CN101628713B - Hydroxylapatite (HA) chromatographic packing calcining process - Google Patents
Hydroxylapatite (HA) chromatographic packing calcining process Download PDFInfo
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- CN101628713B CN101628713B CN2009100180323A CN200910018032A CN101628713B CN 101628713 B CN101628713 B CN 101628713B CN 2009100180323 A CN2009100180323 A CN 2009100180323A CN 200910018032 A CN200910018032 A CN 200910018032A CN 101628713 B CN101628713 B CN 101628713B
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- temperature
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- calcining
- microballoon
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Abstract
The invention discloses a hydroxylapatite (HA) chromatographic packing calcining process, comprising the following steps: adopting tetrahydrated calcium nitrate and diammonium hydrogen phosphate as raw materials to prepare HA slurry by chemical precipitation method; then using a mini-spray dryer to prepare HA microspheres; finally treating HA microspheres by calcining process and obtaining the HA chromatographic packing. In the method of the invention, the calcining temperature and the holding time are controlled so as to ensure the preparation of the HA chromatographic packing which has the advantage of good sphericity, high specific area, good pore size distribution, high pore volume and the like and further widen the application area of the HA material in chromatograph field.
Description
Technical field
The present invention relates to a kind of calcining process of chromatograph packing material, relate in particular to the calcining process of a kind of hydroxyapatite (HA) chromatograph packing material, promptly influence the factor of filler chromatographic property from specific surface area, pore size distribution, pore volume and the size-grade distribution etc. of product, determine the calcining process that a kind of each key index consistence is optimized, and then obtain comparatively ideal HA chromatograph packing material.
Background technology
After people such as Tiselius in 1956 have prepared hydroxyapatite (HA) first, the filler that HA just is used as liquid-phase chromatographic column widely removes biologically active substances such as separation and Extraction protein, enzyme, and obtained tangible result [Barroug A, Fastrez J, Lemattre J, Rouxhet P.Adsorption of succinylatedlysozyme on hydroxyapatite.J Colloid Interf Sci, 1997,189:37-42; Eis C, Griessler R, Maier M, Weinhausel A.Efficient downstream processing ofmaltodextrin phosphorylase from escherichia and stabilization of the enzyme byimmobilization onto hydroxyapatite.J Biotechnol, 1997,58:157].The unit cell of HA is respectively 10 Ca by 44 atomic buildings
2+, 6 PO
4 3-With 2 OH
-[Mar1a V R, Jose Mar1aG C.Calcium phosphates as substitution of bone tissues.Prog in Solid StateChem, 2004,32:1-31].If will distinguish with the difference of locus of living in a kind of ion, can be with the molecular formula Ca of HA
10(PO
4)
6(OH)
2Be written as Ca (1)
4Ca (2)
6[PO (1) O (2) O (3)
2]
6(OH
H)
2[Zhu W H, Wu P.Surface energetics of hydroxyapatite:a DFT study.Chemical Physics Letters 2004,396:38-42], wherein 4 Ca
2+Be positioned at Ca (1) position, i.e. Z=0 and 1/2 each two, other 6 occupy Ca (2) position, i.e. Z=1/4 and 3/4 each three; 6 PO
4 3-Quadridentate lays respectively on Z=1/4 and 3/4 plane of forming, and respectively has 3 on each plane; OH lays respectively on Z=1/4 and 3/4 crystal face.4 Ca (1) are in the octahedra center of Ca-O that 6 O form, 6 Ca (2) then are in the three-fold coordination body center that 3 O form, its polyhedron constitutes parallel c axial screw sixfold symmetry structure channel around six helical axis distribution, OH-between passage by Ca
2+Equilateral triangle center [Madhavi S with Sauerstoffatom formation perpendicular to the c axis plane, Ferraris C, White T J.Synthesis and crystallization of macroporous hydroxyapatite.J Solid State Chem, 2005,178:2838-2845], this microtexture is just like one " ion exchange column ", and ion is wherein easily replaced by other ion.Therefore, HA has the ability of very strong ion-exchange capacity and absorption bioactive molecules.
The HA of traditional method preparation mostly is the irregular crystal of sheet, and is broken easily under the effect of moving phase, and its widespread use is restricted.In recent years, development abroad the crystallite agglomeration technique, this technology mainly is HA crystal grain to be combined become globosity [US Patent 4781904 under the Van der Waals force effect, US Patent 4794171], this method is meant and enters after with the HA slurry atomization that drying becomes spheroidal particle in the high-temperature medium.This has overcome the defective of HA filler poor mechanical property to a certain extent, further widened its use field, but the HA chromatograph packing material intensity of this method preparation is low, broken easily under the moving phase effect, therefore need the follow-up calcination processing of process to improve the bonding strength [US Patent 4874511] of microballoon.In addition, calcining is an important method improving material property, and is all influential to performances such as the phase composite of sample, surface topography, specific surface area, size distribution, porosity, pore size distributions.And the quality of these performances is very big for the performance impact of chromatograph packing material, therefore can improve the use properties of HA chromatograph packing material by calcination processing.The ideal chromatograph packing material requires performances such as its specific surface area height, narrow particle size distribution, even aperture distribution, yet also lacks the calcining process that each key index consistence of a kind of HA chromatograph packing material is optimized in the prior art.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of calcining process that obtains high-performance HA chromatograph packing material.
The basic technical scheme of the calcining process of hydroxyapatite of the present invention (HA) chromatograph packing material is as follows:
With four water-calcium nitrate (Ca (NO
3)
24H
2O) and Secondary ammonium phosphate ((NH
4)
2H (PO
1)) be raw material, adopt chemical precipitation method to prepare the HA slip; Utilize mini spray dryer to prepare the HA microballoon then; Handle the HA microballoon by implementing calcination process at last, promptly adopt the HA chromatograph packing material of different calcining temperatures (500-1000 ℃) and soaking time (0.5-8h) obtained performance excellence respectively.
Further, the calcining process of hydroxylapatite chromatography filler of the present invention is characterized in that, realizes with following steps:
(1) be raw material with four water-calcium nitrate and Secondary ammonium phosphate, respectively with deionized water with its dissolving and by calcium: the phosphorus mol ratio is 1.5～1.8: 1 mixed, with ammoniacal liquor regulator solution pH value is 10-12, and (its reaction formula is: 10Ca (NO to prepare the HA slip with chemical precipitation method
3)
2+ 6 (NH
4)
2HPO
4+ 8NH
4OH → Ca
10(PO
4)
6(OH)
2+ 20NH
4NO
3+ 6H
2O);
(2) with deionized water the HA slip of step (1) preparation being diluted to concentration is 10 ± 2g/L, under 400 ± 50 rev/mins magnetic agitation speed, with nozzle diameter is 0.5 ± 0.1mm, inlet temperature is 170 ± 20 ℃, temperature of outgoing air is 85 ± 5 ℃, inlet amount is that the condition of 15 ± 5ml/min is carried out spraying drying to the HA slurry solution, and the HA slip is transformed into the HA microballoon;
(3) taking by weighing the HA powder that obtains after the spraying drying and place crucible, is 500～1000 ℃ with temperature, and soaking time is the condition of 0.5～8h, places resistance furnace to carry out calcination processing;
(4) calcining finishes, and treats to take out sample after furnace temperature is reduced to 20～100 ℃, and is placed in the drying basin and preserves, and is standby.
In the calcining process of above-mentioned hydroxylapatite chromatography filler, the described calcium of step (1): preferred 1.67: 1 of phosphorus mol ratio.The described pH value of step (1) is 10.5-11.5 preferably.The described HA powder of step (3) is packed into when carrying out calcination processing in the crucible, and sample can not be filled too tight, to prevent microballoon generation agglomeration.The amount of taking by weighing of described HA powder is 20～100g preferably; Most preferably be 40～60g.The described calcining temperature of step (3) preferably is made as 500～700 ℃, and soaking time is preferably 1～4h, and heat-up rate preferably is made as 3-5 ℃/min.Further, the described calcining temperature of step (3) preferably is made as 500 ℃, 600 ℃ or 700 ℃, and soaking time preferably is made as 1h.
The present invention adopt slip synthetic-microballoon preparation-calcination processing three-step approach prepares the HA chromatograph packing material, the performances such as specific surface area, pore size distribution and pore volume, granularity and phase composite thereof of regulating the HA microballoon by reasonable control calcining temperature and soaking time.
Utilize the inventive method, by control to calcining temperature and soaking time, realized that preparation has that good sphericity, specific surface area height, pore size distribution are good, the HA chromatograph packing material of pore volume advantages of higher, has further widened the Application Areas of HA material in chromatographic field.
Test confirms, HA chromatograph packing material regular shape, the epigranular that the inventive method obtained, specific surface area is big, pore size distribution is narrow and pore volume is high, is a kind of ideal chromatograph packing material.
Description of drawings
Fig. 1 shows the SEM figure of the HA microballoon different amplification that the inventive method is prepared;
Fig. 2 show under the different soaking times (get 4 batches of identical samples, calcining temperature is made as 500 ℃, soaking time be made as respectively 0,0.5,1 and 8h) pore size distribution curve of HA microballoon;
Fig. 3 shows the pore size distribution curve of (get 6 batches of identical samples, calcining temperature is made as 500 ℃, 600 ℃ respectively, and 700 ℃, 800 ℃, 900 ℃ and 1000 ℃, soaking time all is made as 1h) HA microballoon under the different calcining temperatures;
Fig. 4 shows the grain size distribution curve of the HA microballoon that the inventive method is prepared.
Embodiment
Below in conjunction with embodiment preparation method of the present invention is further described, but is not limited only to this.
Embodiment 1
(1) being raw material with four water-calcium nitrate and Secondary ammonium phosphate, is 1.67 ratio in calcium phosphorus mol ratio, respectively with deionized water dissolving and to regulate the pH value with ammoniacal liquor be 11.5, prepares the HA slip with chemical precipitation method.
(2) with deionized water prepared HA slip being diluted to 10g/L, under 400 rev/mins magnetic agitation speed, is 0.5mm with the nozzle diameter with above-mentioned mixing solutions, inlet temperature is 170 ℃, temperature of outgoing air is 85 ℃, and inlet amount is the condition of 15ml/min, carries out spraying drying;
(3) taking by weighing the about 50g of HA powder that obtains after the spraying drying and place crucible, is 500 ℃ with temperature, and soaking time is under the condition of 0.5h, places resistance furnace to carry out calcination processing;
(4) furnace cooling takes out sample after furnace temperature is reduced to 50 ℃, and with it as for preserving in the drying basin.
The median size of prepared HA microballoon is about 3.040 μ m, and specific surface area is 66.541m
2/ g, pore volume are 0.3503ml/g, and as seen from Figure 2, the pore size distribution of this microballoon mainly concentrates on 20-50nm.
(1) being raw material with four water-calcium nitrate and Secondary ammonium phosphate, is 1.67 ratio in calcium phosphorus mol ratio, respectively with deionized water dissolving and to regulate the pH value with ammoniacal liquor be 11.5, prepares the HA slip with chemical precipitation method.
(2) with deionized water prepared HA slip being diluted to 10g/L, under 400 rev/mins magnetic agitation speed, is 0.5mm with the nozzle diameter with above-mentioned mixing solutions, inlet temperature is 170 ℃, temperature of outgoing air is 85 ℃, and inlet amount is the condition of 15ml/min, carries out spraying drying;
(3) taking by weighing the about 50g of HA powder that obtains after the spraying drying and place crucible, is 600 ℃ with temperature, and soaking time is under the condition of 1h, places resistance furnace to carry out calcination processing;
(4) furnace cooling takes out sample after furnace temperature is reduced to 20-60 ℃, and with it as for preserving in the drying basin.The median size of prepared HA microballoon is about 3.197 μ m, and specific surface area is 44.135m
2/ g, pore volume are 0.3277ml/g, and as seen from Figure 3, the pore size distribution of this microballoon mainly concentrates on 40-70nm.
(1) being raw material with four water-calcium nitrate and Secondary ammonium phosphate, is 1.67 ratio in calcium phosphorus mol ratio, respectively with deionized water dissolving and to regulate the pH value with ammoniacal liquor be 11.5, prepares the HA slip with chemical precipitation method.
(2) with deionized water prepared HA slip being diluted to 10g/L, under 400 rev/mins magnetic agitation speed, is 0.5mm with the nozzle diameter with above-mentioned mixing solutions, inlet temperature is 170 ℃, temperature of outgoing air is 85 ℃, and inlet amount is the condition of 15ml/min, carries out spraying drying;
(3) taking by weighing the about 50g of HA powder that obtains after the spraying drying and place crucible, is 700 ℃ with temperature, and soaking time is under the condition of 1h, places resistance furnace to carry out calcination processing;
(4) furnace cooling takes out sample after furnace temperature is reduced to 40 ℃, and with it as for preserving in the drying basin.The median size of prepared HA microballoon is about 3.197 μ m, and specific surface area is 26.761m
2/ g, pore volume are 0.1039ml/g, and as seen from Figure 3, the size-grade distribution of this microballoon mainly concentrates on 90-130nm.
Embodiment 4
(1) be raw material with four water-calcium nitrate and Secondary ammonium phosphate, respectively with deionized water with its dissolving and by calcium: the phosphorus mol ratio is 1.67: 1 a mixed, is 11.5 with ammoniacal liquor regulator solution pH value, prepares the HA slip with chemical precipitation method;
(2) with deionized water the HA slip of step (1) preparation being diluted to concentration is 10g/L, under 400 ± 10 rev/mins magnetic agitation speed, with nozzle diameter is 0.5 ± 0.1mm, inlet temperature is 170 ± 10 ℃, temperature of outgoing air is 85 ± 5 ℃, inlet amount is that the condition of 15ml/min is carried out spraying drying to the HA slurry solution, and the HA slip is transformed into the HA microballoon;
(3) take by weighing the HA powder 50g that obtains after the spraying drying and place crucible (getting 4 batches of identical samples respectively), the speed that with heat-up rate is 5 ℃/min rises to 500 ℃ with temperature, the every lot sample of soaking time is made as 0,0.5,1 and the condition of 8h respectively, places resistance furnace to carry out calcination processing;
(4) calcining finishes, and treats to take out sample after furnace temperature is reduced to 40 ℃, and is placed in the drying basin and preserves, and is standby.
Test detects: the pore size distribution song of HA microballoon is seen Fig. 2.
Embodiment 5
(1) be raw material with four water-calcium nitrate and Secondary ammonium phosphate, respectively with deionized water with its dissolving and by calcium: the phosphorus mol ratio is 1.67: 1 a mixed, is 11.5 with ammoniacal liquor regulator solution pH value, prepares the HA slip with chemical precipitation method;
(2) with deionized water the HA slip of step (1) preparation being diluted to concentration is 10g/L, under 400 rev/mins magnetic agitation speed, with the nozzle diameter is 0.5mm, inlet temperature is 170 ℃, temperature of outgoing air is 85 ℃, inlet amount is that the condition of 15ml/min is carried out spraying drying to the HA slurry solution, and the HA slip is transformed into the HA microballoon;
(3) take by weighing the HA powder 50g that obtains after the spraying drying and place crucible (getting 6 batches of identical samples respectively), the speed that with heat-up rate is 5 ℃/min rises to 500 ℃, 600 ℃ respectively with temperature, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃, respectively described 6 batches of identical samples are placed 500 ℃, 600 ℃ then, 700 ℃, 800 ℃, carry out calcination processing in the resistance furnace of 900 ℃ or 1000 ℃ conditions, soaking time all is made as 1h;
(4) calcining finishes, and treats to take out sample after furnace temperature is reduced to 40 ℃, and is placed in the drying basin and preserves, and is standby.
Test detects: the pore size distribution song of HA microballoon is seen Fig. 3.
Claims (1)
1. the calcining process of a hydroxylapatite chromatography filler is characterized in that, realizes with following steps:
(1) be raw material with four water-calcium nitrate and Secondary ammonium phosphate, respectively with deionized water with its dissolving and by calcium: the phosphorus mol ratio is 1.67: 1 a mixed, is 10.5-11.5 with ammoniacal liquor regulator solution pH value, prepares the HA slip with chemical precipitation method;
(2) with deionized water the HA slip of step (1) preparation being diluted to concentration is 10 ± 2g/L, under 400 ± 50 rev/mins magnetic agitation speed, with nozzle diameter is 0.5 ± 0.1mm, inlet temperature is 170 ± 20 ℃, temperature of outgoing air is 85 ± 5 ℃, inlet amount is that the condition of 15 ± 5ml/min is carried out spraying drying to the HA slurry solution, and the HA slip is transformed into the HA microballoon;
(3) taking by weighing the HA powder that obtains after the spraying drying and place crucible, is 600 ℃ or 700 ℃ with temperature, and soaking time is the condition of 1h, places resistance furnace to carry out calcination processing;
(4) calcining finishes, and treats to take out sample after furnace temperature is reduced to 20～100 ℃, and is placed in the drying basin and preserves, and is standby.
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