CN113493323B - Cementing liquid for microbial mineralization and preparation method thereof - Google Patents
Cementing liquid for microbial mineralization and preparation method thereof Download PDFInfo
- Publication number
- CN113493323B CN113493323B CN202110806479.8A CN202110806479A CN113493323B CN 113493323 B CN113493323 B CN 113493323B CN 202110806479 A CN202110806479 A CN 202110806479A CN 113493323 B CN113493323 B CN 113493323B
- Authority
- CN
- China
- Prior art keywords
- cementing
- powder
- liquid
- improves
- cementing liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D3/00—Improving or preserving soil or rock, e.g. preserving permafrost soil
- E02D3/12—Consolidating by placing solidifying or pore-filling substances in the soil
Landscapes
- Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Paleontology (AREA)
- Civil Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Agronomy & Crop Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a cementing liquid for microbial mineralization and a preparation method thereof, and the cementing liquid contains calcium chloride, urea, sodium chloride, soybean peptone and fresh oysterShell powder, jackfruit seed powder, longan leaf powder, glucosyl stevioside, cocoamidopropyl betaine and water. The cementing liquid is applied to cementing of cohesive soil, can inhibit the instant biochemical reaction generated during the mixing of the bacterial liquid cementing liquid to produce flocculation, provides a controllable window period for the effective cementing of MICP, ensures that the mixed liquid is uniformly distributed in a certain depth range of the soil body, and improves CaCO at 24h 3 The chemical conversion rate obviously improves the cementing effect, improves the stress of the soil sample injection end after cementing, obviously improves the saturated structural strength of the surface layer of the cemented soil body, improves the cementing uniformity and improves the erosion resistance of the slope.
Description
Technical Field
The invention relates to the field of cementing liquids, in particular to a cementing liquid for microbial mineralization and a preparation method thereof.
Background
The MICP (microbial induced calcium carbonate deposition) technology has the characteristics of simple construction, environmental friendliness and the like. Due to poor permeability of cohesive soil, cells of the microorganism cannot migrate within pores that are too small in size. Adding cementing liquid into the MICP technology bacteria liquid to produce CaCO for bacteria 3 The crystals provide a source of urea and calcium (CaCl) 2 ). The problems of rapid flocculation, pore blockage and the like easily occur after the bacteria liquid and the cementing liquid are contacted in the traditional single-phase cementing process, so that the mixed liquid of the bacteria liquid and the cementing liquid is difficult to be uniformly distributed in a certain depth range of a soil body, the cementing effect is poor, and the application of the MICP technology to cohesive soil is not facilitated.
Disclosure of Invention
In view of the above, the present invention provides a cementing liquid for microbial mineralization and a preparation method thereof, which solve the above technical problems.
The technical scheme of the invention is realized as follows:
a cementing liquid for microorganism mineralization contains 55-111g of calcium chloride, 30-60g of urea, 0.4-0.5g of sodium chloride, 1.2-1.8g of soybean peptone, 0.5-0.8g of oyster shell powder, 0.8-1.2g of jackfruit seed powder, 1.3-1.5g of longan leaf powder, 0.8-1g of glucose-based stevioside, 0.5-1.0g of cocamidopropyl betaine and the balance of water per liter.
Further, each liter contains 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soybean peptone, 0.7g of oyster shell powder, 1.0g of jack fruit seed powder, 1.4g of longan leaf powder, 0.9g of glucose-based stevioside, 0.8g of cocamidopropyl betaine and the balance of water.
Furthermore, the mesh number of the oyster shell powder is 30-50 meshes.
Furthermore, the mesh number of the jackfruit seed powder is 80-120 meshes.
Furthermore, the mesh number of the longan leaf powder is 60-80 meshes.
The preparation method of the cementing liquid comprises the steps of adding calcium chloride into water, adding oyster shell powder, jackfruit seed powder and longan leaf powder, and stirring at 1800-2000 rpm for 0.6-0.8 h; adding sodium chloride, soybean peptone and glucose-based stevioside, and stirring at 1200-1300 rpm for 1.2-1.5 h; and finally, adding urea and cocamidopropyl betaine, and adjusting the pH value to 4.5-5.5 to prepare the target cementing liquid.
Further, the jackfruit seed powder is prepared by pre-freezing, drying, crushing and sieving jackfruit seeds. Furthermore, the pre-freezing condition is that the jack fruit seeds are pre-frozen for 2 to 3 hours at a temperature of between 15 ℃ below zero and 20 ℃ below zero.
Further, the temperature in the stirring process is controlled to be 5-10 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts calcium chloride, urea, sodium chloride, soybean peptone, oyster shell powder, jackfruit seed powder and longan leaf powder, adds glucose-based stevioside and cocamidopropyl betaine, prefers a certain proportion to prepare a cementing liquid, is applied to cohesive soil cementation, can inhibit instant biochemical reaction generated when a bacterial liquid cementing liquid is mixed to produce flocculation, delays flocculation occurrence time, solves the problems of rapid flocculation, pore blockage and the like after the bacterial liquid and the cementing liquid are contacted in the traditional single-phase cementing process, provides a controllable window period for effective cementation of MICP, enables the mixed liquid to be uniformly distributed in a soil body within a certain depth range, and improves CaCO 24h 3 The chemical conversion rate obviously improves the cementing effect, improves the stress of the soil sample injection end after cementing, obviously improves the saturated structural strength of the surface layer of the cemented soil body, improves the cementing uniformity and improves the erosion resistance of the slope.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
A cementing liquid for microbial mineralization contains 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soybean peptone, 0.7g of oyster shell powder, 1.0g of jackfruit seed powder, 1.4g of longan leaf powder, 0.9g of glucose-based stevioside, 0.8g of cocamidopropyl betaine and the balance of water per liter.
The preparation method of the cementing liquid comprises the following steps:
(1) raw material treatment
Grinding raw oyster shells, and sieving with a 30-mesh sieve to obtain the raw oyster shell powder.
Taking longan leaves, crushing, and sieving by a 60-mesh sieve to obtain longan leaf powder.
Taking jackfruit seeds, pre-freezing for 2 hours at-15 ℃, drying, crushing, and sieving with a 80-mesh sieve to obtain the jackfruit seed powder.
(2) Preparation of the cementing fluid
Respectively taking the raw materials according to the weight, firstly adding calcium chloride into water, adding oyster shell powder, jackfruit seed powder and longan leaf powder, and mechanically stirring for 0.6h at the rotating speed of 2000 rpm; then adding sodium chloride, soybean peptone and glucose-based stevioside, and mechanically stirring for 1.2h at the rotating speed of 1300 rpm; and finally, adding urea and cocamidopropyl betaine, adjusting the pH value to 4.5, and controlling the temperature to be 5-10 ℃ in the stirring process to prepare the target cementing liquid.
Example 2
A cementing liquid for microbial mineralization contains 55g of calcium chloride, 30g of urea, 0.4g of sodium chloride, 1.2g of soybean peptone, 0.5g of oyster shell powder, 1.2g of jackfruit seed powder, 1.5g of longan leaf powder, 1g of glucose-based stevioside, 0.5g of cocamidopropyl betaine and the balance of water per liter. The preparation procedure was in accordance with example 1.
Example 3
A cementing liquid for microbial mineralization contains 111g of calcium chloride, 60g of urea, 0.5g of sodium chloride, 1.8g of soybean peptone, 0.8g of oyster shell powder, 1.2g of jackfruit seed powder, 1.3g of longan leaf powder, 0.8g of glucose-based stevioside, 1.0g of cocamidopropyl betaine and the balance of water per liter. The preparation procedure was in accordance with example 1.
Example 4
A cementing liquid for microbial mineralization contains 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soybean peptone, 0.7g of oyster shell powder, 1.0g of jackfruit seed powder, 1.4g of longan leaf powder, 0.9g of glucose-based stevioside, 0.8g of cocamidopropyl betaine and the balance of water per liter.
The preparation method of the cementing liquid comprises the following steps:
(1) raw material treatment
Grinding the fresh oyster shell, and sieving with a 50-mesh sieve to obtain the fresh oyster shell powder.
Pulverizing folium longan, and sieving with 80 mesh sieve to obtain longan leaf powder.
Taking jackfruit seeds, pre-freezing for 3 hours at the temperature of 20 ℃ below zero, drying, crushing, and sieving with a 120-mesh sieve to obtain the jackfruit seed powder.
(2) Preparation of the cementing fluid
Respectively taking the raw materials according to the weight, firstly adding calcium chloride into water, adding oyster shell powder, jackfruit seed powder and longan leaf powder, and mechanically stirring for 0.8h at the rotation speed of 1800 rpm; then adding sodium chloride, soybean peptone and glucose-based stevioside, and mechanically stirring for 1.5h at the rotating speed of 1200 rpm; and finally, adding urea and cocoanut oil amide propyl betaine, adjusting the pH value to be 5.5, and controlling the temperature to be 5-10 ℃ in the stirring process to prepare the target cementing liquid.
Comparative example 1
And (3) mixing 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride and 1.5g of soybean peptone, and adding water to a constant volume of 1L to obtain the cementing liquid.
Comparative example 2
The formula of the cementing liquid is as follows: each liter of the fertilizer contains 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soyapeptone, 0.1g of oyster shell powder, 0.5g of jackfruit seed powder, 0.5g of longan leaf powder, 0.5g of glucose-based stevioside, 0.1g of cocamidopropyl betaine and the balance of water. The preparation procedure was in accordance with example 1.
Comparative example 3
The formula of the cementing liquid is as follows: each liter of the fertilizer contains 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soyapeptone, 1.0g of oyster shell powder, 1.5g of jack fruit seed powder, 2.0g of longan leaf powder, 1.5g of glucose-based stevioside, 1.5g of cocamidopropyl betaine and the balance of water. The preparation procedure was in accordance with example 1.
Comparative example 4
The main difference from example 1 is that the seeds of jack fruit were selected without pre-freezing. Taking jackfruit seeds, directly crushing the jackfruit seeds, and then sieving the jackfruit seeds with a 80-mesh sieve to obtain the jackfruit seed powder.
Comparative example 5
The main difference from the embodiment 1 is that the temperature during the stirring process is not controlled to be 5-10 ℃, and the temperature during the stirring process is 25-30 ℃.
Test examples
(1) Selection of cohesive soil
This experiment adopted Hainan red clay as the object of modification.
(2) Strain selection
Sporosarcina pasteurii was selected for this test. The strain is stored in a refrigerator at 4 ℃ by plate coating, and is periodically activated to keep the activity. The formulation of the medium (250mL) used in this experiment was Tris base 3.9g, yeast extract 5.0g, (NH) 4 ) 2 SO 4 2.5 g. Taking activated bacteria liquid (OD) for multiple rounds 600 About 1.2), inoculated into 250mL of medium with a pipette at 10 mL. Culturing the bacteria at 30 deg.C and 150rpm for 24h with constant temperature shaking incubator, and measuring OD of the bacteria liquid with spectrophotometer 600 (Unit OD) 600 The value corresponds to about 8.6X 10 per ml 7 Individual bacteria) value of about 1.2. The urease activity of the bacterial solution used in this test was about 3.1mM urea.min －1 。
(3) Cement to window period and CaCO 3 Influence of chemical conversion
Study of the examples and the production of CaCO by bacteria in cement solutions with different ratios 3 The influence of the crystal efficiency is realized by mixing the cementing liquid and the bacterial liquid (sporosarcina pasteurii) (the mixing volume ratio is 30 ml: 30ml), and the influence of the cementing liquid on the chemical conversion rate in the MICP reaction process is researched in a liquid environment.
In the test, the cementing solution of the examples and the comparative examples was mixed with the bacterial solution having a pH of 5.0, and the mixture was left to stand for 24 hours, centrifuged, filtered, and the precipitate was washed and dried. And (5) observing the flocculation condition in the standing process. And by formation of CaCO 3 Mass conversion of the crystals to chemical conversion.
CaCO 3 Chemical conversion means conversion to CaCO 3 Precipitated Ca 2+ The amount of Ca in the solution before the reaction 2+ The amount of (c).
(4) Preparation of soil sample
Firstly, drying and crushing red clay under the original state, sieving the red clay by a 2mm sieve, weighing 750.0g of air-dried soil (the initial water content is 3.7 percent), filling the air-dried soil into a cylindrical mould (the inner diameter is 10.0cm, the height is 8.0cm) in a layering manner, wherein the final height of a soil sample is 6cm, and the dry density is 1.5g cm －3 . The bottom of the mould is perforated for draining water, and meanwhile, double layers of gauze are padded to prevent soil particles from flowing out. And adding water to saturate the sample, naturally drying the sample, repeating 5 rounds, and simulating the natural dry-wet cycle so as to enable the initial structural state of the soil sample to be close to the natural surface soil. The deformation and mechanical properties of the remolded soil sample prepared indoors can basically reach a relatively stable state after 3-5 times of dry-wet circulation. According to the above-described operation, the sample can be repeatedly prepared.
(5) Preparation of cemented soil samples
And (3) adopting a single-phase cementing process, reducing the pH value of a bacterial liquid (sporosarcina pasteurii) to 5.0 by utilizing a 1.0M HCl solution, mixing with the cementing liquid, quickly spraying the mixed solution onto the surface of the sample, allowing the sample to naturally infiltrate, standing for one week, and naturally air-drying at room temperature to obtain the cemented soil sample.
Remarking: the spraying treatment time of each sample is 10-15 min, the sample is in an unsaturated state before being treated, and effusion is not formed on the surface of the sample all the time in the spraying treatment process.
(6) Structural strength test of cemented soil sample
The soil samples treated by different cementing liquids of examples and comparative examples are subjected to a penetration test by using an ultramicro penetrometer SMP-1, and the structural strength of the soil body is reflected by the end resistance of a probe in the process of penetrating into the soil body. Before the penetration, the bottom of the mold is opened to allow water to penetrate from bottom to top, so as to saturate the sample. Different points (more than 2cm apart) are selected for each sample to carry out 3 times of penetration tests, the penetration depth is 20mm each time, and then the results are averaged.
The results show that the cementing fluids of examples 1-4 of the invention can inhibit the instant biochemical reaction during the mixing of the bacteria liquid cementing fluids to produce flocculation, delay the flocculation occurrence time, provide a controllable window period for the effective cementation of MICP, and improve CaCO at 24h 3 The chemical conversion rate improves the stress of the injection end of the cemented soil sample, obviously improves the saturated structural strength of the surface layer of the cemented soil body, and improves the uniformity of cementation.
Comparative example 1 does not adopt the components of the cementing liquid formula, and comparative examples 2 to 3 do not adopt the formula proportion of the cementing liquid, so that the effect is obviously reduced, the flocculation time is fast, the chemical conversion rate of CaCO3 is reduced, the average value of the stress of the soil sample penetration end is reduced after 24 hours, and the cementing is not uniform.
In the comparative example 4, the jack fruit seeds are not pre-frozen, the temperature is not controlled to be 5-10 ℃ in the stirring process of the comparative example 5, the temperature is controlled to be 25-30 ℃ in the stirring process, and CaCO is used 3 The chemical conversion rate is reduced, and the average value of the stress at the penetrating end of the soil sample is also reduced after 24 hours.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A cementing liquid for microbial mineralization is characterized in that each liter contains 55-111g of calcium chloride, 30-60g of urea, 0.4-0.5g of sodium chloride, 1.2-1.8g of soyapeptone, 0.5-0.8g of oyster shell powder, 0.8-1.2g of jackfruit seed powder, 1.3-1.5g of longan leaf powder, 0.8-1g of glucose-based stevioside, 0.5-1.0g of cocamidopropyl betaine and the balance of water;
the preparation method of the cementing liquid comprises the following steps: firstly, adding calcium chloride into water, adding oyster shell powder, jackfruit seed powder and longan leaf powder, and stirring at 1800-2000 rpm for 0.6-0.8 h; adding sodium chloride, soybean peptone and glucose-based stevioside, and stirring at 1200-1300 rpm for 1.2-1.5 h; finally, adding urea and cocamidopropyl betaine, and adjusting the pH value to 4.5-5.5 to prepare a target cementing solution;
the jackfruit seed powder is prepared by prefreezing, drying, crushing and sieving jackfruit seeds, wherein the prefreezing condition is that the jackfruit seeds are prefreezed for 2-3 hours at a temperature of-15 to-20 ℃;
the temperature in the stirring process is controlled to be 5-10 ℃.
2. The microbial mineralization cementing liquid of claim 1, wherein the cementing liquid comprises 111g of calcium chloride, 60g of urea, 0.45g of sodium chloride, 1.5g of soybean peptone, 0.7g of fresh oyster shell powder, 1.0g of jackfruit seed powder, 1.4g of longan leaf powder, 0.9g of glucose-based stevioside, 0.8g of cocamidopropyl betaine and the balance of water per liter.
3. The microbial mineralization cementing liquid of claim 1, wherein the oyster shell powder has a mesh size of 30-50 mesh.
4. The microbial mineralization cementing liquid of claim 1, wherein the mesh size of the jackfruit seed powder is 80-120 mesh.
5. The microbial mineralization cementing liquid of claim 1, wherein the longan leaf powder has a mesh size of 60-80 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110806479.8A CN113493323B (en) | 2021-07-16 | 2021-07-16 | Cementing liquid for microbial mineralization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110806479.8A CN113493323B (en) | 2021-07-16 | 2021-07-16 | Cementing liquid for microbial mineralization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113493323A CN113493323A (en) | 2021-10-12 |
| CN113493323B true CN113493323B (en) | 2022-08-16 |
Family
ID=77996172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110806479.8A Active CN113493323B (en) | 2021-07-16 | 2021-07-16 | Cementing liquid for microbial mineralization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113493323B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8182604B2 (en) * | 2004-12-20 | 2012-05-22 | Murdoch University | Microbial biocementation |
| CN106857761B (en) * | 2017-03-16 | 2020-10-16 | 海南省农垦科学院集团有限公司 | Jackfruit seed whole-powder cookie and preparation method thereof |
| CN108049409A (en) * | 2017-11-14 | 2018-05-18 | 河海大学 | A kind of method of the solid soil of microbes synthase inhibitor slip casing by pressure |
| CN108718586A (en) * | 2018-06-28 | 2018-11-02 | 广东工业大学 | A method of sand being cured by microorganism induction precipitation of calcium carbonate using regeneration calcium source |
| CN111501733A (en) * | 2020-04-21 | 2020-08-07 | 南京大学 | Method for solidifying soil body by utilizing in-situ microorganisms cultured in excitation mode |
| CN111441337B (en) * | 2020-04-30 | 2022-03-18 | 华中科技大学 | Microorganism induced mineralization reinforcement soil body grouting method introducing urease inhibitor |
-
2021
- 2021-07-16 CN CN202110806479.8A patent/CN113493323B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113493323A (en) | 2021-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Factors affecting the performance of microbial-induced carbonate precipitation (MICP) treated soil: a review | |
| Zhang et al. | Aragonite formation induced by open cultures of microbial consortia to heal cracks in concrete: Insights into healing mechanisms and crystal polymorphs | |
| Tang et al. | Application of microbial precipitation in self-healing concrete: A review on the protection strategies for bacteria | |
| Qian et al. | Cementation of sand grains based on carbonate precipitation induced by microorganism | |
| CN106082767B (en) | A kind of string loads the self-repairing cement-base material of microorganism | |
| RU2119923C1 (en) | Method of producing quick-hydrating velanic resin and cement composition based on this resin | |
| Rong et al. | Characterization of microbe cementitious materials | |
| Behzadipour et al. | Biochar-assisted bio-cementation of a sand using native bacteria | |
| CN111827258A (en) | Method for reinforcing soil body by combining organic matters with plant urease | |
| Zhao et al. | Effect of activated carbon on microbial-induced calcium carbonate precipitation of sand | |
| Kim et al. | Engineered bioclogging in coarse sands by using fermentation-based bacterial biopolymer formation | |
| CN109650686A (en) | A method of sludge curing agent and its reinforcing mud based on microorganism | |
| CN113493323B (en) | Cementing liquid for microbial mineralization and preparation method thereof | |
| CA2965072A1 (en) | Process for obtaining a mineral cimentitious substance | |
| ZHANG et al. | Advances in soil cementation by biologically induced calcium carbonate precipitation | |
| CN101874464B (en) | Long-acting powdery attapulgite mud for inserting fresh flowers and production method thereof | |
| CN109650685A (en) | The method of sludge curing agent and its reinforcing mud based on microorganism and flyash | |
| Rong et al. | Cementation of loose sand particles based on bio-cement | |
| RU2133239C1 (en) | Method of producing addition for concrete mixture | |
| CN107353163A (en) | A kind of agricultural water-loss reducer and preparation method thereof | |
| Zheng et al. | Experimental study on MICP aqueous solution under the action of different organic substrates | |
| Rong et al. | Influence of magnesium additive on mechanical properties of microbe cementitious materials | |
| Lo Bianco et al. | BULM technique for increase of the bearing capacity in the pavement layers subjected to biological treatment | |
| CN109593808B (en) | Daptomycin fermentation medium and preparation method thereof | |
| Wang et al. | In situ restoration of the surface defects on cement-based materials by bacteria mineralization with spraying method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |