CN109224900B - Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof - Google Patents
Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof Download PDFInfo
- Publication number
- CN109224900B CN109224900B CN201811173921.2A CN201811173921A CN109224900B CN 109224900 B CN109224900 B CN 109224900B CN 201811173921 A CN201811173921 A CN 201811173921A CN 109224900 B CN109224900 B CN 109224900B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- fatty acid
- acid ester
- sucrose fatty
- enrichment
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/70—Pre-treatment of the materials to be mixed
- B01F23/701—Coating solid materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/51—Methods thereof
- B01F23/511—Methods thereof characterised by the composition of the liquids or solids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a graphene oxide sucrose fatty acid ester enrichment and a preparation method thereof, and relates to the technical field of chemical product production, wherein the enrichment is a mixture obtained by taking sucrose fatty acid ester as a coating agent or a precipitator and coating or coprecipitating graphene oxide from water, and the preparation method comprises the steps of adding a sucrose fatty acid ester solution into a graphene oxide dispersion liquid, uniformly stirring and mixing, adjusting the pH value of a material, separating the sucrose fatty acid ester and the graphene oxide from a water phase in a coating or coprecipitation manner, and obtaining the product by centrifugal sedimentation; compared with the prior art, the preparation method comprises the steps of adding a sucrose fatty acid ester solution into a graphene oxide dispersion liquid, uniformly stirring, uniformly coating or co-precipitating graphene oxide by the sucrose fatty acid ester to obtain a pasty graphene oxide sucrose fatty acid ester concentrate, and drying to obtain a powdery graphene oxide sucrose fatty acid ester concentrate, so that the problems that powdery graphene oxide is easy to agglomerate and is not easy to disperse are well solved.
Description
Technical Field
The invention relates to the technical field of chemical product production, in particular to an enriched graphene oxide sucrose fatty acid ester and a preparation method thereof.
Background
The graphene oxide is an oxide of graphene, is single-layer or multi-layer graphite oxide formed by stripping graphite oxide, contains a plurality of oxygen-containing groups on a sheet layer, has high specific surface energy, good hydrophilicity and mechanical properties, has good dispersion stability in water and most polar organic solvents, and can improve the mechanical properties of products when being applied to the fields of high polymer materials, coatings, papermaking and the like. Graphene oxide is commonly available in the market as a powder and an aqueous dispersion.
The powdered graphene oxide can be obtained by removing moisture through freeze drying and a conventional heating mode, but the powdered graphene oxide is easy to agglomerate and is difficult to disperse in the process of mixing the powdered graphene oxide with other materials, especially the powdered graphene oxide obtained by the heating mode.
The content of graphene oxide in a commercially available graphene oxide aqueous dispersion is usually 0.5-10mg/ml, and the graphene oxide aqueous dispersion needs to remove more water when dispersed in other materials due to too low concentration, which causes inconvenience in operation.
Disclosure of Invention
The invention aims to solve the problem of providing an enriched graphene oxide sucrose fatty acid ester and a preparation method thereof, which can solve the problems of agglomeration and inconvenient use of the existing graphene oxide.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the graphene oxide sucrose fatty acid ester concentrate is a mixture obtained by coating or coprecipitating graphene oxide in water by using sucrose fatty acid ester as a coating agent or a precipitator.
The preparation method of the enriched graphene oxide sucrose fatty acid ester in the technical scheme comprises the following steps: adding a sucrose fatty acid ester solution into the graphene oxide dispersion liquid, uniformly mixing by stirring, adjusting the pH value of the material, separating the sucrose fatty acid ester and the graphene oxide from a water phase in a coating or coprecipitation mode, and obtaining a pasty graphene oxide sucrose fatty acid ester enrichment through centrifugal sedimentation.
Further: drying and grinding the slurry graphene oxide sucrose fatty acid ester enrichment to obtain powder graphene oxide sucrose fatty acid ester enrichment.
Further: the HLB value of the added sucrose fatty acid ester is 7-16; the mass ratio of the graphene oxide to the sucrose fatty acid ester is 1: 0.01-10 in terms of dry matter, and the pH value of the material is 0.5-4.
The above drying method is conventional vacuum drying.
The sucrose fatty acid ester is a nonionic surfactant, and is also a coating agent, a plasticizer and an antistatic agent when applied to plastics. The sucrose fatty acid ester is a mixture of monoester, diester, triester and polyester generated by esterification of sucrose and fatty acid, according to different ester proportions, the sucrose fatty acid ester has a wide HLB value, the HLB value of the sucrose fatty acid ester is between 1 and 16, and the sucrose fatty acid ester has the functions of emulsification, dispersion, stabilization, defoaming, starch aging resistance, viscosity regulation, crystallization inhibition and the like, can be dispersed or dissolved in water, can be dissolved in chloroform, can be easily dissolved in hot ethanol, propylene glycol and the like, is stable under weak acid and weak base, and can be easily hydrolyzed under strong acid and strong base. The molecular structure of the starch/polycaprolactone composite material contains strong hydrophilic sucrose groups and lipophilic fatty acid groups, so that the starch/polycaprolactone composite material has strong surface activity and good emulsification effect on oil and water, is widely applied to the fields of food, medicine and daily chemical industry, is used as a plasticizer to degrade plastics, namely starch/polycaprolactone blends, and has good machining performance.
Sucrose fatty acid esters exhibit different forms of dispersion in water with changes in pH: the sucrose fatty acid ester can be uniformly dispersed into water at a pH value of 5-8 to form stable emulsion; when the pH value of the emulsion is reduced to be below 5, the sucrose fatty acid ester forms semisolid gel and is separated from water, and when the pH value is reduced to be below 1, the sucrose fatty acid ester is precipitated; when the pH value is restored to be above 7, the sucrose fatty acid ester is redispersed in water to form a good emulsion.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the preparation method comprises the steps of adding a sucrose fatty acid ester solution into a graphene oxide dispersion liquid, uniformly mixing by stirring, uniformly coating graphene oxide with sucrose fatty acid ester, and well solving the problems that the powdered graphene oxide is easy to agglomerate and not easy to disperse by using a powdered graphene oxide sucrose fatty acid ester enrichment substance.
2. Compared with the graphene oxide aqueous dispersion with the content of the commercially available graphene oxide of 0.05-1%, the method can obtain the graphene oxide sucrose fatty acid ester pulp with the content of the graphene oxide of up to 7.87%, and has convenience in application.
Drawings
Fig. 1 is an ultraviolet spectrum of a supernatant before and after graphene oxide enrichment and after the enrichment.
In the figure, the number 1 is the graphene oxide before enrichment, the number 2 is the enriched product of the graphene oxide sucrose fatty acid ester, and the number 3 is the supernatant after enrichment.
Detailed Description
The present invention will be described in more detail with reference to specific examples, but the technical scope of the present invention is not limited to these examples.
Example 1:
the preparation method of the enriched graphene oxide sucrose fatty acid ester comprises the following steps of (1) preparing a graphene oxide sucrose fatty acid ester enrichment substance, wherein the mass ratio of graphene oxide to sucrose fatty acid ester is 1:0.05 in terms of dry matter:
100ml of 0.1% graphene oxide dispersion liquid is taken, 0.5ml of sucrose fatty acid ester solution with the HLB value of 16 and the concentration of 1% is dropwise added, the mixture is stirred and mixed uniformly at a high speed, the pH value is adjusted to 4, the mixture is kept still for 30min, the liquid is divided into an upper layer and a lower layer, a separating funnel is used for separating to obtain a supernatant and a lower layer dope, the lower layer dope is centrifugally separated to obtain 1.42g slurry graphene oxide sucrose fatty acid ester enrichment, and the enrichment is subjected to conventional vacuum drying and grinding to obtain 0.107g powder graphene oxide enrichment. The graphene oxide concentrate has good dispersibility in water, can be easily diluted into 0.1% dispersion, and is detected by an ultraviolet-visible spectrophotometer, as shown in fig. 1, the graphene oxide dispersion and the graphene oxide sucrose fatty acid ester concentrate dispersion before enrichment have a C = C bond characteristic absorption peak at 230nm, and the supernatant has no absorption peak at 230nm, which indicates that the graphene oxide is effectively enriched by the sucrose fatty acid ester and separated from the water phase. Based on the enrichment rate of the graphene oxide of 100%, the content of the graphene oxide in the slurry is 7.04%, the content of the graphene oxide in the dried matter is 93.46%, and the rest is sucrose fatty acid ester and moisture.
Example 2:
the preparation method of the enriched graphene oxide sucrose fatty acid ester comprises the following steps of (1) preparing a graphene oxide sucrose fatty acid ester enrichment substance, wherein the mass ratio of graphene oxide to sucrose fatty acid ester is 1:0.01 in terms of dry matter:
taking 100ml of 0.05% graphene oxide dispersion liquid, adding 0.5ml of sucrose fatty acid ester solution with HLB value of 11 and concentration of 0.1%, stirring at high speed, mixing uniformly, adjusting pH to 2, standing for 30min, separating liquid into an upper layer and a lower layer, separating by a separating funnel to obtain a supernatant and a lower layer sticky matter, centrifuging the lower layer sticky matter to obtain 0.635g slurry graphene oxide sucrose fatty acid ester enrichment, and performing conventional vacuum drying and grinding on the enrichment to obtain 0.054g powder graphene oxide sucrose fatty acid ester enrichment. And (3) detecting by an ultraviolet visible spectrophotometer, wherein the supernatant has no C = C bond absorption peak at 230nm, which indicates that the graphene oxide is effectively enriched by the sucrose fatty acid ester and separated from the water phase. Based on the enrichment ratio of the graphene oxide of 100%, the content of the graphene oxide in the slurry is 7.87%, the content of the graphene oxide in the dried matter is 92.59%, and the balance of sucrose fatty acid ester and moisture.
Example 3: a
The preparation method of the enriched graphene oxide sucrose fatty acid ester comprises the following steps of (1) preparing a graphene oxide sucrose fatty acid ester enrichment substance, wherein the mass ratio of graphene oxide to sucrose fatty acid ester is 1:1 in terms of dry matter:
taking 1000ml of 0.5% graphene oxide dispersion liquid, adding 500ml of sucrose fatty acid ester solution with HLB value of 15 and concentration of 1%, stirring and mixing uniformly at a high speed, adjusting the pH value of the material to 0.5, standing for 30min, dividing the obtained liquid into an upper layer and a lower layer, separating by a separating funnel, discarding the supernatant, centrifuging the lower layer of viscous substance to obtain 130.5g slurry graphene oxide sucrose fatty acid ester enrichment, and drying and grinding the enrichment to obtain 10.62g powder graphene oxide sucrose fatty acid ester enrichment. And (3) detecting by an ultraviolet visible spectrophotometer, wherein the supernatant has no C = C bond absorption peak at 230nm, which indicates that the graphene oxide is effectively enriched by the sucrose fatty acid ester and separated from the water phase. Based on the enrichment ratio of the graphene oxide of 100%, the content of the graphene oxide in the slurry is 3.83%, the content of the graphene oxide in the dried matter is 47.08%, and the balance of sucrose fatty acid ester and moisture.
Example 4:
the preparation method of the enriched graphene oxide sucrose fatty acid ester comprises the following steps of (1) preparing a graphene oxide sucrose fatty acid ester enrichment substance, wherein the mass ratio of graphene oxide to sucrose fatty acid ester is 1:10 in terms of dry matter:
taking 5g of sucrose fatty acid ester with HLB value of 7, fully dissolving the sucrose fatty acid ester with 895ml of water, adding 100ml of 0.5% graphene oxide dispersion liquid, stirring and mixing the mixture uniformly at a high speed, adjusting the pH value of the material to 0.5, standing for 30min, dividing the obtained liquid into an upper layer and a lower layer, separating the upper layer and the lower layer by a separating funnel, discarding the supernatant, centrifugally separating the lower layer sticky matter to obtain 90.46g of pulpy graphene oxide sucrose fatty acid ester enrichment, and drying and grinding the enrichment to obtain 6.67g of powdery graphene oxide sucrose fatty acid ester enrichment. And (3) detecting by an ultraviolet visible spectrophotometer, wherein the supernatant has no C = C bond absorption peak at 230nm, which indicates that the graphene oxide is effectively enriched by the sucrose fatty acid ester and separated from the water phase. Based on the enrichment ratio of the graphene oxide of 100%, the content of the graphene oxide in the slurry is 0.55%, the content of the graphene oxide in the dried matter is 7.50%, and the rest is sucrose fatty acid ester and moisture.
Example 5:
the preparation method of the enriched graphene oxide sucrose fatty acid ester comprises the following steps of (1) preparing a graphene oxide sucrose fatty acid ester enrichment substance, wherein the mass ratio of graphene oxide to sucrose fatty acid ester is 1:0.005 in terms of dry matter:
taking 1000ml of 0.1% graphene oxide dispersion liquid, adding 5ml of sucrose fatty acid ester solution with HLB value of 15 and concentration of 0.1%, stirring and mixing uniformly at high speed, adjusting pH to 2, standing for 30min, ensuring liquid delamination not to be obvious, performing centrifugal separation on all materials to obtain 86.6g slurry graphene oxide sucrose fatty acid ester enrichment, and performing conventional vacuum drying and grinding on the enrichment to obtain 1.14g powdered graphene oxide enrichment. The graphene oxide concentrate has good dispersibility in water, can be easily diluted into 0.1% dispersion, and is detected by an ultraviolet-visible spectrophotometer, as shown in fig. 1, the graphene oxide dispersion and the graphene oxide sucrose fatty acid ester concentrate dispersion before enrichment have a C = C bond characteristic absorption peak at 230nm, and the supernatant has no absorption peak at 230nm, which indicates that the graphene oxide is effectively enriched by the sucrose fatty acid ester and separated from the water phase. Based on the enrichment ratio of the graphene oxide of 100%, the content of the graphene oxide in the slurry is 1.15%, the content of the graphene oxide in the dried matter is 87.72%, and the rest components are sucrose fatty acid ester and moisture.
The method for preparing the enriched product of the graphene oxide sucrose fatty acid ester of examples 1 to 5 uses sucrose fatty acid ester having HLB value between 7 and 16. The HLB is lower than 7, the lipophilicity of the sucrose fatty acid ester is enhanced, the water dispersibility is poor, and the sucrose fatty acid ester is not suitable for being used as a carrier for enriching graphene oxide, so the sucrose fatty acid ester with the HLB value of 7-16 is preferably used as the carrier for enriching the graphene oxide in the technical scheme. On the basis of dry matter, the mass ratio of the graphene oxide to the sucrose fatty acid ester is 1: 0.01-10, the mass ratio of the graphene oxide to the sucrose fatty acid ester in example 4 is 1:10, the content of the graphene oxide in the obtained slurry is close to that of the graphene oxide dispersion liquid before enrichment, and the practicability of the graphene oxide sucrose fatty acid ester enrichment slurry is inferior to that of the graphene oxide dispersion liquid when the content of the graphene oxide in the slurry is higher than that of the graphene oxide dispersion liquid before enrichment; the mass ratio of the graphene oxide to the sucrose fatty acid ester in example 5 is less than 1:0.01, liquid layering is not obvious, enrichment of graphene oxide is not facilitated, in order to solve the problem, centrifugal separation needs to be carried out on all materials, the solid content of the obtained slurry is low, a large amount of water needs to be evaporated to obtain a powdery graphene oxide sucrose fatty acid ester enrichment, equipment investment and treatment cost need to be increased for large-scale preparation of the graphene oxide sucrose fatty acid ester enrichment, and economy is not achieved, so the technical scheme preferably selects the mass ratio (calculated by dry matters) of graphene oxide to sucrose fatty acid ester to be 1: 0.01-10. The condition for forming the enriched substance of the oxidized graphene sucrose fatty acid ester is that the pH value of the material is between 0.5 and 4. The pH value is lower than 0.5, the formed enriched substance is hard granular precipitate, and the dispersibility in water and organic solvents is poor when the enriched substance is used, so that the redispersion of the graphene oxide is not facilitated; the pH value is higher than 4, and based on the property of sucrose fatty acid ester, a gel is not easy to form to effectively enrich graphene oxide, so the pH value of the material with the condition of forming the graphene oxide sucrose fatty acid ester enrichment in the technical scheme is between 0.5 and 4.
Claims (4)
1. The enriched graphene oxide sucrose fatty acid ester is characterized in that: the preparation method is a mixture obtained by taking sucrose fatty acid ester as a coating agent or a precipitator and coating or coprecipitating graphene oxide in water.
2. A preparation method of a graphene oxide sucrose fatty acid ester enrichment is characterized by comprising the following steps: adding a sucrose fatty acid ester solution into the graphene oxide dispersion liquid, uniformly mixing by stirring, adjusting the pH value of the material, separating the sucrose fatty acid ester and the graphene oxide from a water phase in a coating or coprecipitation mode, and obtaining a pasty graphene oxide sucrose fatty acid ester enrichment through centrifugal sedimentation.
3. The method for preparing the enriched product of the graphene oxide sucrose fatty acid ester according to claim 2, wherein the method comprises the following steps: drying and grinding the slurry graphene oxide sucrose fatty acid ester enrichment to obtain powder graphene oxide sucrose fatty acid ester enrichment.
4. The method for preparing the enriched product of the graphene oxide sucrose fatty acid ester according to claim 2 or 3, wherein: the HLB value of the added sucrose fatty acid ester is 7-16; the mass ratio of the graphene oxide to the sucrose fatty acid ester is 1: 0.01-10 in terms of dry matter, and the pH value of the material is 0.5-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811173921.2A CN109224900B (en) | 2018-10-09 | 2018-10-09 | Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811173921.2A CN109224900B (en) | 2018-10-09 | 2018-10-09 | Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109224900A CN109224900A (en) | 2019-01-18 |
| CN109224900B true CN109224900B (en) | 2021-05-11 |
Family
ID=65054982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811173921.2A Active CN109224900B (en) | 2018-10-09 | 2018-10-09 | Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109224900B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128817B (en) * | 2019-05-21 | 2022-06-10 | 三门县鸿远塑业有限公司 | Graphene and nylon composite flexible glasses frame |
| CN111470502B (en) * | 2020-04-14 | 2023-03-31 | 南通强生石墨烯科技有限公司 | Graphene disinfectant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992309A (en) * | 2012-11-26 | 2013-03-27 | 同济大学 | Method for quickly preparing high-quality graphene oxide solids in large scale |
| CN104591125A (en) * | 2014-12-30 | 2015-05-06 | 广州聚能生物科技有限公司 | Method for dispersing one-dimensional or two-dimensional nanometer material |
-
2018
- 2018-10-09 CN CN201811173921.2A patent/CN109224900B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992309A (en) * | 2012-11-26 | 2013-03-27 | 同济大学 | Method for quickly preparing high-quality graphene oxide solids in large scale |
| CN104591125A (en) * | 2014-12-30 | 2015-05-06 | 广州聚能生物科技有限公司 | Method for dispersing one-dimensional or two-dimensional nanometer material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109224900A (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108752603B (en) | Preparation method of starch-based Pickering emulsion gel | |
| CN109224900B (en) | Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof | |
| Tatar et al. | Evaluation of hemicellulose as a coating material with gum arabic for food microencapsulation | |
| Wu et al. | Microencapsulation of fish oil by simple coacervation of hydroxypropyl methylcellulose | |
| US9434788B2 (en) | Bio-based fiber gums (BFGs) and processes for producing BFGs | |
| WO2015030852A1 (en) | Oil extraction aids in grain processing | |
| CN110591162B (en) | Nano cellulose powder material, preparation method, re-dispersed nano cellulose pulp containing nano cellulose powder material and application | |
| CN106669608A (en) | Graphene oxide coated metal organic framework material and preparation method thereof | |
| EP3390458B1 (en) | Bimodal cellulose composition | |
| KR100951706B1 (en) | Nanoemulsion, nanoparticle containing resveratrol and method of production thereof | |
| Safian et al. | Utilization of lignocellulosic biomass: A practical journey towards the development of emulsifying agent | |
| CN106757464A (en) | Food oxydating resistance cellulose acetate nanofiber preservative film | |
| CN109679147B (en) | Plant microfine fiber sucrose fatty acid ester enrichment and preparation method thereof | |
| CN113426389B (en) | Preparation method of alcohol soluble protein microcapsule and product | |
| CN115152888B (en) | Cannabin pickering granules and preparation method and application thereof | |
| Cao et al. | Effect of spray drying on the properties of camelina gum isolated from camelina seeds | |
| CN114982939B (en) | Beet pulp full-component emulsifying thickener and preparation method and application thereof | |
| US10233261B1 (en) | Natural polymer nanoparticles from ionic liquid emulsions | |
| JP2022548143A (en) | Homogeneous textile products based on bio-oil and/or water and methods for their production | |
| CN107434898B (en) | Preparation method of polyvinyl alcohol/starch nano composite film | |
| Souza et al. | Preparation and properties of cellulose nanocrystals derived from corn cobs: application as a reinforcing material for “green nanocomposite” films | |
| CN115369685B (en) | High internal phase alkenyl succinic anhydride papermaking sizing agent emulsion and preparation method thereof | |
| CN1712001A (en) | Catechin microcapsules production | |
| Tang et al. | Enzymatic coupled mechanical defibrillation process for the production of corn (Zea mays) cob nanofibrillated cellulose: preparation, characterization and evaluation as Pickering emulsifier for oil-in-water emulsion | |
| CN110583972A (en) | Protein-polyphenol complex and preparation method and application thereof |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220608 Address after: 545112 plant 1, Sifang area, Xinxing Industrial Park, Liujiang District, Liuzhou City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Yuanchang Food Technology Co.,Ltd. Address before: Room 102, Jinhui International Incubator, No. 52, Guantang Avenue, Liuzhou City, Guangxi Zhuang Autonomous Region, 545616 Patentee before: LIUZHOU BEIDIFEN TECHNOLOGY CO.,LTD. |
|
| TR01 | Transfer of patent right |