Kaolin with excellent coagulation performance, preparation method thereof and hemostatic material

Abstract

The invention provides kaolin with excellent coagulation performance, a preparation method thereof and a hemostatic material, and relates to the field of materials. The preparation method of the kaolin with excellent coagulation performance comprises the following steps: crushing kaolin raw ore, and then mixing with water to obtain kaolin coarse mortar; performing first mixing on the kaolin coarse mortar, sodium hydroxide and sodium hexametaphosphate, and performing staged treatment and impurity removal by adopting a spiral desanding and multi-stage cyclone to obtain kaolin fine ore pulp; the kaolin fine ore pulp and sodium hexametaphosphate are mixed for the second time, then magnetic separation impurity removal and wet grinding and stripping treatment are carried out, and kaolin superfine ore pulp is obtained; carrying out dehydration treatment on the kaolin superfine ore pulp, and drying to obtain purified kaolin; and calcining the purified kaolin to obtain the target kaolin. The kaolin prepared by the method provided by the invention has a good activating effect on platelets and excellent coagulation performance.

Description

Technical Field

[0001] The present application relates to the field of materials, and in particular to kaolin with excellent coagulation performance, a preparation method thereof, and a hemostatic material. Background Art

[0002] Kaolin, as a natural mineral material, has shown great potential in the medical field, especially in the development of hemostatic materials, due to its unique physical and chemical properties. Its hemostatic mechanism mainly involves two key aspects: First, the layered structure and micropores of kaolin give it excellent adsorption and ion exchange properties. When kaolin comes into contact with blood, it can quickly absorb water from the blood, thereby concentrating platelets and thrombin. This process promotes the aggregation of coagulation factors and platelets and accelerates hemostasis. Secondly, kaolin has a negative charge on its surface under the pH conditions of blood, which can quickly activate the coagulation factor FXII and convert it into FXIIa, thereby initiating the intrinsic coagulation pathway. Subsequently, this process activates the coagulation factor FXI, triggers the coagulation waterfall, promotes the conversion of fibrinogen into fibrin monomers, and finally forms a stable fibrin clot. These characteristics make kaolin of great value in the development of hemostatic materials. For example, the "battle wound gauze" developed by Z-Medica in the United States uses the hemostatic properties of kaolin to quickly and effectively control bleeding, especially for special situations where tourniquets cannot be used.

[0003] However, the rate of kaolin in the coagulation process and the strength of the formed thrombus may be affected by many factors. In emergency situations, such as traumatic bleeding or surgery, rapid hemostasis is crucial because it can reduce blood loss and improve patient survival. In addition, the strength of the thrombus is directly related to the quality of wound healing; a strong thrombus can provide a stable hemostatic environment for the wound and promote healing. On the contrary, a slow coagulation process and a weak thrombus may increase the risk of bleeding and complications.

[0004] Therefore, researching and developing more effective kaolin application technologies to increase its rate in the coagulation process and the strength of the formed thrombus is of great significance for improving the performance and clinical effects of hemostatic materials. Summary of the invention

[0005] The purpose of the present application is to provide a kaolin with excellent coagulation performance and a preparation method and a hemostatic material thereof to solve the above problems.

[0006] To achieve the above objectives, this application adopts the following technical solutions: A method for preparing kaolin with excellent coagulation performance, comprising: The kaolin ore is crushed and then mixed with water to obtain a kaolin coarse mortar; The kaolin coarse sand slurry, sodium hydroxide and sodium hexametaphosphate are first mixed, and a spiral sand removal and a multi-stage cyclone are used to perform classification treatment and remove impurities to obtain a kaolin fine ore slurry; The kaolin fine slurry is mixed with sodium hexametaphosphate for a second time, and then subjected to magnetic separation and impurity removal and wet grinding treatment to obtain kaolin ultrafine slurry; Dehydrating and drying the ultrafine kaolin slurry to obtain purified kaolin; The purified kaolin is calcined to obtain the target kaolin.

[0007] Preferably, the kaolin ore is taken from Maoming, Guangdong.

[0008] Preferably, the solid content of the kaolin coarse sand mortar is 10-50wt%.

[0009] Preferably, in the first mixing, the amount of sodium hydroxide used is 0.01-0.04wt% of the mass of the dry ore in the coarse kaolin mortar, and the amount of sodium hexametaphosphate used is 0.05-0.1wt% of the mass of the dry ore in the coarse kaolin mortar.

[0010] Preferably, in the second mixing, the amount of sodium hexametaphosphate used is 0.05-0.1wt% of the mass of the dry ore in the kaolin fine slurry.

[0011] Preferably, the fineness of the ultrafine kaolin slurry is such that kaolinite with a particle size of less than 2 μm accounts for 90% or more of the dry weight of kaolin.

[0012] Preferably, the drying temperature is 65-80°C.

[0013] Preferably, the heating rate of the calcination treatment is 4.5-5.5°C / min, the end temperature is 495-505°C, and the holding time is 0.45-1.05h.

[0014] The present application also provides kaolin with excellent coagulation performance, which is prepared using the preparation method of kaolin with excellent coagulation performance.

[0015] The present application also provides a hemostatic material, comprising the kaolin with excellent coagulation performance.

[0016] Compared with the prior art, the beneficial effects of this application include: The preparation method of kaolin with excellent coagulation performance provided in this application first purifies kaolin to remove impurities (quartz, etc.) of the original ore, and the purity can reach 98% or more. The particles obtained by subsequent calcination are finer and more friendly to the wound surface; and after removing impurities, the adverse effects of impurities on the coagulation effect can be effectively eliminated. In addition, the high-purity kaolin also has a high degree of crystallinity, and the crystallinity index Hi is 1.07±0.077, showing a large tightly packed sheet structure. After calcination modification, it is more conducive to the curling of the edge surface, thereby promoting the activation of platelets, and can improve the platelet activation rate and greatly improve the coagulation rate of kaolin during the coagulation process, and increase the coagulation time from no less than 2min to the fastest 1.2min to achieve coagulation. At the same time, the coagulation strength is also greatly improved compared with other kaolins, which provides strong support for the development and application of medical hemostatic kaolin and related hemostatic products, thereby promoting the rational development and utilization of medical hemostatic kaolin.

[0017] This method has the characteristics of simple preparation, fast coagulation speed and high coagulation strength, and can provide effective assistance for the development and performance optimization of medical hemostatic kaolin.

[0018] Kaolin reserves are abundant and can be prepared into hemostatic materials at low cost, which has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0020] Figure 1 The thromboelastograms of different kaolins are shown; Figure 2 This is a graph of platelet activation amounts of different kaolins; Figure 3 This is a diagram of the surface potential of different kaolins; Figure 4 The scanning electron microscope images of different kaolins; Figure 5 XRD patterns of different kaolins; Figure 6 This is a refined quantitative analysis diagram of the kaolin K1 component structure. DETAILED DESCRIPTION

[0021] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0022] Example 1 This embodiment provides a kaolin with excellent coagulation performance, and the preparation method thereof is as follows: Kaolin ore from Maoming, Guangdong was selected, and it was initially crushed and mixed with water to obtain kaolin coarse sand mortar. 0.04wt% of sodium hydroxide and 0.1wt% of sodium hexametaphosphate were added to the kaolin coarse ore slurry based on the dry ore mass of the kaolin coarse ore slurry. The heavy mineral impurities such as sand and gravel in the ore were removed by spiral sand removal. The kaolin coarse ore slurry was graded by a multi-stage cyclone to separate mineral particles of different particle sizes to obtain kaolin fine ore slurry.

[0023] Add 0.1% of the dry ore mass of the kaolin fine slurry to the dispersant sodium hexametaphosphate, and perform 3T superconducting magnetic separation to remove impurities, remove iron impurities in the ore, and improve the whiteness and purity of the kaolin. The kaolin fine slurry after impurities removal is then wet-milled in a rapid ball mill to obtain kaolin ultrafine slurry. The milled kaolin is dehydrated by a filter press, and the kaolin is strongly dried using a drying equipment for subsequent processing and application. The kaolin is sterilized to ensure the hygiene and safety of the product. The obtained kaolin is labeled as K1.

[0024] Weigh 5g of K1 kaolin and place it in a 30ml ceramic crucible for calcination at 500℃, with a heating rate of 5℃ / min. Heat from room temperature to 500℃ for 96 min, and keep it at 500℃ for 0.5h. Take out the calcined kaolin and store it in a sealed and dry environment to obtain the target kaolin K5.

[0025] Example 2 The difference from Example 1 is that the heat preservation time is 1 hour. The obtained kaolin is recorded as K6.

[0026] Comparative Example 1 0.5g of K1 kaolin obtained in Example 1 was mixed with 90mL of 1mol / L citric acid solution in the lining of a 100mL reactor. After being uniformly mixed with a nine-stage electric stirrer for 15 minutes, it was loaded into a reactor and reacted in an electric blast drying oven at 90°C for 8 hours. When it drops to room temperature, the upper clear liquid after the reaction is poured out, and the lower sample is poured into a 100mL centrifuge tube. Centrifuge at a speed of 8000r / min in a centrifuge until the pH of the suspension washed with distilled water is 7, and no precipitation is produced when AgNO3 and BaCl2 are added to the upper clear liquid. Take the lower layer of suspension and dry it at 60°C in a drying oven to obtain acid-modified kaolinite, which is recorded as kaolin K2.

[0027] Comparative Example 2 Suzhou kaolin was taken and purified according to the purification method of Example 1 to obtain kaolin K3.

[0028] Comparative Example 3 Kaolin K1 and kaolin K3 were mixed in a ratio of 1:1, and then added into a ball mill for dry grinding to obtain kaolin K4.

[0029] The composition of kaolin is shown in Table 1 below: Table 1 Kaolin XRF composition (wt%)

[0030] Thromboelastography was performed on several different kaolins: Weigh 50 mg of each sample and add it to a 1.5 ml centrifuge tube. Pipette 1 ml of anticoagulated human venous blood (3.2% sodium citrate) and add it to the centrifuge tube containing the sample. Stir with a pipette tip to mix the sample and blood and then test immediately. Add 1 ml of anticoagulated blood to a blank centrifuge tube as a blank control; add 1 ml of anticoagulated blood to kaolin activator as a positive control (TEG is included in the kaolin kit). When testing, add 20 ul of 0.2 mol / L calcium chloride solution and 340 uL of anticoagulated blood sample containing the sample to the test cup in sequence, and test according to the default settings of the instrument.

[0031] in conclusion: Figure 1 The thromboelastograms of different kaolins are shown in Figure 2. Figure 1As shown, kaolin will advance the start of coagulation time, significantly shorten the hemostasis time, and reduce the MA value of thrombus strength after coagulation, which poses a risk of rebleeding after hemostasis. In addition, kaolin K1 cannot achieve blood coagulation during the entire process. Acid-modified kaolin K2 reduces the blood coagulation time to a minimum of 1.3 minutes, and the MA value of thrombus strength is 11, which is relatively high. Composite modified kaolin reduces the R value of coagulation time to 1.8 minutes, and has strong thrombus strength, with an MA value of 29.1. Among several modified kaolins, calcination modification can greatly improve the coagulation performance of kaolin K1. Compared with K1, kaolin K5 calcined for 0.5 hours increases the start of coagulation time to 1.2 minutes, and the thrombus strength is also significantly improved.

[0032] Platelet activation experiments were performed on several types of kaolin: 30mL of peripheral blood specimens were collected by vacuum vein, and 3.2% sodium citrate was used for anticoagulation; the anticoagulated whole blood was centrifuged at 1000rpm for 10min, and the upper platelet-rich plasma (PRP) was taken and added to a new 15mL centrifuge tube for standby use. 25mg of sample was accurately weighed and added to a 1.5ml centrifuge tube, and 0.5mL of PRP was added, and stirred evenly with a gun tip. 0.5mL of PRP was added to an empty 1.5mL centrifuge tube as a blank control. Three replicates were set for both the sample and the control, and the samples were incubated at 37℃ for 1.5min. After the incubation, the PRP was centrifuged at 2000g for 10min, and the upper plasma was collected for testing according to the operating procedures provided by the ELISA kit.

[0033] in conclusion: Figure 2 The platelet activation amount of different kaolins is shown in Figure 2. Figure 2 As shown in the figure, the platelet activation effect of kaolin was tested by detecting the concentration of platelet characterization factor PF-4. Different kaolins have different degrees of promoting platelet activation. Whether platelets can be activated by the twelve-peptide sequence on fibrinogen (Fib) depends on the conformational state of Fib adsorbed on the surface of the material. Studies have shown that when the Fib molecule presents certain special conformations or orientations or when some special sites of Fib are exposed after being adsorbed on the surface, the Fib molecule will cause platelet adhesion and activation. Kaolin K1 itself has a weak effect on platelet activation, and calcination and acid modification can enhance the activation effect of kaolin on platelets.

[0034] The negative surface potential of kaolin is the key factor for kaolin to activate the intrinsic coagulation pathway. However, in the actual intrinsic coagulation process, the larger the surface negative potential, the better. Therefore, the Zeta potential of several kaolins in aqueous solution before and after modification and compounding was measured: 10 mg of kaolin was weighed into a 10 mL centrifuge tube, and then 10 mL of water was measured with a pipette to prepare a 1 wt‰ kaolin and water dispersion solution. The Zeta potential of different kaolins before and after modification was tested using a Malvern potential analyzer.

[0035] in conclusion: Figure 3 The surface potential size diagram of different kaolins; under natural conditions, kaolinite has a high negative charge on the edge surface of kaolinite due to a large number of broken bonds and dangling bonds. Under pH 7.4 conditions, the Zeta potentials of kaolin K1, K2, K3, K4, K5, and K6 are -29.53, -28.33, -12.83, -5.59, -8.64, and -8.32 mV, respectively. Kaolinite after calcination and acid modification is prone to agglomeration in water, and the Zeta potential is relatively reduced. Correspondingly, the comprehensive coagulation performance of kaolinite is improved to varying degrees. The surface Zeta potential of composite modified kaolinite K4 is reduced, and the thrombus strength MA value is greatly improved.

[0036] Figure 4 Scanning electron microscope images of different kaolins (from left to right: K1, K2, K3, K4, K5). Figure 5 XRD patterns of different kaolins; Figure 6 This is a refined quantitative analysis diagram of the composition structure of kaolin K1. Kaolin K1 has a morphology of closely packed regular hexagonal flakes, and individual particles have a larger particle size. Acid modification of K1 gave kaolin K2, which is relatively loosely packed and has a serrated structure on the edge. Kaolin K3 has a naturally formed mixed morphology of flakes and tubes, with disordered and relatively loose stacking. K4 has more tubular kaolin on its surface. K5 kaolin has a certain degree of warping on the edge surface.

[0037] When selecting kaolin ore, this application selected kaolin ore from Maoming, Guangdong. The reason is that the kaolin in Maoming has a high content of flake structure. After purification, it is mostly a regular hexagonal flake tightly packed morphology with good crystallinity. After calcination, the edge surface is warped, which is conducive to improving coagulation performance. The Suzhou kaolin ore presents a mixed morphology of flakes and tubes, and the tubular structure is not conducive to the improvement of coagulation performance. K4 is obtained by mixing K1 and K3 and ball milling, so that the tubular structure accumulates on the surface, which is not conducive to the performance of coagulation performance.

[0038] In summary, K5 and K6 prepared by the preparation method provided in this application have excellent comprehensive performance. Compared with K2, the preparation method is simpler and suitable for large-scale application.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing kaolin with excellent coagulation performance, characterized in that: include: The kaolin ore is crushed and then mixed with water to obtain a kaolin coarse mortar; The kaolin coarse sand slurry, sodium hydroxide and sodium hexametaphosphate are first mixed, and a spiral sand removal and a multi-stage cyclone are used to perform classification treatment and remove impurities to obtain a kaolin fine ore slurry; The kaolin fine slurry is mixed with sodium hexametaphosphate for a second time, and then subjected to magnetic separation and impurity removal and wet grinding treatment to obtain kaolin ultrafine slurry; Dehydrating and drying the ultrafine kaolin slurry to obtain purified kaolin; The purified kaolin is calcined to obtain the target kaolin.

2. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: The kaolin ore is taken from Maoming, Guangdong.

3. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: The solid content of the kaolin coarse sand mortar is 10-50wt%.

4. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: In the first mixing, the amount of sodium hydroxide used is 0.01-0.04wt% of the mass of the dry ore in the coarse kaolin mortar, and the amount of sodium hexametaphosphate used is 0.05-0.1wt% of the mass of the dry ore in the coarse kaolin mortar.

5. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: In the second mixing, the amount of the sodium hexametaphosphate is 0.05-0.1wt% of the mass of the dry ore in the kaolin fine slurry.

6. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: The fineness of the ultrafine kaolin slurry is that kaolinite with a particle size of less than 2 μm accounts for 90% or more of the dry weight of kaolin.

7. The method for preparing kaolin with excellent coagulation performance according to claim 1, characterized in that: The drying temperature is 65-80°C.

8. The method for preparing kaolin with excellent coagulation performance according to any one of claims 1 to 7, characterized in that: The heating rate of the calcination treatment is 4.5-5.5°C / min, the end temperature is 495-505°C, and the holding time is 0.45-1.05h.

9. A kaolin with excellent coagulation performance, characterized in that: The kaolin having excellent blood coagulation performance is prepared by the preparation method of any one of claims 1 to 8.

10. A hemostatic material, characterized in that: The invention comprises the kaolin with excellent blood coagulation performance as claimed in claim 9.

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