CN116023009B - Light glass microbead and preparation process thereof - Google Patents
Light glass microbead and preparation process thereof Download PDFInfo
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- CN116023009B CN116023009B CN202310126117.3A CN202310126117A CN116023009B CN 116023009 B CN116023009 B CN 116023009B CN 202310126117 A CN202310126117 A CN 202310126117A CN 116023009 B CN116023009 B CN 116023009B
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Abstract
A light glass microbead and a preparation process thereof belong to the technical field of light fillers. The method is characterized in that: the glass consists of glass, the particle size is 0.3 mm-1.0 mm, and bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads. The preparation method comprises the following steps: 1) Crushing the pure glass product with the impurities recovered and removed into glass powder, putting the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt at 1400-1500 ℃; 2) Filling inert gas into the glass melt from the bottom of the melting furnace, and simultaneously, rapidly stirring the glass melt to break the gas into bubbles in the glass melt; 3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; re-crushing the glass frit to glass frit; 4) And 3) preparing the glass powder obtained in the step 3) into glass beads by using a floating electric heating beading method. The light glass microbead is completely made of glass, and does not contain components such as foaming agent, binder and the like, so that the glass microbead has more stable structure and higher individual strength.
Description
Technical Field
A light glass microbead and a preparation process thereof belong to the technical field of light fillers.
Background
The current preparation technology of light/hollow glass microspheres is mature, and most of the microspheres are prepared by heating a foaming agent and ground glass powder/powder to a temperature at which glass begins to soften by flame. At the heating temperature, the blowing agent becomes or generates gas, causing the glass powder to expand and form light/hollow glass microspheres.
Wherein the blowing agent is typically a chemical blowing agent that releases a foaming gas at elevated temperatures by one or more of combustion, thermal decomposition, or gasification. May consist of, for example, elemental sulfur or compounds containing sulfur and oxygen, such as sulfates or sulfites. Useful sulfates include, in particular, zinc sulfate, sodium sulfate, potassium sulfate, lithium sulfate, rubidium sulfate, magnesium sulfate, calcium sulfate, barium sulfate, and lead sulfate. In addition to sulfur oxides, other foaming agents, such as CO, may be included 2 、O 2 Or N 2 . In particular O 2 Are often present as residues of sulfate ions. CO 2 May be produced from carbonates and bicarbonates or from carbonaceous compositions in glass melts under oxidizing conditions, and N 2 May be produced from nitrate or nitrite.
These blowing agents, while capable of foaming glass spheres/beads after use, form light/hollow glass microspheres. However, the bubbles formed by the foaming agent are large, so that the individual strength of the light/hollow glass microspheres is low, and the foaming agent can form nodes of metal oxides such as zinc, magnesium, calcium, barium or lead on the inner walls of the bubbles after the foaming agent is used for discharging gas, so that the individual strength of the light/hollow glass microspheres is reduced.
In addition, in the traditional preparation method of the light/hollow glass microspheres, because the bubbles are generated by expanding the gas generated by the foaming agent in the glass liquid beads, the gas is easy to directly break the glass spheres in the generation process, so that the glass spheres are irregular in shape or have pore channels communicated with the inside and the outside; when the glass ball with irregular shape is used as a filler, the roller lubrication effect of the glass ball can be greatly reduced, and the water absorption rate of the glass ball with the pore canal communicated with the inside and the outside can be greatly increased, so that the overall heat conductivity and density adjustment capability are affected.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a light glass microsphere with higher individual strength and a preparation process thereof.
The technical scheme adopted for solving the technical problems is as follows: the light glass microbead is characterized in that: the glass consists of glass, the particle size is 0.3 mm-1.0 mm, and bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads.
The light glass microbead is completely made of glass, and does not contain components such as foaming agent, binder and the like, so that the glass microbead has more stable structure and higher individual strength.
Preferably, the light glass beads have a bulk density of 240kg/m 3 ~280kg/m 3 And the cylinder pressure is 3.4-4.1 MPa. The light glass microbead has higher individual strength and can maintain higher strength with higher porosity.
The preparation process of the light glass beads comprises the following preparation steps:
1) Crushing the pure glass product with the impurities recovered and removed into glass powder, putting the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt at 1400-1500 ℃;
2) Filling inert gas into the glass melt from the bottom of the melting furnace, and simultaneously, rapidly stirring the glass melt to break the gas into bubbles in the glass melt;
3) Pouring the glass melt containing bubbles into a mold, cooling the glass melt into glass frit, and re-crushing the glass frit into glass powder;
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled to be 600-650 ℃, and the heating time is 30-50 s.
The invention provides a method for preparing light glass beads by twice melting, wherein glass is melted into glass melt with proper fluidity by high temperature for the first time, the fluidity of the glass melt at the moment ensures that bubbles of inert gas can float upwards, the bubbles are continuously broken in the floating process, the volume of the bubbles is gradually reduced, and the buoyancy of an individual is reduced along with the reduction of the volume of the bubbles. The fluidity of the glass melt is also required to be such that when the size of the bubbles reaches the size required by the present invention, the bubbles cannot emerge from the glass melt, thereby allowing the microbubbles to be eventually and uniformly dispersed in the glass melt. And cooling to obtain the light glass frit densely covered with bubbles. The glass frit is crushed into glass powder again, and the surface of the glass powder is softened by a floating electrothermal beading method, so that the light glass microbeads with smooth surfaces are obtained after cooling. The temperature and time are controlled in the beading process to only achieve the softening degree of the surface of the glass powder, so that bubbles in the glass beads are maintained, and the light property of the glass beads is maintained.
The preparation method of the light glass beads does not need to add auxiliary materials such as a foaming agent, a binding agent and the like, overcomes the problem that bubbles are easy to break due to internal foaming, and the obtained light glass beads have smooth surfaces and more regular shapes and show better roller lubrication effect when used as a filler. Meanwhile, the obtained light glass beads are higher in individual strength, and the displayed barrel pressure intensity is higher.
The preferred preparation process of the light glass beads comprises the step 1), wherein the particle size of the glass powder is smaller than 3mm. The particle size of the preferable glass powder can be melted rapidly at the melting temperature, and the porosity of the preferable glass powder can keep a proper amount of bubbles reserved uniformly everywhere after the melting, so that better fluidity can be achieved.
The preferable preparation process of the light glass beads comprises the step 1) that the temperature of the glass melt is 1420-1450 ℃. The molten glass having a preferable melting temperature is in a flowing state, and a molten glass having fine bubbles densely distributed therein can be obtained more efficiently.
Specifically, in the preparation process of the light glass beads, the inert gas adopts a multi-point filling mode, and at least four inert gas outlets are uniformly arranged at the bottom of the melting furnace. The inert gas is filled in a plurality of points, so that uniform dispersion of bubbles can be achieved more quickly, and the preparation efficiency is higher.
In the preparation process of the light glass beads, the total introducing rate of the inert gas is 0.3L/min-0.6L/min per kilogram of glass melt, the charging time of the inert gas is 5 min-10 min per kilogram of glass melt, and the inert gas is continuously and rapidly stirred for 1 h-2 h after charging. The preferable filling rate and filling amount of the inert gas are matched with the flowing state of the glass melt, so that more micro bubbles can be reserved in the glass melt after rapid stirring.
Specifically, in the preparation process of the light glass beads, the rapid stirring is carried out by adopting a flat stirring paddle to carry out shearing stirring, the stirring paddle is at least provided with an upper layer and a lower layer, the distance between the upper adjacent stirring paddle and the lower adjacent stirring paddle is not less than 30cm, and the distance from the plane of the lowest stirring paddle to the inert gas outlet is not more than 10cm. The design of the stirring paddle provided by the invention can more efficiently crush bubbles continuously.
In the preparation process of the light glass beads, the rotating speed of the stirring paddle for rapid stirring is 200-300 r/min. In order to break up the bubbles into micro-bubbles as much as possible, the paddles need to rotate rapidly, preferably at a rotational speed that meets the bubble breaking requirements of the present invention.
In the preferred preparation process of the light glass beads, the particle size of the glass powder in the step 3) is smaller than 1.5mm. When the glass frit is crushed, larger bubbles existing in the frit are used as the breaking points for connecting and crushing, so that the glass frit can be crushed more easily, and the required micro bubbles can be protected. When the particle size of the glass powder is crushed to be smaller than 1.5mm, the residual micro bubbles can meet the requirements of the light glass beads.
Compared with the prior art, the light glass microbead and the preparation process thereof have the beneficial effects that: the light glass microbead is completely made of glass, and does not contain components such as foaming agent, binder and the like, so that the glass microbead has more stable structure and higher individual strength. The preparation method of the invention is a twice melting method, and the light glass frit densely covered with bubbles is prepared by the first melting. And (3) crushing and softening the glass frit again, and obtaining the light glass microbeads with smooth surfaces by a floating electrothermal beading method. The preparation method of the light glass beads does not need to add auxiliary materials such as foaming agents, binders and the like, and the obtained light glass beads are smooth in surface and more regular in shape and show better roller lubrication effect when used as a filler. Meanwhile, the obtained light glass beads are higher in individual strength, and the displayed barrel pressure intensity is higher.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, of which example 1 is the best mode.
Example 1
1) And crushing the pure glass product with the recovered and purified impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt with the temperature of 1425 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.4L/min per kilogram of the glass melt, and the filling time of the nitrogen is 8min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of adjacent stirring paddles is 25cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 5cm, and the rotating speed of the stirring paddle is 250r/min. After the aeration is finished, the gas is continuously and rapidly stirred for 1h to be smashed into bubbles in the glass melt.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 620 ℃, and the heating time is 40s.
The particle diameter of the lightweight glass beads obtained in the example is 0.3 mm-1.0 mm, bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads, and the stacking density is 262kg/m 3 Barrel pressure intensity is 4.1MPa; the product yield was 98.4%.
Example 2
1) And crushing the pure glass product with the recovered impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt with the temperature of 1420 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.4L/min per kilogram of the glass melt, and the filling time of the nitrogen is 8min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of stirring paddles is 20cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 10cm, and the rotating speed of the stirring paddle is 220r/min. After the aeration is finished, the gas is continuously and rapidly stirred for 1.2 hours to be broken into bubbles in the glass melt.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 620 ℃, and the heating time is 45s.
The particle diameter of the lightweight glass beads obtained in the example is 0.3 mm-1.0 mm, bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads, and the stacking density is 257kg/m 3 Barrel pressure is 3.9MPa; the product yield was 98.1%.
Example 3
1) Crushing the pure glass product with the recovered and purified impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt with the temperature of 1450 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.5L/min per kilogram of the glass melt, and the filling time of the nitrogen is 6min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of stirring paddles is 30cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 8cm, and the rotating speed of the stirring paddle is 280r/min. After the aeration is finished, the gas is continuously and rapidly stirred for 1.5 hours to be broken into bubbles in the glass melt.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 630 ℃, and the heating time is 35s.
The particle diameter of the lightweight glass beads obtained in the example is 0.3 mm-1.0 mm, bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads, and the stacking density is 267kg/m 3 Barrel pressure intensity is 4.1MPa; the product yield was 98.3%.
Example 4
1) And crushing the pure glass product with the recovered impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt at 1500 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.6L/min per kilogram of the glass melt, and the filling time of the nitrogen is 5min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of stirring paddles is 25cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 10cm, and the rotating speed of the stirring paddle is 300r/min. After the aeration is finished, the gas is continuously and rapidly stirred for 1h to be smashed into bubbles in the glass melt.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 600 ℃, and the heating time is 50s.
The particle diameter of the lightweight glass beads obtained in the example is 0.3 mm-1.0 mm, bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads, and the stacking density is 241kg/m 3 Barrel pressure is 3.4MPa; the product yield was 97.8%.
Example 5
1) And crushing the pure glass product with the recovered impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt at 1400 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.3L/min per kilogram of the glass melt, and the filling time of the nitrogen is 10min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of stirring paddles is 30cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 10cm, and the rotating speed of the stirring paddle is 200r/min. After the aeration is finished, the gas is continuously and rapidly stirred for 2 hours to be smashed into bubbles in the glass melt.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled to be 650 ℃, and the heating time is 30s.
The particle diameter of the lightweight glass beads obtained in the example is 0.3 mm-1.0 mm, the glass beads are densely distributed with bubbles with the diameter of 0.01 mm-0.2 mm, and the stacking density is 278kg/m 3 Barrel pressure is 3.8MPa; the product yield was 98.1%。
Comparative example 1
1) And crushing the pure glass product with the recovered and purified impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt with the temperature of 1200 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 0.4L/min per kilogram of the glass melt, and the filling time of the nitrogen is 8min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of adjacent stirring paddles is 25cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 5cm, and the rotating speed of the stirring paddle is 250r/min. Stirring is continued for 1h after the aeration is finished.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 620 ℃, and the heating time is 40s.
The particle size of the lightweight glass beads obtained in this example is 0.3 mm-1.0 mm, and the bulk density is 1124kg/m 3 。
Comparative example 2
1) And crushing the pure glass product with the recovered and purified impurities into glass powder with the particle size of 1.5 mm-3 mm, placing the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt with the temperature of 1425 ℃.
2) Filling nitrogen into the glass melt from the bottom of the melting furnace, wherein the nitrogen adopts a multi-point filling mode, four nitrogen outlets are uniformly arranged at the bottom of the melting furnace, the total filling rate of the nitrogen is 1L/min per kilogram of the glass melt, and the filling time of the nitrogen is 8min per kilogram of the glass melt; and simultaneously, rapidly stirring the glass melt, wherein the rapid stirring is realized by adopting a flat stirring paddle to perform shearing stirring, the stirring paddle is provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of adjacent stirring paddles is 25cm, the distance from the plane of the lowest layer of stirring paddle to a nitrogen outlet is 5cm, and the rotating speed of the stirring paddle is 80r/min. Stirring is continued for 1h after the aeration is finished.
3) Pouring the glass melt containing bubbles into a mold and cooling the glass melt into glass frit; and re-crushing the glass frit into glass powder with the particle size of 0.5 mm-1.5 mm.
4) And 3) preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled at 620 ℃, and the heating time is 40s.
The particle size of the lightweight glass beads obtained in this example is 0.3mm to 1.0mm, and the bulk density is 873kg/m 3 。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (3)
1. A light glass microbead, which is characterized in that: the glass consists of glass, wherein the particle size is 0.3 mm-1.0 mm, and bubbles with the diameter of 0.01 mm-0.2 mm are densely distributed in the glass beads; bulk density of 240kg/m 3 ~280kg/m 3 The cylinder pressure is 3.4-4.1 MPa; the preparation method comprises the following steps:
1) Crushing the pure glass product with the impurities recovered and removed into glass powder, putting the glass powder into a melting furnace for melting, and continuously heating the glass powder into glass melt at 1400-1500 ℃; 2) Filling inert gas into the glass melt from the bottom of the melting furnace, and simultaneously, rapidly stirring the glass melt to break the gas into bubbles in the glass melt;
3) Pouring the glass melt containing bubbles into a mold, cooling the glass melt into glass frit, and re-crushing the glass frit into glass powder;
4) Preparing glass beads from the glass powder obtained in the step 3) by using a floating electric heating beading method, wherein the temperature of a heating pipe in the floating electric heating beading method is controlled to be 600-650 ℃, and the heating time is 30-50 s;
the inert gas adopts a multi-point filling mode, and at least four outlets of the inert gas are uniformly arranged at the bottom of the melting furnace;
the total introducing rate of the inert gas is 0.3L/min-0.6L/min per kilogram of glass melt, the inert gas is filled for 5 min-10 min per kilogram of glass melt, and the inert gas is continuously and rapidly stirred for 1 h-2 h after the inert gas is filled;
the rapid stirring is shearing stirring by adopting a flat stirring paddle, wherein the stirring paddle is at least provided with an upper layer and a lower layer, the distance between the upper layer and the lower layer of adjacent stirring paddles is not less than 30cm, and the distance from the plane of the lowest layer of stirring paddle to an inert gas outlet is not more than 10cm;
the rotating speed of the stirring paddle for rapid stirring is 200 r/min-300 r/min;
the particle size of the glass powder in the step 3) is less than 1.5mm;
the inert gas is N 2 。
2. A lightweight glass microbead as in claim 1, wherein: the particle size of the glass powder in the step 1) is less than 3mm.
3. A lightweight glass microbead as in claim 1, wherein: the temperature of the glass melt in the step 1) is 1420-1450 ℃.
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| CN115044140A (en) * | 2022-07-01 | 2022-09-13 | 安徽卡洛塑业科技有限公司 | Preparation process of environment-friendly flame-retardant polystyrene material |
| CN115093122A (en) * | 2022-07-15 | 2022-09-23 | 中钢集团马鞍山矿山研究总院股份有限公司 | Preparation method of high-strength and low-density hollow glass microspheres |
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| CN116023009A (en) | 2023-04-28 |
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Denomination of invention: A lightweight glass microbead and its preparation process Effective date of registration: 20230726 Granted publication date: 20230623 Pledgee: Zibo Zichuan sub branch of China Construction Bank Co.,Ltd. Pledgor: Zibo Kangjian technology Ceramics Co.,Ltd. Registration number: Y2023980049943 |