaster 9 hours that are filled with nitrogen; Take out honeycombed grain after heating finishes, the massfraction that contains that joins 3.5 times is 8% glutaraldehyde, controls the pH=7.6 of reaction soln, stirs 6 hours under 24 ℃ of conditions; Taking out honeycombed grain, is 3.5% bovine serum albumin with its massfraction that contains that joins again 3.5 times, controls the pH=7.7 of reaction soln, stirs 9 hours under 4 ℃; Take out particulate matter, and it is dried naturally, obtain target product.The reaction mother liquor in each stage reclaims respectively standby.
The molecular sieve that aforesaid method is obtained be placed in laboratory scale simulation moving-bed in, adopting racemic lactic acid solution is raw material, carries out 5 circulations and separates, separating effect sees Table 2:
Table 2: the dedicated molecular sieve used application result of laboratory simulation moving-bed (unit: Bx)
Embodiment 3
At first will contain massfraction and be 3.5% aqueous solution of urea and water content and be 9.4% kaolin mixes according to the mass ratio of 1: 2 and forms lyosol; Lyosol is put into 300 ℃ of calcinations of retort furnace 4 hours, take out and be cooled to room temperature; The concrete dynamic modulus solid polishing that obtains is formed the particle that several diameters are about 5mm; These particles are added to contain massfraction after adjusting be that the dry toluene of 5% 3-aminopropyl triethoxysilane reclaims in solution and soaks, this solidliquid mixture is placed in the 300 ℃ of heating of blind roaster 8 hours that are filled with nitrogen; Take out honeycombed grain after heating finishes, the massfraction that contains after adjusting that joins 4 times is 10% glutaraldehyde, controls the pH=6.6 of reaction soln, stirs 7 hours under 25 ℃ of conditions; Taking out honeycombed grain, is 5.5% bovine serum albumin with its massfraction that contains after adjusting that joins again 4 times, controls the pH=7.6 of reaction soln, stirs 10 hours under 6 ℃; Take out particulate matter, and it is dried naturally, obtain target product.The reaction mother liquor in each stage reclaims respectively standby.
The molecular sieve that aforesaid method is obtained be placed in laboratory scale simulation moving-bed in, adopting racemic lactic acid solution is raw material, carries out 5 circulations and separates, separating effect sees Table 3:
Table 3: the dedicated molecular sieve used application result of laboratory simulation moving-bed (unit: Bx)
Claims (4)
1. a simulation moving-bed separating L-lactic acid and the dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid, it is characterized in that: comprise colloidal sol, calcining, cooling, polishing, primary first-order equation, filter, secondary reaction, filter, third-order reaction, filter and dry operation, first adopt sol-gel method and calcining preparation honeycombed grain carrier, by chemical reaction for the first time, the honeycombed grain carrier surface is combined with the 3-aminopropyl triethoxysilane, adding glutaraldehyde to carry out chemical reaction for the second time in chemical reactant for the first time, and then carry out chemical reaction for the third time with bovine serum albumin, obtain the dedicated molecular sieve used product of simulation moving-bed separating L-lactic acid and D-ALPHA-Hydroxypropionic acid,
The preparation of described honeycombed grain carrier is first will contain the kaolin of aqueous solution of urea that massfraction is 3.5-8.5% and water content≤10% to be mixed with colloidal sol with the ratio of 1:1-2, again 300-500 ℃ temperature lower calcination 2-4 hour, cooling, polishing is shaped, and obtains the honeycombed grain carrier of diameter 5-10mm;
Described primary first-order equation is that prepared honeycombed grain carrier is added massfraction is to soak in the dry toluene mixed solution of 3-aminopropyl triethoxysilane of 3-5%, then be filled with nitrogen, heat up, chemical reaction is carried out in stirring one time, obtains the reactant that concrete dynamic modulus solid particles surface and 3-aminopropyl triethoxysilane form chemical bond;
Described secondary reaction is concrete dynamic modulus solid particles surface and 3-aminopropyl triethoxysilane to be formed the reactant of chemical bond, adds that more than 3 times, massfraction is the glutaraldehyde of 6-10%, controls the pH=6.5-8.0 of reaction soln, stirs 4-7 hour under room temperature;
Described third-order reaction is after the concrete dynamic modulus solid particulate finishes with this and 3-aminopropyl triethoxysilane and glutaraldehyde reaction, filter, again it is added and contain the bovine serum albumin that massfraction is 2.5-5.5% more than 3 times, control the pH=6.5-8.0 of reaction soln, stirring reaction, take out particle after finishing, it is dried naturally, namely obtain molecular sieve.
2. simulation moving-bed separating L-lactic acid according to claim 1 and the dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid, is characterized in that: 150-300 ℃ of described primary first-order equation control temperature of reaction, reaction times 8-10 hour.
3. simulation moving-bed separating L-lactic acid according to claim 1 and the dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid, is characterized in that: 3-6 ℃ of described third-order reaction control temperature of reaction, reaction times 8-10 hour.
4. simulation moving-bed separating L-lactic acid according to claim 1 and the dedicated molecular sieve used preparation method of D-ALPHA-Hydroxypropionic acid, it is characterized in that: the reaction mother liquor in described each stage reclaims respectively, reuses.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157930A (en) * | 2002-05-30 | 2008-04-09 | 卡吉尔道有限责任公司 | Fermentation process using specific oxygen uptake rates as a process control |
| JP2008237101A (en) * | 2007-03-27 | 2008-10-09 | Toray Ind Inc | Method for producing chemical by continuous fermentation |
| CN101308124A (en) * | 2008-06-17 | 2008-11-19 | 江南大学 | D-type and / or L-type phenyl-lactic acid rapid checking method |
| CN101333554A (en) * | 2008-08-05 | 2008-12-31 | 山东大学 | Method for producing D-lactic acid by enzyme resolution of D,L-lactic Acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157930A (en) * | 2002-05-30 | 2008-04-09 | 卡吉尔道有限责任公司 | Fermentation process using specific oxygen uptake rates as a process control |
| JP2008237101A (en) * | 2007-03-27 | 2008-10-09 | Toray Ind Inc | Method for producing chemical by continuous fermentation |
| CN101308124A (en) * | 2008-06-17 | 2008-11-19 | 江南大学 | D-type and / or L-type phenyl-lactic acid rapid checking method |
| CN101333554A (en) * | 2008-08-05 | 2008-12-31 | 山东大学 | Method for producing D-lactic acid by enzyme resolution of D,L-lactic Acid |
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