CN112619614B - Hydroxyapatite composite porous material, preparation method and application thereof - Google Patents
Hydroxyapatite composite porous material, preparation method and application thereof Download PDFInfo
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- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
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- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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Abstract
The invention discloses a hydroxyapatite composite material, which comprises hydroxyapatite and konjac glucomannan, wherein the mass fraction of the hydroxyapatite is 66.7-97.2, and the mass fraction of the konjac glucomannan is 2.8-33.3; the hydroxyapatite composite material is of a porous structure; the hydroxyapatite composite material takes a three-dimensional network formed by the konjac glucomannan as a frame, the hydroxyapatite as a filler, and the hydroxyapatite Dan Baoguo is in the konjac glucomannan. The invention also discloses a preparation method of the hydroxyapatite composite material and application of the hydroxyapatite composite material in tobacco adsorption and harm removal.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a hydroxyapatite composite porous material, a preparation method thereof and application of the hydroxyapatite composite porous material in adsorbing harmful substances in tobacco.
Background
With the increasingly prominent smoking and health problems and the increased awareness of consumers to health, low-harm cigarettes also become a necessary development trend in the tobacco industry. In the process of developing low-harm cigarettes, the purposes of tar and harm reduction are generally realized by methods of blending tobacco sheets, blending expanded cut tobacco and expanded cut stems, perforating, ventilating and diluting filter sticks, adding an adsorption material into the filter sticks, applying high-permeability cigarette paper and the like. The method for adding the adsorbing material into the filter stick is an effective method, and a great deal of research is carried out on the adsorbing material added into the filter stick in the tobacco industry at home and abroad in recent years. The currently reported adsorbing materials for filter sticks comprise activated carbon, sepiolite, molecular sieves, zeolite, silica gel and the like. Researches find that the general cigarettes mainly depend on the following two factors in achieving the tar and harm reducing effects: 1. the material has the porous characteristic, and the physical adsorption effect brought by mesopores/micropores on the surface of the material is utilized; 2. the filtering device constructed by the porous material comprises a filtering membrane, a filtering rod (nozzle) and the like, and the whole adsorption capacity of the porous material is enhanced through macroscopic aggregation. The above materials such as activated carbon, sepiolite, molecular sieve, zeolite, silica gel, etc. have good effects in reducing tar and harm, but can bring about problems of smoke attenuation, introduction of bad smell, absorption resistance, etc. Considering the aspects of harm and tar reduction effect, resistance absorption and the like of the adsorption material comprehensively, the base material is required to have the following characteristics: 1. the porous material has a certain porous structure, and can be used for further searching for novel porous materials on the basis of original activated carbon, sepiolite, molecular sieves and the like; 2. secondary pore forming is considered, namely, the pore distribution and the pore size of the secondary pore forming can meet the requirement of enhancing the adsorption effect and simultaneously have no influence on the resistance to suction; 3. the secondary pore-forming process can realize pore distribution and adjustable pore size, meanwhile, the pore-forming process can realize continuous production, and the produced macro-filtration device is convenient for assembly operation on a filter tip production line.
The hydroxyapatite is porous microsphere, and its component is Hydroxyapatite (HAP), and the molecular formula of HAP is Ca 10 (PO 4 ) 6 (OH) 2 Belonging to the hexagonal system, P63/m space group; HAP is a typical biomedical material, and has the characteristics of no toxicity, environmental friendliness, wide sources, low cost and the like. The HAP microsphere with porous surface is an intermediate form in the preparation of HAP whisker, and is formed by outward diffusion of lamella or whisker which is not separated from nucleation growth points, and the appearance of secondary particles is similar to 'petals' or 'acupuncture'; gaps between the sheets or whiskers form the porous structure of the microsphere. In addition, the appearance of the microspheres can further create new pores when stacked. The basic unit lamella of the porous HAP microsphere or the whisker has highly ordered atomic structure arrangement and good structural integrity, the strength is approximately equal to the theoretical strength of valence bond force among atoms, and the whisker has the characteristics of high specific strength, high specific modulus, good creep resistance and the like in form. In addition, the short fiber morphology of the whisker can enable the porous HAP microsphere to absorb energy through bridging, crack deflection and pull-out effects, and stress concentrated at the tip of a crack is eliminated to enhance the toughness of the matrix. The HAP porous microspheres show good adsorption performance due to the excellent structure and mechanical properties. The patent CN1720828A uses hydroxyapatite in tobacco, and the hydroxyapatite has a good effect on adsorbing harmful substances in smoke, but still has a poor suction resistance effect, and cannot meet the requirement on adsorption and harm removal of a cigarette filter.
Konjac Glucomannan (KGM) is an organic biomass material, is a water-soluble natural polysaccharide, and has a main chain with a tertiary structure, wherein the primary structure is a linear structure which is formed by combining glucose and mannose serving as repeating units according to a certain molar ratio; the secondary structure is a double-folded spiral structure presented by stretching the KGM molecular chain; the tertiary structure is a three-dimensional structure presented by the rotation of KGM molecules in a three-dimensional space; because of its unique structure, KGM has the advantages of good cross-linking property, simple forming process, certain toughness, etc. In addition, the special physical and chemical properties of the material also have the following unique properties: a. thickening property, wherein the viscosity of the konjac powder sol with the mass fraction of 1% can reach thousands of mPa/s; b. gelling, the KGM is a non-newtonian fluid, exhibits a high viscosity at low concentrations, and gels upon standing; c. the water-retaining property, KGM contains a large amount of hydrophilic groups, so the water-retaining capacity can be 40 times higher than the self weight, and the water-retaining lubricating effect is better. KGM is derived from the root and tuber extracts of Amorphophallus konjac of the Araceae family, a species specific to China; the konjak belongs to the most species in Yunnan, has large planting amount, and has the advantages of wide raw material source, low cost, easy extraction and the like.
The composite porous material of the Hydroxyapatite (HAP) and the KGM is prepared by taking the HAP porous microspheres and the KGM as raw materials, and when the composite porous material is used in tobacco, the composite porous material has excellent effect on adsorption and harm reduction and has small suction resistance. Meanwhile, the preferable weighting agent is added for improving the density of the composite porous material. The composite material is prepared for the first time.
Disclosure of Invention
The invention prepares the composite porous material of HAP and KGM for the first time, and the composite porous material is an organic-inorganic composite porous material with good pore structure, pore size and porosity. Meanwhile, in order to ensure that the density of the composite porous material is matched with that of a common cigarette filter stick, a preferred weighting agent is added. The composite porous material particles are used in tobacco, so that the composite porous material particles have excellent effects on adsorption and harm reduction, and simultaneously have no influence on the resistance to adsorption and no introduction of bad smell.
The technical scheme of the invention is as follows:
the invention discloses a hydroxyapatite composite material, which comprises hydroxyapatite and konjac glucomannan, wherein the mass fraction of the hydroxyapatite is 66.7-97.2, and the mass fraction of the konjac glucomannan is 2.8-33.3; the hydroxyapatite composite material is of a porous structure; the hydroxyapatite composite material takes a three-dimensional network formed by the konjac glucomannan as a frame, the hydroxyapatite as a filler, and the hydroxyapatite Dan Baoguo is in the konjac glucomannan.
Preferably, the hydroxyapatite composite material also contains a weighting agent, and the weight percentage of the weighting agent is 5.0-35.0; the weighting agent is one or the combination of powdery barium sulfate, barium phosphate or zirconium dioxide.
Preferably, the hydroxyapatite is porous particles, the particle diameter of the hydroxyapatite is 10-100 μm, the pore diameter of the hydroxyapatite is 1-50 μm, and the porosity of the hydroxyapatite is 10-70%.
Preferably, the hydroxyapatite composite material is granular, the particle diameter of the hydroxyapatite composite material is 0.45mm-2mm, the porosity of the hydroxyapatite composite material is 10% -85%, and the pore diameter of the hydroxyapatite composite material is 0.05 μm-225 μm; the specific surface area is 0.1523m 2 /g-7.5482m 2 /g。
The second aspect of the invention discloses a preparation method of a hydroxyapatite composite material, which comprises the following steps:
(1) Preparing a suspension of hydroxyapatite porous particles and a weighting agent;
(2) Adding a cross-linking agent into the suspension obtained in the step (1), and uniformly mixing to obtain a mixed solution;
(3) Adding konjac glucomannan into the mixed solution obtained in the step (2), and mixing to obtain a gel mixture;
(4) Reacting the gel-like mixture obtained in the step (3) at 50-120 ℃ for 2-8 h;
(5) Freeze-drying the reaction product obtained in the step (4) until the dehydration is completed to form xerogel;
(6) And (4) crushing and screening the xerogel obtained in the step (5) step by step to obtain particles with the particle size of 0.45mm-2mm, namely the hydroxyapatite composite material.
Preferably, the cross-linking agent in the step (2) is one of ammonia water, sodium hydroxide and sodium bicarbonate or a combination thereof, and the amount of the cross-linking agent is 0.5-5.0wt% of the amount of water in the step (1); the addition amount of the konjac glucomannan in the step (3) is 1/50-1/10 of the water amount in the step (1), and the addition amount of the konjac glucomannan is 2.8-33.3% of the mass percentage of the konjac glucomannan in the hydroxyapatite composite material.
Preferably, the freeze-drying temperature of step (4) is-20 ℃ to-50 ℃.
Preferably, the preparation of the hydroxyapatite porous particles in the step (1) comprises the following steps:
(1) mixing calcium salt, phosphorus salt and a precipitator to form a mixed solution;
(2) adjusting the pH value of the mixed solution in the step (1) to 1.50-3.50;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2);
(4) and (4) filtering the mixed solution obtained in the step (3), and cleaning and drying the solid to obtain the hydroxyapatite porous particles.
Preferably, the calcium salt in step (1) is one of calcium chloride, calcium nitrate and calcium hydrophosphate or a combination thereof, and the calcium salt is added in an amount of 0.01mol/L to 1.67mol/L; the phosphorus salt is one or the combination of sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate, and the addition amount of the phosphorus salt is 0.005mol/L-1mol/L; the precipitator is urea, and the addition amount of the precipitator is 0.08-2.5 mol/L; step (2) using concentrated nitric acid, concentrated phosphoric acid or concentrated ammonia water to adjust the pH value of the mixed solution; the hydrothermal reaction temperature of the step (3) is 50-150 ℃, the reaction time is 6-72 h, and the self pressure of the reaction vessel is 0.01-1 MPa.
The third aspect of the invention discloses the application of the hydroxyapatite composite material in tobacco adsorption and harm removal.
The invention has the beneficial effects that:
1. the hydroxyapatite in the hydroxyapatite composite material is in a porous microspherical shape. The invention regulates and controls the components, the particle size, the surface pore size, the porosity and the like of the hydroxyapatite porous microsphere by regulating and controlling the molar concentration ratio of calcium salt/phosphorus salt, the dosage of a precipitator, the hydrothermal reaction temperature, the hydrothermal reaction time and the like, so that the prepared hydroxyapatite is microspherical and has a better surface porous structure. The diameter of the microsphere is 10-100 μm, pores are formed by mutually stacking and assembling whisker-shaped HAPs, the surface of the microsphere is in a porous structure, the pore size range is 1-50 μm, and the porosity reaches 10-70%; the description of the morphology also includes "petaloid" or "needle-punched" microspheres.
2. The preparation method of the hydroxyapatite composite particle provided by the invention adjusts the mass ratio of the porous hydroxyapatite microspheres to the konjac glucomannan, the dosage of deionized water, the type and dosage of an alkali cross-linking agent, the time and temperature of a cross-linking reaction, the size range of a particle product and the like, so that the prepared composite porous particle shows better biological safety, component integrity, and porous penetration and low resistance to draw. The particle structure of the hydroxyapatite composite material is characterized in that a three-dimensional network structure formed by KGM is used as a basic frame, HAP porous microspheres are used as fillers, and the HAP porous microspheres are wrapped in the KGM through crosslinking to form a 'raw material HAP porous + KGM secondary pore structure formed after freeze drying dehydration of the KGM'; the KGM crosslinked composite material shows good structural and component stability, and a porous structure of the composite material has certain through hole morphology characteristics; the specific surface area of the composite porous particles is 0.1523m in the particle size range of 0.45mm-2mm 2 /g-7.5482m 2 Per gram, porosity of 10-85%, pore size of 0.05-225 μm. The hydroxyapatite composite material has higher porosity and pore size, and is an ideal porous structure material. The tobacco smoke absorbing agent is used for absorbing and removing harm of the tobacco filter stick, the tobacco fragrance is not attenuated, and no absorption resistance or small absorption resistance is realized.
3. After human embryonic kidney epithelial cells (HEK 293T), mouse embryonic osteoblast precursor cells (MC 3T3-E1 cells) and monkey bone marrow mesenchymal stem cells (mBMSC) are soaked in leaching liquor of the particles of the hydroxyapatite composite material with the concentration of 0.1-0.5g/ml for 24 hours, the relative cell proliferation degree (RGR) is more than 90 percent. Therefore, the hydroxyapatite composite material has no cytotoxicity and shows better biological safety. The method is used for adsorbing and removing harm of tobacco, has no introduction of bad smell, and is safe to use.
4. The compact packing density (tap density) of the particles of the hydroxyapatite composite material is lower without adding weighting agent, and the hydroxyapatite composite material is directly used in a tobacco filter stick and can not meet the requirements of industrial production and assembly of the tobacco filter tip; meanwhile, in the smoking action process, the composite material particles in the filter tip are easy to escape, and the smoking experience of consumers is influenced. After the optimized weighting agent is added, the density of the particles of the composite material can be adjusted to be matched with the density of the tobacco filter stick, the requirements of industrial production and assembly of the tobacco filter tip can be met, meanwhile, the scattering phenomenon does not occur during smoking, and the smoking experience of consumers is improved. The preferable weighting agent is barium sulfate, barium phosphate or zirconium dioxide, and aims to achieve the purpose of weight increment, ensure that the composite material has no cytotoxicity and ensure that the composite material shows biological safety. The adsorbent is used for adsorbing and removing harm of the tobacco filter tip, ensures no bad smell and is safe to use.
Drawings
Fig. 1 is an XRD pattern of the hydroxyapatite porous microsphere prepared in example 1 of the present invention.
Fig. 2 is an SEM electron microscope morphology of the hydroxyapatite porous microsphere prepared in example 1 of the present invention, wherein (a) is a morphology of a porous microsphere group, and (b) is a typical "needle-punched" morphology of a specific porous microsphere after amplification.
Fig. 3 is a fourier transform infrared spectrum of hydroxyapatite porous microspheres prepared in example 1 of the present invention.
FIG. 4 is a basic morphology diagram of porous particles of hydroxyapatite composite material prepared in example 1 of the present invention; the method comprises the following steps of (a) obtaining an overall morphology of porous particles of the hydroxyapatite composite material, (b) obtaining a further enlarged local pore structure morphology, and (c) obtaining new pores formed by surface damage caused by KGM dehydration.
Fig. 5 shows relative cell proliferation rates of the porous particles of the hydroxyapatite composite material prepared in example 1 of the present invention, HEK293T cells, MC3T3-E1 cells, and bmsc cells after culturing in a leaching solution with a concentration of 0.1 to 0.5g/ml for 24 hours.
Detailed Description
The following examples are a series of detailed descriptions of the preparation method and features of the present invention, and are not to be construed as limiting the claims of the present invention. It is also noted that several alternatives and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.
Example 1
Preparing the hydroxyapatite porous microspheres. Preparing a mixed solution of calcium salt, phosphorus salt and a precipitator, wherein the calcium salt is calcium nitrate and the molar concentration is 0.05mol/L; the phosphorus salt is ammonium dihydrogen phosphate, and the molar concentration is 0.03mol/L; the molar concentration of the precipitator urea is 0.2mol/L; step (2) selecting concentrated nitric acid to adjust the pH value of the mixed solution in the step (1) to 3.50; step (3) putting the mixed solution with the effective volume of 70% into a reaction kettle for hydrothermal reaction; the hydrothermal reaction temperature is 75 ℃, the reaction time is 36h, and the self pressure of the reaction kettle is 0.1MPa; and (4) filtering the synthesized Hydroxyapatite (HAP) porous microspheres, and cleaning and drying to obtain the hydroxyapatite porous microspheres.
The X-ray diffraction (XRD) pattern of the prepared Hydroxyapatite (HAP) porous microsphere is shown in figure 1. As can be seen from fig. 1: the basic phase component of the hydroxyapatite porous microsphere is Hydroxyapatite (HAP). Calculated by JADE6.0, the unit cell parameters of the hydroxyapatite porous microsphere meet the following requirements: cell parameters
Cell volume
The crystallinity was 87.38%.
The SEM electron microscope appearance of the prepared Hydroxyapatite (HAP) porous microsphere is shown in figure 2. As can be seen from fig. 2 (a): the basic morphology of the hydroxyapatite porous microsphere material is microsphere, and the average size is about 55 μm; further enlarging to the figure (b), the surface is formed by stacking HAPs in a needle-punched or whisker shape, pores are formed among the HAPs in the needle-punched or whisker shape, and the pore size is about 2-15 mu m; the porosity measured by the suspended weight method was 58.38%.
The Fourier infrared spectrum of the prepared Hydroxyapatite (HAP) porous microsphere is shown in figure 3. As can be seen from the spectrum of FIG. 3, OH of the porous microspheres of hydroxyapatite is mainly the main component - Radical, PO 4 3- Radical and CO 3 2- Absorption peak of radical. OH (OH) - Radical, PO 4 3- The presence of the groups further indicates that the basic phase of the porous microspheres is hydroxyapatite, with the presence of CO 3 2- The radicals indicate part of OH in the HAP phase - Radicals being substituted, CO 3 2- Based on the decomposition products CO of urea 2 Partial dissolution of (2); and introducing CO 3 2- The anion end of the HAP porous microsphere is closer to inorganic components in human bone tissues, and the biological safety is higher.
The porous particles of the hydroxyapatite composite material are prepared by using the prepared porous hydroxyapatite microspheres as raw materials. The mass fraction of the hydroxyapatite porous microsphere is 80, and the mass fraction of the konjac glucomannan is 20. Preparing a suspension of hydroxyapatite porous microspheres; wherein the dosage of the solvent deionized water is 30 times of that of the konjac glucomannan; adding a cross-linking agent, wherein the cross-linking agent is a combination of an alkali cross-linking agent ammonia water and sodium bicarbonate, and the using amount of the cross-linking agent is 1.5wt% of the deionized water; adding KGM, and continuously stirring until the KGM is converted into gel; performing a crosslinking reaction on the gel-like mixture in the step (4), wherein the crosslinking reaction temperature is 80 ℃, and the reaction time is 8h; step (5), placing the mixture at-50 ℃ for freeze drying and dehydration until the dehydration is complete to form xerogel; and (6) crushing and screening the xerogel step by step to obtain porous particles of the hydroxyapatite composite material with the particle size range of 0.85mm-1 mm.
The basic morphology of the porous particles of the hydroxyapatite composite material is shown in fig. 4 (a), (b) and (c). FIG. 4 (a) shows the overall morphology of a composite porous particle with a transverse end dimension of about 1.36mm, which satisfies the particle size range after sieving; the konjac glucomannan is in a lamellar shape on the surface and has a characteristic wave or fold shape. At the circled position in fig. 4 (b), the thickness is significantly increased, indicating that the HAP porous microspheres are encapsulated inside themselves by the swollen KGM when crosslinked. As shown by further enlargement in FIG. 4 (b), the composite porous particle surface shows distinct pores due to dehydration, and the pore size of the pores is different, and the size of the macropores is about 100 μm. As shown in FIG. 4 (c), the pore structure of the material has pores surrounded by KGM, and some pores are formed by KGM self-destruction during dehydration, and the pore size is below 100 μm.
The prepared porous particles of the hydroxyapatite composite material are tested by a mercury intrusion instrument, the pore size range is 200nm-50 mu m, and the average pore size is 28.5 +/-5.2 mu m.
The prepared porous particles of the hydroxyapatite composite material are respectively tested for cytotoxicity by adopting human embryonic kidney epithelial cells (HEK 293T), mouse embryonic osteoblast precursor cells (MC 3T3-E1 cells) and monkey bone marrow mesenchymal stem cells (mBMSC). The leaching solution concentrations of the porous particles of the hydroxyapatite composite material obtained by the double preparation were 0.1g/ml, 0.2g/ml, 0.4g/ml and 0.5g/ml, the culture time of the above cells in the leaching solution was 24 hours, and the relative proliferation degree (RGR) results are shown in FIG. 5. As shown in FIG. 5, the cell proliferation ranges of the three cells HEK293T, MC T3-E1 and mBMSC are 81.5% -105.3%, and are all larger than 80% as a whole. According to the national standard GB/T14233.2-2005, the cellular toxicity reaction grades of the porous particles of the hydroxyapatite composite material prepared by the invention are all 0 or 1 grade, the porous particles can be regarded as non-toxic, and the material has better biological safety.
The prepared porous particles of the hydroxyapatite composite material are tested by a full-automatic specific surface and porosity analyzer, and the BET specific surface area is 1.0358m 2 The cumulative specific surface area of the adsorption holes at 2nm-300nm is 0.4530m 2 The average pore diameter of the mesopores during adsorption is 13.9024nm.
The packing compactness (namely tap density) of the porous particles of the hydroxyapatite composite material is measured by adopting a packing method, and the prepared porous particles of the hydroxyapatite composite material have the compact packing density (tap density) of 0.632g/cm 3 。
Example 2
The procedure of example 1 was repeated to prepare a porous hydroxyapatite microsphere material.
The procedure for preparing porous particles of hydroxyapatite composite material is the same as in example 1, except that in the step (1), 10 mass percent of zirconium dioxide is added when preparing the suspension of porous HAP microspheres. The other steps are the same.
The results of the tests on the porous particles of the hydroxyapatite composite material prepared were similar to those of example 1, but the density was 1.479g/cm 3 Is matched with the cigarette filter.
Example 3
The procedure of example 1 was repeated to prepare a porous hydroxyapatite microsphere material.
The procedure for preparing porous particles of hydroxyapatite composite material was also the same as in example 1, except that barium sulfate was added in a mass fraction of 10 when the suspension of HAP porous microspheres was prepared in step (1). The other steps are the same.
The test results of the porous particles of the hydroxyapatite composite material prepared were similar to those of example 1, but the density was 1.466g/cm 3 Is matched with the cigarette filter.
Example 4
The procedure of example 1 was repeated to prepare porous hydroxyapatite microsphere material.
The procedure for preparing porous particles of hydroxyapatite composite material was also the same as in example 1, except that barium phosphate was added in a mass fraction of 10 when the suspension of HAP porous microspheres was prepared in step (1). The other steps are the same.
The test results of the porous particles of the hydroxyapatite composite material prepared were similar to those of example 1, but the density was 1.398g/cm 3 Is matched with the cigarette filter.
Example 5
The porous particles of the hydroxyapatite composite material prepared in the embodiment 1 and the embodiment 2 are added into a cigarette filter rod, and 1-3mg of the porous particles of the hydroxyapatite composite material are added into a standard cigarette filter rod per millimeter to carry out an adsorption test. A common cigarette filter rod without porous particles of hydroxyapatite composite material was used as a control. The results are shown in the following table.
In the embodiment 1, the porous particles of the hydroxyapatite composite material are difficult to be added into the tobacco filter stick and can not meet the requirements of industrial production and assembly of the tobacco filter. And the reference sample added into the tobacco filter stick is dissipated during smoking, so that the smoking experience of consumers is influenced. The hydroxyapatite composite material in the embodiment 2 is easily added into the tobacco filter stick, the industrial production and assembly requirements of the tobacco filter tip can be met, and after the hydroxyapatite composite material is added into the tobacco filter stick, no dissipation phenomenon exists during smoking, so that the smoking experience of consumers is improved.
TABLE 1 cigarette physical parameters
As can be seen from Table 1, the average smoking resistance of the cigarettes is relatively close, and the smoking requirements of the cigarettes can be met.
Table 2 detection results of 7 components in flue gas
As can be seen from table 2 above, compared with the control sample, the cigarette added with the porous particles made of the hydroxyapatite composite material has the advantages that the CO in the smoke is reduced by 6.06%, the NNK is reduced by 9.51%, the crotonaldehyde is reduced by 15.11%, the HCN is reduced by 20.10%, the NH3 is reduced by 9.06%, and the phenol is reduced by 26.71%. The 7 harmful substances are reduced to different degrees, and particularly the reducing effect on phenol, HCN and crotonaldehyde is obvious. Therefore, the porous particles of the hydroxyapatite composite material have obvious effect of adsorbing and removing the harmful substances.
TABLE 3 sensory evaluation scoring table
As can be seen from table 3 above, compared with the control sample, the cigarette added with the porous particles of the hydroxyapatite composite material has the sensory evaluation score improved by 1.2, so that the sensory quality of the cigarette is obviously improved, the whole style of the cigarette is kept unchanged, the change of the aroma and the smoke concentration is small, the irritation is obviously reduced, the aftertaste is obviously improved, and the smoking comfort is improved.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed.
Claims (5)
1. The preparation method of the hydroxyapatite composite material is characterized in that the hydroxyapatite composite material comprises hydroxyapatite and konjac glucomannan, wherein the mass fraction of the hydroxyapatite is 66.7-97.2, and the mass fraction of the konjac glucomannan is 2.8-33.3; the hydroxyapatite composite material is of a porous structure; the hydroxyapatite composite material takes a three-dimensional network formed by the konjac glucomannan as a frame, takes the hydroxyapatite as a filling material, and takes the hydroxyapatite Dan Baoguo in the konjac glucomannan; the hydroxyapatite composite material is granular, the diameter of the granules is 0.45mm-2mm, the porosity is 10% -85%, and the pore diameter is 0.05-225 μm; the specific surface area of the material is 0.1523m 2 /g - 7.5482 m 2 (ii)/g; the hydroxyapatite composite material also contains a weighting agent, and the weight percentage of the weighting agent is 5.0-35.0; the weighting agent is one or the combination of powdery barium sulfate, barium phosphate or zirconium dioxide; the hydroxyapatite is porous particles, the particle diameter of the hydroxyapatite is 10-100 mu m, the aperture of the hydroxyapatite is 1-50 mu m, and the porosity of the hydroxyapatite is 10-70%;
the preparation method of the hydroxyapatite composite material comprises the following steps:
(1) Preparing a suspension of hydroxyapatite porous particles and a weighting agent;
(2) Adding a cross-linking agent into the suspension liquid obtained in the step (1), and uniformly mixing to obtain a mixed liquid;
(3) Adding konjac glucomannan into the mixed solution obtained in the step (2), and mixing to obtain a gel mixture;
(4) Reacting the gel-like mixture obtained in the step (3) at 50-120 ℃ for 2h-8h;
(5) Freeze-drying the reaction product obtained in the step (4) until the dehydration is completed to form xerogel;
(6) Crushing and screening the xerogel obtained in the step (5) step by step to obtain particles with the particle size of 0.45mm-2mm, namely the hydroxyapatite composite material;
the preparation method of the hydroxyapatite porous particles in the step (1) comprises the following steps:
(1) mixing calcium salt, phosphorus salt and a precipitator to form a mixed solution;
(2) adjusting the pH value of the mixed solution in the step (1) to 1.50-3.50;
(3) carrying out hydrothermal reaction on the mixed solution in the step (2);
(4) and (4) filtering the mixed solution obtained in the step (3), and cleaning and drying the solid to obtain the hydroxyapatite porous particles.
2. The preparation method according to claim 1, wherein the cross-linking agent in step (2) is one or a combination of ammonia water, sodium hydroxide and sodium bicarbonate, and the amount of the cross-linking agent is 0.5-5.0wt% of the amount of water in step (1); the addition amount of the konjac glucomannan in the step (3) is 1/50-1/10 of the water amount in the step (1), and the addition amount of the konjac glucomannan is 2.8-33.3% of the mass percentage of the konjac glucomannan in the hydroxyapatite composite material.
3. The preparation method according to claim 1, wherein the freeze-drying temperature in the step (4) is-20 ℃ to-50 ℃.
4. The preparation method according to claim 1, wherein the calcium salt in step (1) is one or a combination of calcium chloride, calcium nitrate and calcium hydrogen phosphate, and the calcium salt is added in an amount of 0.01-1.67 mol/L; the phosphorus salt is one or the combination of sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium dihydrogen phosphate, and the addition amount of the phosphorus salt is 0.005mol/L-1mol/L; the precipitator is urea, and the addition amount of the precipitator is 0.08-2.5 mol/L; step (2) using concentrated nitric acid, concentrated phosphoric acid or concentrated ammonia water to adjust the pH value of the mixed solution; the hydrothermal reaction temperature of the step (3) is 50-150 ℃, the reaction time is 6h-72h, and the self pressure of the reaction container is 0.01-1 MPa.
5. The hydroxyapatite composite material prepared by the preparation method according to any one of claims 1 to 4 is used for absorbing and removing harm, reducing absorption resistance and having no dissipation of tobacco.
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