CN114316655B - Preparation process and application of graphene oxide/nano barium sulfate composite material - Google Patents
Preparation process and application of graphene oxide/nano barium sulfate composite material Download PDFInfo
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- CN114316655B CN114316655B CN202210051314.9A CN202210051314A CN114316655B CN 114316655 B CN114316655 B CN 114316655B CN 202210051314 A CN202210051314 A CN 202210051314A CN 114316655 B CN114316655 B CN 114316655B
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Abstract
The invention relates to a preparation process and application of a superfine graphene oxide/barium sulfate composite material, belonging to the field of nano composite materials and being characterized by comprising the following steps: taking pretreated graphene oxide waste sulfuric acid and prefabricated barium carbonate slurry as raw materials, respectively conveying the barium carbonate slurry and the waste sulfuric acid into a reaction kettle through a pipeline, adding the barium carbonate slurry into the reaction kettle in a continuous dripping mode, spraying the waste sulfuric acid on barium carbonate/waste water slurry drops in a spraying mode, and controlling the pH and the temperature of materials in the reaction kettle; aging after the reaction is finished; filtering the aged material to obtain a graphene oxide/barium sulfate composite material; according to the invention, the graphene waste acid and wastewater are used as raw materials, the barium sulfate composite material with a smaller oil absorption value is obtained, waste is changed into valuable, the addition amount of barium sulfate in the downstream field application is increased, and the uniformity of barium sulfate in blending with graphene oxide in a downstream system is improved.
Description
Technical Field
The invention relates to the field of nano composite materials, in particular to a preparation process and application of a graphene oxide/nano barium sulfate composite material.
Background
Barium sulfate is an important inorganic chemical product, and is widely used in the industries of paint, pigment, coating, printing ink, storage battery, papermaking, plastics, rubber, ceramic, enamel, spice and the like due to low price, wide raw material sources and no toxicity.
The common barium sulfate is used as a filling agent to only play roles in compatibilization and cost reduction, and the barium sulfate with different microscopic appearances has respective advantages when being applied to different fields. The superfine barium sulfate has the functions of reinforcing, and the coating prepared from the superfine barium sulfate has the adhesion force far higher than that of the coating prepared from the common barium sulfate, and is used for stone impact prevention coatings of automobile chassis, special coatings in the aerospace field and the like. The preparation method of the ultrafine barium sulfate is very attractive, and in order to prepare the ultrafine barium sulfate, the conventional method is carried out by an impinging stream reactor, and under the condition of adding an auxiliary agent, the spherical barium sulfate with the particle size range of nano-scale, submicron-scale and micron-scale is prepared.
At present, barium sulfate is used as a filler, and the addition amount of barium sulfate in the coating is limited due to the large oil absorption value of barium sulfate. This is because the filler has a large oil absorption value and a strong ability to absorb the solvent of the system, so that the filler with a large oil absorption value can make the viscosity of the system larger than that of the filler with a small oil absorption value under the same addition amount. However, since the coating material has high requirements for fluidity and coatability, the amount of the filler having a large oil absorption value is limited in order to ensure the viscosity and other properties of the system.
In recent years, due to the excellent performance of graphene, graphene is also widely applied to anticorrosive or other functional coatings, when graphene and ultra-fine barium sulfate are used as raw materials to prepare corresponding coatings, the existing method is generally used by independently adding graphene, barium sulfate and other raw materials, and due to the property of easy agglomeration of graphene, the problems of uneven mixing of components in the mixing process and the like are easily caused. In order to improve the condition, the prior art often adopts a method of adding a dispersion aid agent in raw materials, so that the condition can be improved to a certain extent, but other substances are introduced, so that the original performance of the coating is often influenced to a certain extent. In addition, in the process of preparing the nano composite material, the particle size of the particles is often controlled by controlling the process conditions in the prior art, and the process conditions are difficult to control, so that the particle size difference of the particles is easy to cause to be larger.
Generally, graphite is used as a raw material for preparing graphene, graphene oxide is prepared first, and then graphene is obtained through reduction, wherein the preparation method comprises the following steps: feeding oxidation (a large amount of sulfuric acid is needed to provide an acidic environment), dilution reduction, solid-liquid separation (graphene oxide solid materials and a large amount of dilute sulfuric acid are obtained), and acid washing (the obtained graphene oxide solid materials are washed to generate a large amount of acidic wastewater).
In the above process, a large amount of waste acid and wastewater is generated, for example, 1 ton of common graphene oxide is produced, and 100 tons of dilute sulfuric acid (with a concentration of 20% -60%) containing graphene oxide and 300 tons of chlorine-containing wastewater can be simultaneously produced in the production process, so that the amounts of the dilute sulfuric acid and the wastewater are huge. The produced dilute sulfuric acid contains SO 4 2- Besides, the material also contains a large amount of graphene oxide and K + 、Mn 2+ (ii) a The wastewater contains Cl - Small amount of SO 4 2- 、K + 、Mn 2+ . Not only causes environmental pollution and large sewage discharge pressure, but also causes resource waste because manufacturing enterprises have to convey the acid and the wastewater to a wastewater treatment company for treatment, thereby generating a large amount of environmental protection cost and wasting a large amount of materials.
Disclosure of Invention
The invention provides a preparation process and application of an ultrafine graphene oxide/nano barium sulfate composite material aiming at the problems in the prior art, and aims to solve the technical problems that: the composite material of barium sulfate with a smaller oil absorption value is obtained by using the graphene waste acid wastewater as a raw material, so that waste is turned into wealth, the addition amount of barium sulfate in the application of the downstream field is increased, and the dispersion uniformity of barium sulfate in the downstream system when the barium sulfate is blended with graphene oxide is improved.
The technical scheme for solving the technical problems is as follows:
in a first aspect, the invention provides a preparation process of an ultrafine graphene oxide/nano barium sulfate composite material, which is characterized by comprising the following steps:
taking pretreated graphene oxide waste sulfuric acid and prefabricated barium carbonate slurry as raw materials, respectively conveying the barium carbonate slurry and the waste sulfuric acid into a reaction kettle through pipelines, simultaneously starting stirring in the feeding and mixing process, controlling the pH and the temperature of materials in the reaction kettle, and reacting for a period of time;
after the reaction is finished, aging at 5-90 ℃ for 0.5-24 h; during the aging process, extremely small particles can go through the dissolving-regrowth process, so that the particle size of the product tends to be uniform;
and filtering the aged material to obtain the mixture with the mass ratio of graphene oxide to nano barium sulfate being 1:100000-1: the particle size of the 100 graphene oxide/nano barium sulfate composite material is 10nm-10 mu m.
Furthermore, the pretreatment method of the graphene oxide waste sulfuric acid comprises the following steps: taking a reacted mixture obtained by preparing graphene oxide as a raw material, and selecting a flux of 0.1-20L/m 2 S, filtering through a filter cloth to obtain a filtrate; carrying out ultrasonic treatment on the filtrate, and controlling the particle size of graphene oxide to be 1 nm-50 μm; obtaining waste sulfuric acid containing graphene oxide.
Further, the content of the graphene oxide in the waste sulfuric acid containing the graphene oxide is 0.1 ppm-1%.
Further, the filtrate contains graphene oxide, sulfuric acid, potassium sulfate and manganese sulfate.
Wherein, the contents of sulfuric acid, potassium sulfate and manganese sulfate in the filtrate are respectively 5-80%, 1-15% and 5 ppm-10%.
The ultrasonic treatment adopts one or more than 2 of ultrasonic bars, ultrasonic units and groove type ultrasonic equipment for combination.
Further, the method for preparing the barium carbonate slurry comprises the following steps: adding a certain mass of barium carbonate into washing wastewater generated in the graphene oxide preparation process, and fully dispersing to prepare barium carbonate/wastewater slurry containing 10-70% of solid.
Furthermore, the washing wastewater contains hydrochloric acid, sulfuric acid, potassium sulfate, manganese sulfate, water-soluble polymer and graphene oxide.
Wherein, the full dispersion mode is one or more of mechanical stirring, a sand mill, a ball mill and a high-speed stirrer.
Further, the pH value in the reaction kettle is controlled to be 1-6.5.
Further, the temperature in the reaction kettle is controlled to be 5-90 ℃.
In a second aspect, the invention provides an application of the preparation process, which is characterized in that the preparation process is applied to preparation of downstream products containing graphene and ultrafine barium sulfate, and specifically, the preparation process is firstly adopted to prepare the ultrafine graphene oxide/nano barium sulfate composite material, and then the ultrafine graphene oxide/nano barium sulfate composite material is blended with other components required by the downstream products to prepare the downstream products, such as anticorrosive coatings and the like.
The invention has the beneficial effects that:
1. compared with a barium sulfate body, the superfine graphene oxide/nano barium sulfate composite material prepared by the process is used as a modification means of barium sulfate, the particle size of the obtained composite material is smaller, the oil absorption value is smaller, and the addition amount of the modified barium sulfate in the downstream field application is larger. And under the condition of certain viscosity, the filling amount of the filler with small oil absorption value is higher, and the coating cost is lower.
2. The process condition of the invention has good controllability, which is embodied in that: the preparation process can regulate and control the particle size of the composite material by adjusting the particle size of the graphene oxide, and has instructive significance for the field of preparing nano materials; this is because the barium sulfate grows on the surface of the barium sulfate with the graphene oxide in the system as a crystal nucleus. The existence of the graphene oxide with different sizes provides crystal nuclei for the growth of the precipitated barium sulfate, the crystal nuclei are rich, the generation of the superfine barium sulfate can be promoted, and the generation of large-particle barium sulfate is reduced. If the particle size of graphene oxide in the solution is small and the concentration is high, the number of crystal nuclei is large, that is, the number of growing points of barium sulfate is large, and thus the particle size of barium sulfate is smaller. On the contrary, the particle size of barium sulfate is large.
3. The process raw materials of the invention fully utilize the waste materials generated in the production process of the graphene oxide, realize the reutilization of waste acid and waste water, change waste into valuable, solve the environmental protection problem in the production process of the graphene oxide, realize real green production and prepare byproducts with additional values;
4. the process is applied to preparing downstream products containing graphene and ultrafine barium sulfate, such as anticorrosive coatings and the like, and the process sequence of preparing the ultrafine graphene oxide/nano barium sulfate composite material and then mixing the ultrafine graphene oxide/nano barium sulfate composite material with other components required by the downstream products to prepare the downstream products is adopted, so that the mixing uniformity of the graphene oxide and the barium sulfate can be greatly improved, and the problem of uneven mixing caused by respectively adding the graphene oxide and the barium sulfate in the application of the downstream products is solved.
Drawings
FIG. 1 is an SEM image of the resulting products of examples 1 to 4 of the present invention and comparative example 1.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The preparation process of the graphene oxide comprises the working procedures of feeding oxidation, dilution reduction, solid-liquid separation and washing, wherein the dilution reduction working procedure obtains a material, namely a mixture after reaction, and a large amount of waste sulfuric acid is contained. The embodiment of the invention is carried out by taking the reaction mixture and the washing wastewater generated in the washing process as raw materials.
Example 1
The preparation process of the embodiment comprises the following steps:
1) Pretreatment of graphene oxide waste sulfuric acid: taking the reacted mixture obtained by preparing the graphene oxide, and carrying out filter pressing treatment on the reacted mixture, wherein the filter pressing selection flux is 0.1L/m 2 S, the filtrate contains 0.1 ppm of graphene oxide, 5% of sulfuric acid, 1% of potassium sulfate and 5ppm of manganese sulfate.
2) And (3) conveying the filtrate to ultrasonic circulation equipment, and further controlling the particle size of the graphene oxide to be about 1 nm to obtain dilute sulfuric acid containing the graphene oxide.
3) Adding barium carbonate into the washing wastewater, and mechanically stirring and dispersing the barium carbonate into 1 h to prepare slurry with the solid content of 10%.
4) And (4) conveying the slurry in the step 3) into a reaction kettle 1 through a conveying pipeline, simultaneously conveying 40 kg waste sulfuric acid into the reaction kettle 1 through a pipeline, and opening a stirring rod, a heating device and a pH value detection device simultaneously in the feeding and mixing process to enable the material to react for 0.5 h in the reaction kettle with the pH =1 at 25 ℃.
5) After the reaction, the stirring was stopped and the mixture was aged at 5 ℃ for 0.5 h.
6) And conveying the aged material to a filter press through a pipeline for filter pressing to obtain the graphene oxide/nano barium sulfate composite material. The composite material can be used in the fields of anticorrosive paint, printing ink and the like.
Example 2
1) Taking the reacted mixture obtained by preparing the graphene oxide, and carrying out filter pressing treatment on the reacted mixture, wherein the filter pressing selection flux is 10L/m 2 S. filter cloth, the filtrate contains 0.3% of graphene oxide, 30% of sulfuric acid, 5% of potassium sulfate and 5% of manganese sulfate.
2) And (3) conveying the filtrate to ultrasonic circulation equipment, and controlling the particle size of the graphene oxide to be about 5 mu m to obtain dilute sulfuric acid containing the graphene oxide.
3) Adding barium carbonate into the washing wastewater, and dispersing 1.5 h by a sand mill to prepare slurry with the solid content of 40%.
4) And (3) conveying the slurry in the step 3) to a reaction kettle 1 through a conveying pipeline, conveying 6.7 kg waste sulfuric acid to the reaction kettle 1 through a pipeline, and opening a stirring rod, a heating device and a pH value detection device simultaneously in the feeding and mixing process to enable the material to react in the reaction kettle with the pH =2 at 40 ℃ to obtain 2 h.
5) After the reaction, the stirring was stopped and 12 h was aged at 60 ℃.
6) And conveying the aged material to a filter press through a pipeline for filter pressing to obtain the graphene oxide/nano barium sulfate composite material. The composite material can be used in the fields of anticorrosive paint, printing ink and the like.
Example 3
1) Taking and preparing oxygenCarrying out filter pressing treatment on the reacted mixture obtained by graphene conversion, wherein the filter pressing selection flux is 15L/m 2 S. filter cloth, the filtrate contains 0.7% of graphene oxide, 50% of sulfuric acid, 10% of potassium sulfate and 7% of manganese sulfate.
2) And (3) conveying the filtrate to ultrasonic circulation equipment, and controlling the particle size of the graphene oxide to be about 7 mu m to obtain dilute sulfuric acid containing the graphene oxide.
3) Adding barium carbonate into the washing wastewater, and performing ball milling dispersion on the barium carbonate to obtain 2 h to prepare slurry with the solid content of 50%.
4) And (2) conveying the slurry in the step 3) into a reaction kettle 1 through a conveying pipeline, conveying 4 kg waste sulfuric acid into the reaction kettle 1 through a pipeline, and opening a stirring rod, a heating device and a pH value detection device simultaneously in the feeding and mixing process to enable the material to react with 3 h in the reaction kettle with the pH =4 at the temperature of 60 ℃.
5) After the reaction, the stirring was stopped and the mixture was aged at 70 ℃ for 14 h.
6) And conveying the aged material to a filter press through a pipeline for filter pressing to obtain the graphene oxide/nano barium sulfate composite material. The composite material can be used in the fields of anticorrosive paint, printing ink and the like.
Example 4
1) Taking the reacted mixture obtained by preparing the graphene oxide, and carrying out filter pressing treatment on the reacted mixture, wherein the flux for filter pressing is 20L/m 2 S. the filter cloth, the filtrate contains 1% of graphene oxide, 60% of sulfuric acid, 15% of potassium sulfate and 10% of manganese sulfate.
2) And (3) conveying the filtrate to ultrasonic circulation equipment, and controlling the particle size of the graphene oxide to be about 10 mu m to obtain dilute sulfuric acid containing the graphene oxide.
3) Adding barium carbonate into washing wastewater, and dispersing 3 h at a high speed to prepare slurry with the solid content of 70%.
4) And (3) conveying the slurry in the step 3) to a reaction kettle 1 through a conveying pipeline, conveying 3.5 kg waste sulfuric acid to the reaction kettle 1 through a pipeline, and opening a stirring rod, a heating device and a pH value detection device simultaneously in the feeding and mixing process to enable the material to react in a reaction kettle with pH =6.5 at 90 ℃ to obtain 6 h.
5) After the reaction, the stirring was stopped and the mixture was aged at 90 ℃ for 24 h.
6) And conveying the aged material to a filter press through a pipeline for filter pressing to obtain the graphene oxide/nano barium sulfate composite material. The composite material can be used in the fields of anticorrosive paint, printing ink and the like.
Comparative example 1
The preparation method of the barium sulfate of the comparative example comprises the following steps:
1) A60% strength dilute sulphuric acid 3.5 kg is prepared.
2) Adding barium carbonate into the washing wastewater, and dispersing the barium carbonate into 3 h at a high speed to prepare slurry with the solid content of 70%.
3) Conveying the slurry in the step 2) to a reaction kettle 1 through a conveying pipeline, conveying 3.5 kg waste sulfuric acid to the reaction kettle 1 through a pipeline, and opening a stirring rod, a heating device and a pH value detection device simultaneously in the feeding and mixing process to enable the materials to react in the reaction kettle with pH =6.5 at 90 ℃ to obtain 6 h.
4) After the reaction, the stirring was stopped and the mixture was aged at 90 ℃ for 24 h.
5) And conveying the aged material to a filter press through a pipeline for filter pressing to obtain a barium sulfate product.
The morphology of the samples obtained in the above examples and comparative examples is detected by an electron tunneling microscope (SEM); detecting the particle size distribution by a particle size analyzer; the oil absorption value is tested by a method for detecting the oil absorption value in industrial precipitated barium sulfate of national standard GBT-2899-2017.
The results are shown in table 1:
TABLE 1 testing of the Properties of the materials
| Sample(s) | D 50 μm | Oil absorption value g/100 g |
| Example 1 | 0.1 | 17.7 |
| Example 2 | 2 | 19.3 |
| Example 3 | 2.8 | 21.4 |
| Example 4 | 4.8 | 22.5 |
| Comparative example 1 | 7 | 29.7 |
As can be seen from Table 1, the particle size and oil absorption of the product obtained in the examples are much smaller than those of the comparative examples. The barium sulfate is used for growing graphene oxide as crystal nucleus, so that the generated particles are more regular in appearance, less in surface defects, small in gaps among particles during stacking, and smaller in oil absorption value. In examples 1 to 4, the particle size of the composite material obtained was increased in the order of increasing the particle size of graphene oxide, and this indicates that the particle size of the composite material can be controlled by adjusting the particle size of graphene oxide, which is extremely important in the field of producing nanomaterials.
In addition, the superfine graphene oxide/nano barium sulfate composite material is prefabricated by the method and then applied to downstream products, and the dispersion uniformity of the composite material is remarkably improved.
Claims (6)
1. A preparation process of a graphene oxide/nano barium sulfate composite material is characterized by comprising the following steps:
taking pretreated graphene oxide waste sulfuric acid and prefabricated barium carbonate slurry as raw materials, respectively conveying the barium carbonate slurry and the waste sulfuric acid into a reaction kettle through pipelines, simultaneously starting stirring in the feeding and mixing process, controlling the pH and the temperature of materials in the reaction kettle, and reacting for a period of time; controlling the pH value in the reaction kettle to be 1-6.5 and controlling the temperature in the reaction kettle to be 5-90 ℃;
the pretreatment method of the graphene oxide waste sulfuric acid comprises the following steps: taking the reacted mixture obtained by preparing the graphene oxide as a raw material, and selecting the flux of 0.1-20L/m 2 S, filtering through a filter cloth to obtain a filtrate; carrying out ultrasonic treatment on the filtrate, and controlling the particle size of graphene oxide to be 1 nm-50 μm; obtaining waste sulfuric acid containing graphene oxide;
the method for preparing the barium carbonate slurry comprises the following steps: adding a certain mass of barium carbonate into washing wastewater generated in the graphene oxide preparation process, and fully dispersing to prepare barium carbonate/wastewater slurry with solid content of 10-70%;
aging after the reaction is finished;
and filtering the aged material to obtain the graphene oxide/nano barium sulfate composite material.
2. The preparation process of the graphene oxide/nano barium sulfate composite material according to claim 1, wherein the content of graphene oxide in the waste sulfuric acid containing graphene oxide is 0.1 ppm-1%.
3. The preparation process of the graphene oxide/nano barium sulfate composite material according to claim 1, wherein the sulfuric acid content in the waste graphene oxide sulfuric acid is 5-80%.
4. The preparation process of the graphene oxide/nano barium sulfate composite material according to claim 1, wherein the ultrasonic treatment is performed by using one or more of an ultrasonic rod, an ultrasonic unit and a tank type ultrasonic device.
5. The preparation process of the graphene oxide/nano barium sulfate composite material according to claim 1, wherein the sufficient dispersion manner is one or more of mechanical stirring, a sand mill, a ball mill and a high-speed stirrer.
6. The application of the graphene oxide/nano barium sulfate composite material is characterized by being applied to preparation of downstream products containing graphene and barium sulfate, and specifically, the graphene oxide/nano barium sulfate composite material is prepared by the preparation process of any one of claims 1 to 5, and then is blended with other components required by the downstream products to prepare the downstream products.
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| GB427220A (en) * | 1933-03-07 | 1935-04-17 | Titan Co Inc | Improvements in or relating to the production of barium sulphate and composite titanium pigments containing the same |
| CN101823754A (en) * | 2009-04-13 | 2010-09-08 | 王嘉兴 | Method for co-production of carbon dioxide in preparation of nano barium sulfate by barium carbonate |
| CN105576240B (en) * | 2016-01-20 | 2018-09-18 | 中国科学院过程工程研究所 | A kind of nano barium sulfate carbon composite and its preparation method and application |
| CN106829927A (en) * | 2017-01-16 | 2017-06-13 | 中国科学院合肥物质科学研究院 | A kind of metal oxide graphene composite material and preparation method thereof |
| CN107285304B (en) * | 2017-06-16 | 2019-03-29 | 北京师范大学 | A method of removing sulfate radical foreign matter in graphene oxide synthetic system |
| CN110330046A (en) * | 2019-05-21 | 2019-10-15 | 河北辛集化工集团有限责任公司 | The technique that nano barium sulfate is prepared by microreactor as raw material using barium carbonate |
| CN113247888B (en) * | 2021-04-27 | 2024-03-22 | 佛山市胜锦洁金属表面技术有限公司 | Graphene composite material and preparation method thereof |
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