A shell crushing device for preparing hydroxyapatite

Abstract

The present invention provides a shell crushing device for preparing hydroxyapatite, and relates to the technical field of hydroxyapatite preparation. The device comprises a frame and a crushing mechanism, a cleaning mechanism and a grinding mechanism installed on the frame. The crushing mechanism is used for the first-level coarse crushing of shells. The crushing mechanism comprises a crushing shell, a feeding hopper and a discharging hopper. The cleaning mechanism is used for the cleaning, soaking and hot air drying of shells. The cleaning mechanism comprises a cleaning shell, a cleaning inner cylinder unit, a hot air drying unit and a sewage discharge unit. The grinding mechanism is used for the second-level fine crushing of shells. The grinding mechanism comprises a grinding frame and a grinding shell. A screen is provided inside the grinding shell, and a material receiving box is provided below the grinding mechanism. The device can automatically clean, soak, dry, grind and filter shells, thereby improving the efficiency of obtaining shell powder and the purity of the obtained shell powder.

Description

Technical Field

[0001] The invention relates to the technical field of hydroxyapatite preparation, in particular to a shell crushing device for preparing hydroxyapatite. Background Art

[0002] Hydroxyapatite (HAp) has good biocompatibility, bioactivity, chemical stability and solid alkalinity, and is widely used in many fields such as biomedicine, tissue engineering, drug controlled release, catalysis, materials, etc. The development and research of high-purity hydroxyapatite is of great significance.

[0003] At present, the common methods for preparing hydroxyapatite on the market include using soluble calcium salts, calcium-containing substances or biomass calcium sources, such as using calcium nitrate as a calcium source to prepare hydroxyapatite, and using coral reef stones, shells, and calcium glass as calcium sources to prepare hydroxyapatite.

[0004] A large number of discarded shells are produced in coastal areas. The accumulation of a large number of shells has caused environmental pollution and prevented the effective use of resources. The use of shells to prepare hydroxyapatite not only alleviates environmental problems, but also makes full use of waste resources and turns waste into treasure. However, the discarded shells themselves carry a large amount of mud or foreign matter, and often emit peculiar smells. In order to obtain high-purity shell powder, the shell powder needs to be repeatedly cleaned and soaked in hydrochloric acid. For example, under laboratory conditions, the shells are soaked in tap water overnight and then taken out. After being soaked in hydrochloric acid, impurities on the surface and in the gaps are removed with a brush. After naturally drying, the shells are crushed with a grinder. There is a lack of a shell crushing device for obtaining shell powder efficiently, saving time and effort, and a method for preparing hydroxyapatite based on this device. Under industrial production conditions, there is also a lack of a shell crushing device for automatically cleaning, soaking, drying, grinding, and filtering shells, and a method for preparing hydroxyapatite based on this device. Summary of the invention

[0005] The purpose of the present invention is to provide a shell crushing device for preparing hydroxyapatite, which can automatically clean, soak, dry, grind and filter shells, thereby improving the efficiency of obtaining shell powder and the purity of the obtained shell powder. At the same time, a method for preparing hydroxyapatite based on this device is provided to obtain a high-purity hydroxyapatite product.

[0006] To this end, the technical solution of the present invention is a shell crushing device for preparing hydroxyapatite, which includes a frame and a crushing mechanism, a cleaning mechanism and a grinding mechanism installed on the frame, the crushing mechanism is used for the first-level coarse crushing of the shells, the crushing mechanism includes a crushing shell, a feeding hopper and a discharging hopper, the interior of the crushing shell is provided with an active crushing tool and a passive crushing tool, the active crushing tool is connected with a crushing motor and a reducer, the cleaning mechanism is used for cleaning, soaking and hot air drying of the shells, the cleaning mechanism includes a cleaning shell, a cleaning inner drum unit, a hot air drying unit and a sewage discharge unit, a soaking liquid barrel and a cleaning liquid barrel are provided above the cleaning shell, a soaking liquid recovery barrel and a cleaning liquid recovery barrel are provided below the cleaning shell, the grinding mechanism is used for the second-level fine crushing of the shells, the grinding mechanism includes a grinding frame and a grinding shell, the interior of the grinding shell is provided with a screen, the screen divides the interior of the grinding shell into a grinding chamber and a discharge chamber, the interior of the grinding chamber is provided with an active grinding wheel and a passive grinding wheel, and a receiving box is provided below the grinding mechanism.

[0007] Furthermore, an inclined surface and a sewage outlet are provided on the bottom plate of the cleaning shell.

[0008] Furthermore, the inner drum cleaning unit includes an inner drum body, an inner drum motor, a switch retaining ring, a switch motor, an upper support body and a lower support body.

[0009] Furthermore, cleaning holes are arranged on the outer ring surface of the inner cylinder, and the cleaning holes are arranged in multiple rows and distributed in a ring shape on the inner cylinder.

[0010] Furthermore, a plurality of inner cylinder material openings are provided in the middle of the outer annular surface of the inner cylinder, and the inner cylinder material openings are used for feeding and discharging materials of the inner cylinder.

[0011] Furthermore, a plurality of transverse shifting plates are provided in the middle of the inner annular surface of the inner cylinder, the transverse shifting plates are evenly spaced in a ring shape, two spiral shifting plates are symmetrically provided on both sides of the transverse shifting plates, and the spiral shifting plates are spirally distributed on the inner annular surface of the inner cylinder.

[0012] Furthermore, a switch retaining ring is provided outside the inner cylinder material opening of the outer ring surface of the inner cylinder body.

[0013] Furthermore, the hot air drying unit includes a heater and a blower located outside the cleaning shell, and an air intake duct located inside the cleaning shell, the air intake duct is provided with multiple air intake nozzles, the ends of the air intake nozzles point to the inner cylinder, and an exhaust duct is provided on one side of the cleaning shell.

[0014] Furthermore, the sewage discharge unit includes a sewage trough, a left sewage pipe and a right sewage pipe. The sewage trough is installed at the sewage outlet of the cleaning shell. The left sewage pipe and the right sewage pipe are both provided with electric valves. A sewage discharge screw is provided inside the sewage trough, and one side of the sewage discharge screw is transmission-connected to the sewage discharge motor.

[0015] Furthermore, the active grinding wheel is provided with inner active blades and outer active blades, the inner active blades are in the shape of a right-angled trapezoid, and the outer active blades are in the shape of a rectangle. The passive grinding wheel is provided with passive blades, and the passive blades are distributed in a circular array around the center of the passive grinding wheel.

[0016] The beneficial effect of the present invention is that a shell crushing device for preparing hydroxyapatite includes a frame, a crushing mechanism, a cleaning mechanism and a grinding mechanism. The crushing mechanism performs the first-level coarse crushing on the shells. After the shells are coarsely crushed by the crushing mechanism, they enter the cleaning mechanism.

[0017] The cleaning mechanism cleans, soaks and hot-air dries the shells. After coarse crushing, the mud attached to the shells is easier to clean off. After coarse crushing, the shells are more exposed to the wind due to a larger area and avoid mutual occlusion caused by the original shape of the shells, which makes it easier to use hot air drying. The coarsely crushed shells are soaked in an acidic solution to remove foreign matter and odors on the shells. Clean water can be used to rinse off the mud or residual soaking liquid on the shells. The cleaned shells are dried by hot air.

[0018] The cleaned shells enter the grinding mechanism from the cleaning mechanism. The grinding mechanism is used for the second-level fine crushing of the shells. The ground shell powder is filtered through a screen to finally obtain shell powder. This realizes the automatic cleaning, soaking, drying, grinding and filtering of the shells, improves the production efficiency, improves the purity of the shell powder, and provides a basis for obtaining high-purity hydroxyapatite products.

[0019] A method for preparing hydroxyapatite, the method is based on the above-mentioned shell crushing device for preparing hydroxyapatite, weighing the shell powder obtained by the device, dissolving it with acetic acid, filtering and retaining the filtrate, adding distilled water to the filtrate and stirring it, slowly dropping a phosphoric acid solution into the above solution to obtain a first reaction solution, adding sodium citrate and keeping stirring to obtain a second reaction solution, transferring the second reaction solution to a constant temperature water bath and heating it in water, adding urea, stirring and dissolving it, and standing it until a white precipitate is precipitated, washing the above white precipitate with pure water and anhydrous ethanol in turn and drying it to obtain a high-purity hydroxyapatite product. After experimental verification, the prepared hydroxyapatite sample was tested by X-ray diffractometer. The results showed that the sample obtained by this method can correspond to the standard peaks of the standard spectrum of hydroxyapatite XRD (PDF#09-0432), such as the diffraction peaks of 2θ at 25.88°, 31.77°, 32.20°, 34.05°, 46.71°, 49.47° and 53.14°, which correspond to HAP (002), (211), (112), (202), (222), (213) and (004) crystal planes, respectively. No other impurity peaks were found, indicating that the obtained sample is pure hydroxyapatite, free of other impurities and of high purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic diagram of the overall structure of the present invention;

[0021] Figure 2 yes Figure 1 A schematic diagram of the structure from another angle;

[0022] Figure 3 yes Figure 1 The main view of

[0023] Figure 4 It is a structural diagram of the crushing mechanism;

[0024] Figure 5 yes Figure 4 The main view of

[0025] Figure 6 It is a structural diagram of the cleaning mechanism;

[0026] Figure 7 yes Figure 6 A cross-sectional view of

[0027] Figure 8 is a structural schematic diagram of a hot air drying unit;

[0028] Fig. 9 It is a schematic diagram of the structure of the sewage discharge unit;

[0029] Fig.10 It is a structural schematic diagram of the inner cylinder cleaning unit;

[0030] Fig.11 yes Fig.10 A cross-sectional view of

[0031] Fig.12 yes Fig.10 A cross-sectional view from another angle;

[0032] Fig.13 It is a schematic diagram of the structure of the switch retaining ring;

[0033] Fig.14 is a schematic diagram of the structure of the lower support body;

[0034] Fig.15 is a cross-sectional view of a cleaning shell;

[0035] Fig.16 It is a structural schematic diagram of the grinding mechanism;

[0036] Fig.17 yes Fig.16 A cross-sectional view of

[0037] Fig.18 It is a schematic diagram of the structure of the grinding wheel set;

[0038] Fig.19 It is a schematic diagram of the structure of the passive grinding wheel;

[0039] Fig. 20 It is a schematic diagram of the structure of the active grinding wheel;

[0040] Fig.21 is a scanning electron microscope image of hydroxyapatite;

[0041] Fig. 22 is the X-ray diffraction spectrum of hydroxyapatite;

[0042] Fig.23 It is the nitrogen adsorption-desorption curve of hydroxyapatite.

[0043] Explanation of symbols in the figure:

[0044] 1. Frame; 2. Crushing mechanism; 21. Crushing shell; 211. Active crushing tool; 212. Passive crushing tool; 213. Crushing baffle; 22. Feeding hopper; 23. Discharging hopper; 24. Crushing motor; 25. Speed ​​reducer; 3. Cleaning mechanism; 31. Cleaning shell; 311. Inclined surface; 312. Drain port; 32. Cleaning inner cylinder unit; 321. Inner cylinder; 3211. Cleaning hole; 3212. Inner cylinder material port; 3213. Horizontal paddle; 3214. Spiral paddle; 322. Inner cylinder motor; 323. Switch baffle ring; 3231. Ring rack; 3232. Switch material port; 324. Switch motor; 325. Upper support; 326. Lower support; 3261. Discharging channel; 32 62. Lower support plate; 33. Hot air drying unit; 331. Air intake duct; 3311. Air intake nozzle; 332. Heater; 333. Blower; 34. Exhaust duct; 35. Sewage discharge unit; 351. Sewage discharge trough; 352. Left sewage discharge pipe; 353. Right sewage discharge pipe; 354. Sewage discharge screw; 355. Sewage discharge motor; 4. Grinding mechanism; 41. Grinding frame; 42. Grinding shell; 43. Screen; 44. Active grinding wheel; 441. Inner active blade; 442. Outer active blade; 45. Passive grinding wheel; 451. Passive blade; 46. Pulley; 47. Grinding motor; 48. Belt; 5. Soaking liquid barrel; 6. Soaking liquid recovery barrel; 7. Cleaning liquid barrel; 8. Cleaning liquid recovery barrel; 9. Material receiving box. DETAILED DESCRIPTION

[0045] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] like Figure 1-Figure 20 As shown, a shell crushing device for preparing hydroxyapatite of the present invention comprises a frame 1 and a crushing mechanism 2, a cleaning mechanism 3 and a grinding mechanism 4 installed on the frame 1, wherein the crushing mechanism 2 is located above the cleaning mechanism 3, and the grinding mechanism 4 is located below the cleaning mechanism 3. After being roughly crushed by the crushing mechanism 2, the shell enters the cleaning mechanism 3, and the cleaning mechanism 3 cleans, soaks and hot-air dries the shell. The cleaned shell enters the grinding mechanism 4, and the grinding mechanism 4 finely crushes the shell. The shell is the outer shell of a mollusk, such as one or more of mussel shells, oyster shells, pearl shells, mother-of-pearl shells, and river clam shells.

[0047] Specifically, the crushing mechanism 2 is used for the first-level coarse crushing of the shells to facilitate the cleaning and drying of the shells. After the coarse crushing, the mud attached to the shells is easier to clean off. After the coarse crushing, the shells are more exposed to the wind because the area, and avoid mutual occlusion caused by the original shape of the shells, it is also more convenient to use hot air drying. The cleaning mechanism 3 is used for cleaning, soaking and hot air drying of the shells. The shells after coarse crushing are soaked in an acidic solution to remove foreign matter and odor on the shells. The mud on the shells can be rinsed off with clean water. The cleaned shells are dried by hot air. The grinding mechanism 4 is used for the second-level fine crushing of the shells to finally obtain shell powder.

[0048] The crushing mechanism 2 includes a crushing shell 21, a feeding hopper 22 and a discharging hopper 23. An active crushing tool 211 and a passive crushing tool 212 are arranged inside the crushing shell 21. Crushing baffles 213 are arranged on both sides of the active crushing tool 211 and the passive crushing tool 212. One end of the active crushing tool 211 and the passive crushing tool 212 are connected to each other through gears. A crushing motor 24 and a reducer 25 are connected to the active crushing tool 211. The crushing motor 24 drives the active crushing tool 211 and the passive crushing tool 212 to perform the first level of coarse crushing on the shells. The particle size of the coarsely crushed shells can be adjusted by replacing different tools.

[0049] The cleaning mechanism 3 includes a cleaning shell 31, a cleaning inner cylinder unit 32, a hot air drying unit 33 and a sewage discharge unit 35. An inclined surface 311 and a sewage discharge port 312 are provided on the bottom plate of the cleaning shell 31. When the liquid in the cleaning shell 31 is discharged, the liquid is collected to the sewage discharge port 312 through the inclined surface 311. The cleaning inner cylinder unit 32 is installed in the middle of the cleaning shell 31, and both ends of the cleaning inner cylinder unit 32 are rotatably connected to the cleaning shell 31 through bearings.

[0050] The cleaning inner cylinder unit 32 includes an inner cylinder body 321, an inner cylinder motor 322, a switch baffle ring 323, a switch motor 324, an upper support body 325 and a lower support body 326. The inner cylinder motor 322 is transmission-connected to the inner cylinder body 321. The inner cylinder motor 322 is used to drive the inner cylinder body 321 to rotate forward or reversely. Cleaning holes 3211 are provided on the outer ring surface of the inner cylinder body 321. The cleaning holes 3211 are circular, square, diamond or other regular shapes. The cleaning holes 3211 are in multiple rows and distributed in a ring on the inner cylinder body 321. The cleaning holes 3211 are mainly used to isolate coarsely crushed shells and facilitate the cleaning liquid and soaking liquid to enter the inner cylinder body 321.

[0051] A plurality of inner cylinder material openings 3212 are provided in the middle of the outer ring surface of the inner cylinder body 321 , and the inner cylinder material openings 3212 are used for feeding and discharging the inner cylinder body 321 . The inner cylinder material openings 3212 are evenly spaced in a ring shape. Preferably, the number of the inner cylinder material openings 3212 is 4, and the 4 inner cylinder material openings 3212 are evenly spaced on the inner cylinder material opening 3212 .

[0052] A plurality of transverse plates 3213 are provided in the middle of the inner annular surface of the inner cylinder 321. The transverse plates 3213 are parallel to the central axis of the inner cylinder 321. The transverse plates 3213 are evenly spaced and distributed in a ring shape. The number of the transverse plates 3213 is less than or equal to the number of the inner cylinder material openings 3212. There is at least one inner cylinder material opening 3212 between two transverse plates 3213. For example, when the number of the inner cylinder material openings 3212 is 4 and the number of the transverse plates 3213 is also 4, each transverse plate 3213 is located in the middle position of two adjacent inner cylinder material openings 3212.

[0053] Two spiral paddles 3214 are symmetrically arranged on both sides of the transverse paddle 3213. The spiral paddles 3214 are spirally distributed on the inner ring surface of the inner cylinder 321. The design of the transverse paddle 3213 plus the spiral paddle 3214 is for the thorough cleaning of the shells and the discharge of the shells after cleaning. For example, when the inner cylinder 321 rotates forward, the transverse paddle 3213 and the spiral paddle 3214 drive the shells to turn upside down in the inner cylinder 321. At the same time, under the action of the spiral inclined surface of the spiral paddle 3214, the shells gather to the middle part of the inner cylinder 321. When the inner cylinder 321 rotates reversely, the transverse paddle 3213 and the spiral paddle 3214 drive The shells flip up and down in the inner cylinder 321, and under the action of the spiral inclined surface of the spiral plate 3214, the shells gather at the two ends of the inner cylinder 321. Therefore, when the shells are cleaned, when the inner cylinder 321 rotates forward and reverse, the shells flip up and down in the inner cylinder 321, and alternately flip and gather toward the middle and both ends of the inner cylinder 321, so that the shells are cleaned more cleanly; after the shells are cleaned, the inner cylinder 321 rotates forward, and the shells gather toward the middle of the inner cylinder 321 in the inner cylinder 321, and are discharged from an inner cylinder material port 3212 at the lowest point, thereby realizing the discharge of the shells after cleaning.

[0054] A switch baffle ring 323 is provided on the outside of the inner cylinder material opening 3212 of the outer ring surface of the inner cylinder body 321, and the switch baffle ring 323 is rotationally connected to the inner cylinder body 321. An annular rack 3231 is provided on one side of the outer ring surface of the switch baffle ring 323, and a switch material opening 3232 is provided on the inner side of the annular rack 3231. The annular rack 3231 is connected to the gear transmission of the switch motor 324, and the switch motor 324 is fixedly connected to the cleaning shell 31. The switch motor 324 drives the switch baffle ring 323 to rotate through the annular rack 3231.

[0055] A lower support body 326 is provided directly below the switch retaining ring 323, and a discharge channel 3261 is provided inside the lower support body 326. A lower support plate 3262 is provided at the upper end of the lower support body 326. The lower support plate 3262 is an arc-shaped plate, and an arc-shaped slide groove is provided inside the lower support plate 3262. Similarly, an upper support body 325 is provided directly above the switch retaining ring 323, and a feed channel is provided inside the upper support body 325. An upper support plate is provided at the lower end of the upper support body 325. When the switch motor 324 drives the switch retaining ring 323 to rotate When the switch material port 3232 is connected to the feed channel of the upper support body 325, and at the same time the switch material port 3232 is connected to the inner cylinder material port 3212, the coarsely crushed shells enter the inner cylinder 321 of the cleaning mechanism 3 from the crushing mechanism 2; the switch baffle ring 323 continues to rotate, and when the switch material port 3232 is connected to the unloading channel of the lower support body 326, and at the same time the switch material port 3232 is connected to the inner cylinder material port 3212, the cleaned shells enter the grinding mechanism 4 from the inner cylinder 321 of the cleaning mechanism 3.

[0056] The unique design of the above cleaning mechanism 3 solves the problem of loading and unloading shells in the middle of the inner cylinder 321, and takes into account the functions of cleaning flipping and unloading flipping, realizing both the flipping function of shell cleaning and the flipping function of shell unloading.

[0057] The hot air drying unit 33 includes a heater 332 and a blower 333 located outside the cleaning shell 31, and an air intake duct 331 located inside the cleaning shell 31. The air intake duct 331 is U-shaped and has two single air intake pipes. The air intake duct 331 is provided with multiple air intake nozzles 3311, and the ends of the air intake nozzles 3311 point to the inner cylinder 321. An exhaust duct 34 is provided on one side of the cleaning shell 31. After the shells are cleaned, they are dried by hot air through the hot air drying unit 33, and the dried shells enter the grinding mechanism 4.

[0058] The sewage unit 35 includes a sewage trough 351, a left sewage pipe 352 and a right sewage pipe 353. The sewage trough 351 is installed at the sewage outlet 312 of the cleaning shell 31. The left sewage pipe 352 and the right sewage pipe 353 are both provided with electric valves. A sewage screw 354 is provided inside the sewage trough 351. One side of the sewage screw 354 is transmission-connected to the sewage motor 355. The left sewage pipe 352 and the right sewage pipe 353 are respectively used for discharging the soaking liquid and the cleaning liquid. The sewage screw 354 is used to remove sludge and impurities in the cleaning liquid.

[0059] A soaking liquid barrel 5 and a cleaning liquid barrel 7 are provided above the cleaning shell 31. The soaking liquid barrel 5 and the cleaning liquid barrel 7 are respectively connected to the interior of the cleaning shell 31 through pipes. An electric valve for switch control is also provided on the pipe. A soaking liquid recovery barrel 6 is provided below the left sewage pipe 352, and a cleaning liquid recovery barrel 8 is provided below the right sewage pipe 353.

[0060] The soaking liquid in the soaking liquid barrel 5 is an acidic solution, such as a 0.1 mol / L hydrochloric acid solution. In order to ensure that the interior of the cleaning mechanism 3, the soaking liquid barrel 5 and the soaking liquid recovery barrel 6 is not corroded by the acidic solution, an acid-proof coating, such as a polytetrafluoroethylene coating, is provided therein.

[0061] The grinding mechanism 4 includes a grinding frame 41 and a grinding shell 42. A screen 43 is provided inside the grinding shell 42. The screen 43 divides the inside of the grinding shell 42 into a grinding chamber and a discharge chamber. An active grinding wheel 44 and a passive grinding wheel 45 are provided inside the grinding chamber. The active grinding wheel 44 is provided with an inner active blade 441 and an outer active blade 442. The number of the inner active blades 441 is multiple, and the shape of the inner active blades 441 is a right-angled trapezoid. The inner active blades 441 are evenly distributed around the center of the active grinding wheel 44. The number of the outer active blades 442 is multiple, and the outer active blades 442 are located outside the inner active blades 441. The outer active blades 44 2 is arranged in a circular array around the center of the active grinding wheel 44, the outer active blade 442 is in a rectangular shape, and an angle is set between the plane where the outer active blade 442 is located and the plane where the inner active blade 441 is located. The passive grinding wheel 45 is provided with a passive blade 451, and the passive blade 451 is arranged in a circular array around the center of the passive grinding wheel 45, and the middle section of the passive blade 451 is parallel to a section of the passive grinding wheel 45, and the inner side and outer side of the passive blade 451 are both provided with concave surfaces. After the active grinding wheel 44 and the passive grinding wheel 45 are installed, the passive blade 451 is located between the inner active blade 441 and the outer active blade 442. A pulley 46 is provided on the outer side of the active grinding wheel 44, and a grinding motor 47 is provided below the pulley 46. The pulley 46 and the grinding motor 47 are connected by a belt 48. A material receiving box 9 is provided below the grinding mechanism 4, and the material receiving box 9 is used for recovering shell powder.

[0062] The shells that have been coarsely crushed, cleaned, soaked and dried in sequence enter the grinding mechanism 4, and then are sheared and ground at high speed by the active grinding wheel 44 and the passive grinding wheel 45 inside the grinding chamber. The ground shell powder is filtered through the screen 43 and falls into the receiving box 9 below the grinding mechanism 4. The sieve hole size of the screen 43 is 80 to 100 meshes.

[0063] The present invention provides a shell crushing device for preparing hydroxyapatite, which includes a frame 1, a crushing mechanism 2, a cleaning mechanism 3 and a grinding mechanism 4. Shells are added to the crushing mechanism 2 through a feeding hopper 22, and a crushing motor 24 drives an active crushing tool 211 and a passive crushing tool 212 to perform a first-level coarse crushing of the shells. The particle size of the coarsely crushed shells can be adjusted by replacing different tools. After the shells are coarsely crushed by the crushing mechanism 2, when the switch material port 3232 is connected to the feed channel of the upper support body 325, the coarsely crushed shells enter the cleaning mechanism 3 through the discharge hopper 23 and the upper support body 325.

[0064] The cleaning mechanism 3 cleans, soaks and hot-air dries the shells. The coarsely crushed shells are sequentially cleaned, soaked and hot-air dried, or the coarsely crushed shells are sequentially cleaned, soaked, cleaned a second time and hot-air dried. After coarse crushing, the mud attached to the shells is easier to clean off. After coarse crushing, the area of ​​the shells exposed to the wind becomes larger and mutual occlusion caused by the original shape of the shells is avoided, which makes it more convenient to use hot air drying. The coarsely crushed shells are soaked in an acidic solution to remove foreign matter and odor on the shells. The mud or residual soaking liquid on the shells can be rinsed off with clean water. The cleaned shells are dried by hot air.

[0065] When the switch material port 3232 is connected to the unloading channel of the lower support body 326, and at the same time the switch material port 3232 is connected to the inner cylinder material port 3212, the cleaned shells enter the grinding mechanism 4 from the inner cylinder 321 of the cleaning mechanism 3. The grinding mechanism 4 is used for the second-level fine crushing of the shells. The coarsely crushed shells are sheared and ground into shell powder by the active grinding wheel 44 and the passive grinding wheel 45 inside the grinding chamber at high speed. The ground shell powder is filtered through the screen 43 and falls into the receiving box 9 below the grinding mechanism 4 to finally obtain shell powder.

[0066] The present invention provides a method for preparing hydroxyapatite, which adopts the above shell crushing device for preparing hydroxyapatite, and specifically comprises the following steps:

[0067] 1. Add the shells into the crushing mechanism 2 through the feeding hopper 22. The crushing motor 24 drives the active crushing tool 211 and the passive crushing tool 212 to perform the first-level coarse crushing of the shells. The particle size of the coarsely crushed shells can be adjusted by replacing different tools.

[0068] 2. After being roughly crushed by the crushing mechanism 2, the shells fall into the discharge hopper 23.

[0069] 3. The switch motor 324 of the cleaning mechanism 3 drives the switch baffle ring 323 to rotate. When the switch material port 3232 of the switch baffle ring 323 is connected with the feed channel of the upper support body 325, and the switch material port 3232 is connected with the inner cylinder material port 3212, the coarsely crushed shells enter the inner cylinder 321 of the cleaning mechanism 3 from the discharge hopper 23 of the crushing mechanism 2.

[0070] 4. The cleaning mechanism 3 cleans, soaks and hot-air dries the coarsely crushed shells. The coarsely crushed shells are sequentially cleaned, soaked and hot-air dried, or the coarsely crushed shells are sequentially cleaned, soaked, cleaned twice and hot-air dried.

[0071] The specific cleaning process is as follows: the electric valve of the cleaning liquid barrel 7 is opened, and the cleaning liquid flows into the interior of the cleaning shell 31 through the pipeline, and the cleaning liquid completely submerges the inner cylinder 321; when the inner cylinder motor 322 drives the inner cylinder 321 to rotate forward, the horizontal paddle plate 3213 and the spiral paddle plate 3214 drive the shells to turn up and down in the inner cylinder 321. At the same time, under the action of the spiral inclined surface of the spiral paddle plate 3214, the shells gather to the middle part of the inner cylinder 321. When the inner cylinder motor 322 drives the inner cylinder 321 to rotate reversely, the horizontal paddle plate 3213 and the spiral paddle plate 3214 drive the shells to turn up and down in the inner cylinder 321. 1, and at the same time, under the action of the spiral inclined surface of the spiral plate 3214, the shells gather at the two ends of the inner cylinder 321, and the shells alternately move. That is, during the shell cleaning process, the inner cylinder 321 performs alternating forward and reverse rotations. While the shells are turned upside down in the inner cylinder 321, they are alternately turned and gathered toward the middle and both ends of the inner cylinder 321, so that the shells are cleaned more cleanly; the electric valve on the right sewage pipe 353 is opened, and the sewage motor 355 drives the sewage screw 354 to rotate, and the cleaning liquid and the sludge in the cleaning liquid are simultaneously discharged into the cleaning liquid recovery bucket 7. The cleaning liquid is pure water or pure water with detergent added.

[0072] The specific process of soaking is as follows: the electric valve of the soaking liquid barrel 5 is opened, and the soaking liquid flows into the interior of the cleaning shell 31 through the pipeline, and the soaking liquid completely submerges the inner cylinder 321; after the shell is soaked in the inner cylinder 321 for a certain period of time, the electric valve on the left sewage pipe 352 is opened to discharge the soaking liquid into the soaking liquid recovery barrel 6. The soaking liquid is an acidic solution, such as a 0.1 mol / L hydrochloric acid solution. The shell is soaked in the inner cylinder 321 for 30-40 minutes.

[0073] During the soaking process of the shell in the inner cylinder 321, the inner cylinder 321 may also perform alternating forward rotation and reverse rotation. The time interval of the alternating motion of the inner cylinder 321 during the soaking process is less than or equal to the time interval during the cleaning process.

[0074] The specific process of hot air drying is as follows: the blower 333 sends air into the heater 332 for heating, the heated air is sent into the interior of the cleaning shell 31 through the air intake pipe 331, and the heated air is then passed through multiple air intake nozzles 3311 on the air intake pipe 331 to perform hot air drying on the shells inside the inner cylinder 321, and the exhaust gas is discharged through the exhaust pipe 34.

[0075] In order to improve the efficiency of hot air drying, during the hot air drying process, the inner cylinder 321 can also perform alternating forward rotation and reverse rotation. The time interval of the alternating movement of the inner cylinder 321 during the hot air drying process is less than or equal to the time interval during the cleaning process.

[0076] 5. After the shells are cleaned, the inner cylinder 321 rotates forward, and the shells gather inside the inner cylinder 321 toward the middle of the inner cylinder 321 and are discharged from an inner cylinder material port 3212 at the lowest point, thereby achieving the discharge of the shells after cleaning.

[0077] The switch motor 324 of the cleaning mechanism 3 drives the switch baffle ring 323 to rotate. When the switch material port 3232 is connected to the unloading channel of the lower support body 326, and the switch material port 3232 is connected to the inner cylinder material port 3212, the cleaned shells enter the grinding mechanism 4 from the inner cylinder 321 of the cleaning mechanism 3.

[0078] 6. The grinding motor 47 of the grinding mechanism 4 drives the active grinding wheel 44 to rotate at high speed. The coarsely crushed shells are sheared and ground into shell powder at high speed by the active grinding wheel 44 and the passive grinding wheel 45 inside the grinding chamber. The ground shell powder is filtered through the screen 43 and falls into the receiving box 9 below the grinding mechanism 4 to finally obtain shell powder.

[0079] 7. Weigh the above shell powder and dissolve it with 10% acetic acid. Carbon dioxide gas will be produced during the dissolution process. The dissolution reaction time is 2-6 hours. After the reaction is complete, filter it and discard the residue to keep only the filtrate.

[0080] 8. Add distilled water to the filtrate, turn on the stirring device for stirring, and slowly drop 0.12 mol / L phosphoric acid solution into the above solution to obtain a first reaction solution.

[0081] 9. Add sodium citrate (solid powder) to the first reaction solution and keep stirring for 30-50 minutes to obtain a second reaction solution.

[0082] 10. Transfer the second reaction solution to a constant temperature water bath at 80-90 degrees and heat it in water. Add urea, stir to dissolve, and let it stand for 4-6 hours until a white precipitate is formed.

[0083] 11. The white precipitate is washed with purified water and anhydrous ethanol in turn and then dried to obtain a hydroxyapatite product.

[0084] Specifically, under laboratory conditions, weigh 1.0g of shell powder, dissolve it with 40ml of acetic acid, the concentration of acetic acid is 10%, filter it after the reaction is completed for 4 hours, discard the residue and keep only the filtrate. Add distilled water to the filtrate to a total volume of 100ml. Turn on the magnetic stirrer for stirring. Slowly add 100ml of 0.12mol / L phosphoric acid solution to the above solution. After the addition is completed, add 0.04612g of sodium citrate and keep stirring for 40min. Transfer the above solution to a constant temperature water bath at a temperature of 85 degrees and heat it in water. Add 24g of urea, stir and dissolve it, and let it stand for 5 hours until a white precipitate is precipitated. The above precipitate is washed with pure water and anhydrous ethanol in turn and then dried to obtain a hydroxyapatite product.

[0085] like Figure 21-23 As shown, Fig.21 The present invention discloses a shell crushing device for preparing hydroxyapatite and a method for preparing hydroxyapatite, and a scanning electron microscope image (magnified 100,000 times) of the prepared hydroxyapatite.

[0086] Fig. 22 The X-ray diffraction spectrum of the prepared hydroxyapatite is shown in Figure 1. After the prepared hydroxyapatite sample is tested by an X-ray diffractometer, the results show that the sample obtained by this method can correspond to the standard peaks of the standard spectrum of hydroxyapatite XRD (PDF#09-0432) one by one, such as the diffraction peaks of 2θ at 25.88°, 31.77°, 32.20°, 34.05°, 46.71°, 49.47° and 53.14° respectively corresponding to the HAP (002), (211), (112), (202), (222), (213) and (004) crystal planes. No other impurity peaks are found, indicating that the obtained sample is pure hydroxyapatite, free of other impurities and of high purity.

[0087] The specific surface area and pore structure of HAP were analyzed by nitrogen adsorption measurement, such as Fig.23 This is the N2 adsorption-desorption isotherm of HAP. It is not difficult to find that HAP has an obvious hysteresis loop, which is caused by the capillary condensation phenomenon in the pores. It belongs to the IV type adsorption curve, indicating that the synthesized material is a mesoporous structure. The pore size of HAP is mostly distributed in the range of 10-40nm. The data show that the specific surface area of ​​HAP is as high as 39.68m 2 ·g -1 , pore volume is 0.303cm 3 ·g -1 , the average pore size is 25.86nm.

[0088] However, the above description is only a specific embodiment of the present invention and should not be used to limit the scope of implementation of the present invention. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the scope of protection of the present invention should still fall within the scope covered by the claims of the present invention.

Claims

1. A shell crushing device for preparing hydroxyapatite, characterized in that: The invention comprises a frame and a crushing mechanism, a cleaning mechanism and a grinding mechanism installed on the frame, wherein the crushing mechanism is used for the first-stage coarse crushing of shells, the crushing mechanism comprises a crushing shell, a feeding hopper and a discharging hopper, an active crushing tool and a passive crushing tool are arranged inside the crushing shell, a crushing motor and a reducer are connected to the active crushing tool, the cleaning mechanism is used for cleaning, soaking and hot air drying of shells, the cleaning mechanism comprises a cleaning shell, a cleaning inner cylinder unit, a hot air drying unit and a sewage discharge unit, the cleaning shell is used for holding cleaning liquid and soaking liquid, the cleaning inner cylinder unit comprises an inner cylinder body, an inner cylinder motor, a switch retaining ring, a switch motor, an upper support body and a lower support body, the inner cylinder motor is used for driving the inner cylinder body to rotate forward or reversely, a plurality of inner cylinder material ports for feeding and discharging are arranged in the middle of the outer annular surface of the inner cylinder body, and the inner cylinder material on the outer annular surface of the inner cylinder body is provided with a plurality of inner cylinder material ports for feeding and discharging. A switch baffle ring is provided on the outside of the mouth, and the switch baffle ring is rotatably connected to the inner cylinder body. A lower support body is provided directly below the switch baffle ring, and a unloading channel is provided inside the lower support body. An upper support body is provided directly above the switch baffle ring, and a feeding channel is provided inside the upper support body. The feeding channel connects the inner cylinder body of the crushing mechanism and the cleaning mechanism, and the unloading channel connects the inner cylinder body of the cleaning mechanism and the grinding mechanism. A soaking liquid barrel and a cleaning liquid barrel are provided above the cleaning shell body, and a soaking liquid recovery barrel and a cleaning liquid recovery barrel are provided below the cleaning shell body. The grinding mechanism is used for the second-level fine crushing of shells. The grinding mechanism includes a grinding frame and a grinding shell body. A screen is provided inside the grinding shell body, and the screen divides the interior of the grinding shell into a grinding chamber and a discharge chamber. An active grinding wheel and a passive grinding wheel are provided inside the grinding chamber, and a receiving box is provided below the grinding mechanism.

2. A shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: An inclined surface and a sewage outlet are arranged on the bottom plate of the cleaning shell.

3. A shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: The outer ring surface of the inner cylinder is provided with cleaning holes, and the cleaning holes are arranged in multiple rows and annularly distributed on the inner cylinder.

4. A shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: A plurality of transverse shifting plates are arranged in the middle of the inner annular surface of the inner cylinder, and the transverse shifting plates are evenly spaced in a ring shape. Two spiral shifting plates are symmetrically arranged on both sides of the transverse shifting plates, and the spiral shifting plates are spirally distributed on the inner annular surface of the inner cylinder.

5. The shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: The hot air drying unit includes a heater and a blower located outside the cleaning shell, and an air intake duct located inside the cleaning shell. The air intake duct is provided with a plurality of air intake nozzles, the ends of the air intake nozzles point to the inner cylinder, and an exhaust pipe is provided on one side of the cleaning shell.

6. A shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: The sewage discharge unit includes a sewage trough, a left sewage pipe and a right sewage pipe. The sewage trough is installed at the sewage outlet of the cleaning shell. The left sewage pipe and the right sewage pipe are both provided with electric valves. A sewage discharge screw is provided inside the sewage trough, and one side of the sewage discharge screw is transmission-connected to the sewage discharge motor.

7. A shell crushing device for preparing hydroxyapatite according to claim 1, characterized in that: The active grinding wheel is provided with inner active blades and outer active blades, the inner active blades are in the shape of a right-angled trapezoid, the outer active blades are in the shape of a rectangle, and the passive grinding wheel is provided with passive blades, which are distributed in a circular array around the center of the passive grinding wheel.

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