CN110980725B - Method for removing metal impurities and residual graphite in diamond material - Google Patents
Method for removing metal impurities and residual graphite in diamond material Download PDFInfo
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- CN110980725B CN110980725B CN201911068332.2A CN201911068332A CN110980725B CN 110980725 B CN110980725 B CN 110980725B CN 201911068332 A CN201911068332 A CN 201911068332A CN 110980725 B CN110980725 B CN 110980725B
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Abstract
The application relates to the field of diamond, in particular to a method for removing metal impurities and residual graphite in a diamond material. The method comprises the following steps: mixing and reacting the material containing the hybrid diamond and a rusting agent until metal impurities are oxidized and rusted to obtain a first product; roasting and oxidizing the first product in an aerobic atmosphere until residual metal impurities are continuously oxidized and residual graphite is oxidized to obtain a second product; and mixing the second product with a rust remover for reaction. The method of firstly rusting and then derusting is adopted to remove residual metal impurities and oxidized residual graphite in the diamond material, strong acid is not needed, the generation of waste acid gas is greatly reduced, the method is more environment-friendly, the method is simple, the equipment is simple, and the cost is lower.
Description
Technical Field
The application relates to the field of diamond, in particular to a method for removing metal impurities and residual graphite in a diamond material.
Background
In the superhard material industry, when diamond is synthesized, an iron-nickel metal catalyst (generally 65-70% of iron and about 35-30% of nickel) is required to be adopted at present. The post-treatment process for purifying diamond by using synthetic rod is characterized by that firstly, it adopts electrolysis method to extract iron-nickel metal catalyst from synthetic rod, but the diamond separated in the subsequent step also contains a small quantity of catalyst and residual graphite.
At present, the traditional method for removing the catalyst and the residual graphite in the diamond adopts strong acid such as sulfuric acid, nitric acid, hydrochloric acid and the like and adopts a reaction kettle way for treatment. Generally, concentrated sulfuric acid and nitric acid are adopted to carry out heating reaction in a reaction kettle to remove residual graphite, then diluted acid (sulfuric acid + nitric acid + hydrochloric acid) is used to carry out reaction to remove metal catalyst, and then deacidification, pure water cleaning and drying are carried out to obtain a clean diamond single crystal product. The production of diamond powder is that after the diamond monocrystal is physically crushed into powder, the residual graphite and metal catalyst also need to be heated and reacted by a reaction kettle with strong acid such as sulfuric acid, nitric acid and hydrochloric acid, even perchloric acid, etc. to remove impurities such as residual graphite and metal catalyst.
The post-treatment purification method adopting strong acid generates a large amount of waste acid gas by the reaction of the strong acid, thereby bringing about serious environmental protection problems. In order to remove the waste acid gas, it is common that firstly, the reaction kettle reaction needs acid mist treatment equipment of an acid mist adsorption tower, the waste acid after the reaction needs to be neutralized by adding alkali, then the solid content of the reaction liquid is separated by a filter press and discharged as dangerous waste, and therefore, the cost is high, and the content of harmful metal ions and nitrogen oxides in the neutralized waste water is controlled, and the problem that the waste acid is difficult to treat is also solved.
Disclosure of Invention
An object of the embodiment of this application is to provide a method for removing metallic impurity and residual graphite in diamond material, it aims at improving the problem that need use strong acid when current diamond edulcoration is handled.
The application provides a technical scheme:
a method for removing metal impurities and residual graphite from a diamond material, comprising the steps of:
mixing and reacting a diamond material and a rusting agent until metal impurities are oxidized and rusted to obtain a first product;
roasting the first product in an aerobic atmosphere to continuously oxidize residual metal impurities and residual graphite to obtain a second product;
and mixing the second product with a rust remover for reaction, and removing rusted oxides to obtain the clean diamond.
The diamond material is oxidized and rusted by adopting the rusting agent, so that residual metal catalyst in the diamond material reacts with the rusting agent, and metal is oxidized into oxide. Then, the residual metal catalyst in the diamond material is further oxidized by a method of oxidizing and roasting, and simultaneously, the residual graphite in the diamond material is oxidized. Finally, the diamond material is derusted by the deruster, so that residual metal catalyst and residual graphite in the diamond material can be removed, and pure diamond single crystals or powder can be obtained. The method does not need strong acid, greatly reduces the generation of waste acid gas, is more environment-friendly, and has simple method, simple equipment and lower cost.
In other embodiments of the present application, the step of mixing the diamond material and the rusting agent for reaction comprises:
mixing the diamond material and a rusting agent and reacting for at least 30 minutes;
optionally, the mixture of diamond material, rust agent is stirred during the reaction.
In other embodiments of the present application, the rust agent is mixed with the diamond material in a total mass ratio of between 8-40%.
In another embodiment of the present application, the step of calcining and oxidizing the first product in an oxygen-containing atmosphere includes:
roasting at 450-600 ℃ for 0.5-5 hours.
The high-temperature roasting can further promote the oxidation, and because the diamond material to be cleaned also contains a small amount of graphite (C), the catalyst also contains graphite (C); on one hand, the metal catalyst is promoted to be further fully oxidized during roasting, and on the other hand, the residual graphite reacts with oxygen to generate CO or CO2While nickel also forms nickel oxide. In the above temperature range, not only the oxidation reaction can be efficiently performed, but also waste acid gas is hardly generated, thereby greatly reducing pollution.
In other embodiments of the present application, when the second product is mixed with the rust remover, the total mass ratio of the rust remover to the second product is between 10 and 30%.
In other embodiments of the present application, the temperature for mixing and reacting the second product with the rust remover and water is below 100 ℃ and the reaction time is at least 1 hour;
optionally, the temperature of the reaction is 60-90 ℃;
the reaction time is 1.5-5 hours.
In other embodiments of the application, the rust inhibitor and the rust remover are not used by adding water, or are used after being diluted by adding water;
wherein, when the water is added for dilution, the mass ratio is as follows:
a rust agent: water is within 1: 3; or
Rust remover: the water is within 1: 3.
In other embodiments of the present application, the method further comprises:
cleaning the product of the mixed reaction of the second product, the rust remover and water;
optionally, the cleaning step comprises removing waste liquid from the product to obtain a precipitate, cleaning the precipitate to neutrality, and drying at a temperature below 200 ℃ to obtain a clean diamond product.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic flow diagram of a cleaning process for hybrid diamond using two components of rust and rust removers;
FIG. 2 is a photograph taken with a microscope (which is gray scale processed) of a hybrid diamond-containing single crystal provided in examples 1 and 3 of the present application before processing;
FIG. 3 is a photograph taken with a microscope (which is gray scale processed) of the hybrid diamond-containing single crystal provided in examples 1 and 3 of the present application after treatment;
fig. 4 is a photographed picture (a picture is subjected to gray scale processing) of the hybrid diamond-containing powder provided in examples 2 and 4 of the present application before processing;
fig. 5 is a photograph of the heterodiamond-containing powder provided in examples 2 and 4 of the present application after treatment (the photograph was subjected to a gray scale treatment).
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. It should be further explained that the rust agent and the rust remover related to the invention can be prepared by self according to the formula, and all the formula applications achieving the effects of the rust agent and the rust remover are in the protection scope of the invention.
Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
The embodiment of the application provides a method for removing metal impurities and residual graphite in a diamond material, which comprises the following steps:
mixing and reacting a diamond material, a rusting agent and water until metal impurities are oxidized and rusted to obtain a first product;
roasting the first product in an aerobic atmosphere until the residual metal is oxidized and the residual graphite is oxidized to obtain a second product;
and mixing the second product with a rust remover and water for reaction.
The diamond material is oxidized and rusted by adopting the rusting agent, so that residual metal catalyst in the diamond material reacts with the rusting agent, and metal is oxidized into oxide. Then, the residual metal catalyst in the diamond material is further and thoroughly oxidized by a method of oxidizing and roasting, and simultaneously, the residual graphite in the diamond material is also oxidized. Finally, the diamond material is derusted by the deruster, so that residual metal catalyst and residual graphite in the diamond material can be removed, and pure diamond single crystals or powder can be obtained.
Referring to fig. 1, in some embodiments of the present application, a method of removing metallic impurities and residual graphite from a diamond mass, comprises the steps of:
and step S1, mixing and reacting the diamond material and the rusting agent until metal impurities are oxidized and rusted to obtain a first product.
The metal catalyst used for diamond production is Fe70Ni30 alloy, the catalyst is dissolved C to reach saturation state after ultrahigh pressure and high temperature synthesis, and the content of carbon (C) reaches about 6-6.5% after analysis of the synthesized catalyst, thus becoming the high-carbon catalyst component. Thus, rust inhibitors and their reactions primarily oxidize Fe and Ni to oxides. Specifically, the iron component mainly generates iron oxide, and the nickel component has poor corrosion resistance under the carbon-containing condition and can also generate NiO oxides by corrosion; for example, the 201-class 304 stainless steel is very easily oxidized under the oxidation condition of the rusting agent.
In the description of the examples, the rust inhibitor and the rust remover are commercially available products, and the rust inhibitor is generally A, B two-component products, and also one-component products. Of course, the formula is obtained according to the action principle of the rust agent and the rust remover and by adopting reverse engineering, the rust agent and the rust remover can be prepared by self, and the concentration can be mastered by self.
Therefore, the method provided by the embodiment of the application utilizes the rust remover to enable the iron-based metal impurities in the diamond material to be oxidized and rusted firstly, and then uses the rust remover to remove the iron rust, so that the method replaces the traditional process that strong acid is used for direct reaction. Avoids the pollution caused by using strong acid. The commercial rusting agent is generally neutral or slightly weakly acidic, only weak waste acid gas is generated when the rusting agent is added for reaction, and waste gas can be adsorbed by using small-displacement alkaline adsorption equipment. Compared with the traditional method for treating diamond by strong acid, the method greatly reduces pollution.
Further, the step of mixing and reacting the impurity-containing diamond material and the rusting agent (and water) comprises the following steps:
according to the technical scheme, a commercially available A, B two-component rusting agent is adopted, and according to the use specification, a diamond material is firstly reacted with the A component rusting agent for a plurality of minutes, and then the B component rusting agent is added for reaction for at least more than 30 minutes.
Generally, rust and rust removers are commercially available. The rust remover and the rust remover are not used by adding water, or are used after being diluted by adding water.
When the water is added for dilution, the mass ratio is as follows:
a rust agent: water is within 1: 3; or
Rust remover: the water is within 1: 3.
It should be noted that commercially available rust and rust removers generally have an original concentration, and when diluted with water, the original concentration is calculated.
Specifically, when the rust inhibitor is used, water is added for dilution and then is mixed with materials, and the purpose of adding water is to match the diluted concentration to meet the total amount of oxidized metal impurities and the solid-liquid ratio of the mixed wet materials, so that the materials are completely soaked in the rust inhibitor for reaction.
Further alternatively, during the rusting reaction, stirring may be performed to homogenize the reaction.
Further, when the rusting agent is mixed with the diamond material, the mass total ratio of the two components A, B of the rusting agent to the diamond material is 8-40% and the two components are basically equal according to the impurity content of the diamond containing impurities.
Further optionally, when the rusting agent is mixed with the diamond monocrystal material containing the impurities, the mass total ratio of the two-component rusting agent to the diamond monocrystal material is 8-20%.
Further optionally, when the rusting agent is mixed with the diamond powder material, the mass total ratio of the two components of the rusting agent to the diamond powder material is 15-40% respectively. (since the diamond powder has a larger specific surface area than the single crystal, a larger amount is required to ensure infiltration).
Illustratively, when the rusting agent is mixed with the diamond material, the mass total ratio of the bi-component A, B rusting agent to the diamond material containing the impurities is 8 percent respectively; 12 percent; 16 percent; 20 percent; 24 percent; 28%; 32 percent; 36 percent; 40%, etc.
Further, when the rust inhibitor is mixed with the diamond material, the content of water is selected according to the wetting condition of the diamond and the rust inhibitor.
Optionally, when the rust agent is mixed with the diamond material, the content of water is selected to just completely wet the diamond and the rust agent, but the material with high impurity content can be higher than the surface of the material due to the increase of the amount of the rust agent.
In other alternative embodiments, the rust agent and the diamond material may be mixed and selected according to the instructions for use of the rust agent.
When the rusting agent and the material containing the hybrid diamond are mixed, the rusting agent and water are mixed firstly, and the mass ratio of the rusting agent to the water is 1: 0-1: 3. Then, the diluted rusting agent is mixed with the diamond material, the mixture is uniformly stirred, and the rusting reaction is carried out for a certain time, so that the metal impurities in the diamond material are oxidized and rusted, and the first product is prepared.
Illustratively, the rust inhibitor takes a commercially available product as an original concentration, and the mass ratio of the rust inhibitor to water is selected to be 1: 0; 1: 1; 1: 1.5; 1: 2; 1:2.5 or 1:3, etc. (materials with high impurity content can be diluted without adding water)
It should be noted that, when the rusting agent and the diamond material are mixed, the total proportion of the rusting agent needs to be adjusted according to the content of impurity metals in different diamond materials. For example, when the diamond material contains more metal impurities, the proportion of the rusting agent can be properly increased to reduce the water content, and even the raw solution can be directly used for reaction; when the metal impurity content in the diamond material is less, the total proportion of the rusting agent can be properly reduced, and the water content is increased. In a word, the total proportion of the rusting agent is determined according to the impurity content of the materials, and the proper amount of water is diluted, so that the materials are soaked uniformly or submerge the materials to fully react.
Further, when the diamond material, the rusting agent and the water are mixed, an acid-resistant container can be selected. Such as acid resistant tubs, etc. A reaction container with a stirrer for uniformly stirring the materials and the rusting agent can be selected, or manual stirring can be adopted.
In an alternative embodiment of the present application, the rust inhibitor may be an A, B two-component rust inhibitor available on the market. A first product is made by a two-step reaction of A, B two-component rust agent to cause oxidation rusting of metal impurities in the heterodiamond-containing material.
In other alternative embodiments of the present application, the rust inhibitor may be a single-component strong oxidant, such as a commercially available single-component rust inhibitor, and may also be, for example, potassium chlorate, sodium chlorate, potassium permanganate, or the like.
The rust inhibitor is a single-component rust inhibitor sold in the market, and the use instruction is referred. For example, with potassium chlorate, it is necessary to dissolve the potassium chlorate in water and then wet the material to produce the first product. The mass ratio of the potassium chlorate to the diamond containing impurities is 1-3%.
And step S2, roasting the first product in an aerobic atmosphere to continue to be completely oxidized and oxidize residual graphite to obtain a second product.
The high-temperature roasting can further promote the oxidation, and because the diamond material to be cleaned also contains a small amount of graphite (C), the catalyst also contains graphite (C); on one hand, the metal catalyst is promoted to be further fully oxidized during roasting, and on the other hand, the residual graphite reacts with oxygen to generate CO or CO2While nickel also forms nickel oxide. Therefore, by roasting and oxidizing the first product prepared in the step S1 in an aerobic atmosphere until the residual graphite is oxidized, not only the residual graphite impurities in the diamond material can be effectively removed, but also the metal impurities which are not oxidized and rusted in the step S1 can be further removed, so that the metal impurities and the residual graphite in the diamond material are thoroughly removed, and a pure diamond product is obtained. In the process, the rust agent and the diluted water are dried, and since the acidity of the rust agent is very low, little waste acid gas is generated, and the water is evaporated.
Further, the step of roasting and oxidizing the first product in an oxygen atmosphere comprises the following steps:
roasting at 200-600 ℃ for at least 1.5 hours.
For example, when the first product is roasted and oxidized in an oxygen atmosphere, the roasting temperature can be selected as follows: 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃ or 600 ℃. When the first product is calcined and oxidized in an oxygen atmosphere, the calcination time may be selected to be 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, or 5.0 hours.
In the temperature range, in the low-temperature stage of less than 200 ℃, the rusting agent liquid of the first product is evaporated, a small amount of waste acid gas is generated at the moment, and the waste gas can be adsorbed by using a small-displacement alkaline adsorption device, so that the pollution is greatly reduced.
Further optionally, the temperature for roasting the first product in an oxygen atmosphere is selected to be 500-550 ℃, which is the optimal temperature range of the graphite oxide. Within this calcination temperature range, the reaction rate is greatly increased.
In other optional embodiments of the present application, the firing temperature and the firing time may also be adaptively adjusted according to the content of metal impurities and residual graphite in the diamond material.
Through the roasting process, the residual metal in the diamond material is further oxidized and rusted, and the residual graphite is oxidized, so that the residual metal and the residual graphite in the diamond material are further removed, and a second product is prepared.
The first product, made of the one-component rust agent, is also treated by the above method.
And step S3, mixing and reacting the second product with a rust remover.
The rust remover reacts with the metal oxide in the second product prepared in step S2 by mixing and reacting the second product with the rust remover to remove rust. For example, the rust remover is caused to react with the rust or the like in the second product, and the rust is dissolved in the rust remover to remove the rust.
When the rust remover is used for reaction, only a small amount of waste gas is discharged, and only acid mist adsorption equipment is needed for adsorption. Compared with the common method for treating the diamond by strong acid at present, the method greatly reduces the pollution of waste gas.
Further, when the second product is mixed with the rust remover, the mass ratio of the rust remover to the second product is 10-30%. The diamond with high impurity content has large weight ratio, and conversely, the diamond has small weight ratio.
Illustratively, when the second product is mixed with the rust remover, the mass ratio of the rust remover to the second product is selected as follows: the mass ratio of the rust remover to the second product is 10 percent; 12 percent; 15 percent; 18 percent; 22 percent; 25 percent; 30 percent.
The rust remover is diluted by water for use, and the purpose and the dilution amount of the water for adding the rust remover are the same as those of the rust remover.
Further, the temperature for mixing and reacting the second product with the rust remover and water is below 100 ℃, and the reaction time is at least 1 hour.
Further optionally, the temperature for mixing the second product with the rust remover and water for reaction is 60-90 ℃.
Illustratively, the temperature at which the second product is mixed with the rust remover and water to react is 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 90 ℃.
At the above reaction temperature, the removal of rust from the second product can be ensured.
Further optionally, mixing the second product with a rust remover and water for reaction for 1-5 hours.
Illustratively, the reaction time for mixing the second product with the rust remover and water is 1 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3 hours, 4 hours, or 5 hours.
Under the reaction time, rust in the second product can be removed.
And step S4, cleaning the product of the mixed reaction of the second product prepared in the step S3, the rust remover and the water.
The rust remover remaining from the reaction in step S3 can be removed by cleaning, thereby obtaining a pure diamond product.
Further, the washing step comprises removing waste liquid from the product to obtain a precipitate, and washing the precipitate to be neutral.
Because the diamond products are all contained in the precipitate, the precipitate is cleaned by removing the waste liquid in the step S3, the cleaning efficiency can be effectively improved, and the pure diamond products can be obtained.
Alternatively, the waste liquid can be removed by discharging the product of the mixed reaction of the second product, the rust remover and water into a centrifugal dehydrator or a suction filter box. Cleaning to neutrality may be carried out by placing the material in a container, such as a commercially available plastic or stainless steel tub or basin, a dedicated elutriator, or the like.
In other alternative embodiments of the present invention, the waste liquid after the reaction is removed, and the curing agent can be directly changed into a small amount of solid waste. By adopting the method, the detection of the extract content can be realized without exceeding the standard, and the extract can be directly discharged or the comprehensive utilization of solid waste can be carried out. And a little alkali is added into the water of the elutriated material for neutralization, and the sediment can reach the discharge standard after being filtered.
Further, the cleaning step comprises elutriating the precipitate to neutrality, and then drying to obtain a clean diamond product.
Further optionally, drying the precipitated diamond at the temperature of 80-200 ℃.
And drying to obtain pure diamond single crystal or diamond powder material.
In the steps S1-S4, the rust remover and rust remover are neutral or slightly weakly acidic, only a very small amount of waste gas is generated in the process, and the discharged waste rust remover liquid is slightly weakly acidic, so that the waste rust remover liquid can be treated by simple environment-friendly equipment.
Illustratively, in the above steps S1-S4, a negative pressure air extraction device with an alkaline water tank is used, and weakly acidic gas generated from the container for holding the rust reaction, the high temperature roaster and the rust removal reaction container is extracted to the negative pressure air extraction device, so that the weakly acidic gas is adsorbed and reacts with alkaline water in a neutralization manner.
After the wastewater from which the rust remover is removed is neutralized to neutrality by adding alkali, the wastewater and the elutriation wastewater neutralized by the alkali are subjected to pressure filtration by a filter press to obtain a filter cake with solid content, and the filter cake is discharged as solid waste.
Compared with the conventional method for treating the diamond material by adopting the strong acid, the method provided by the embodiment of the application avoids using the strong acid, and reduces the environmental pollution to the greatest extent.
In the traditional method, because the reaction generates strong waste acid gas, the waste acid gas is introduced into a purification tower to be adsorbed by alkaline water, and alkaline water for adsorbing the waste acid gas enters a waste acid water treatment system. Removing waste acid liquor from the reacted materials, and discharging the waste acid liquor into a waste acid treatment system for alkali addition and neutralization; the acidic cleaning water containing residual acid in the elutriation material is also discharged into a waste acid water treatment system. The waste acid water treatment system adds alkali to the waste acid water to neutralize to neutrality, then uses a filter press to dewater, discharges solid matters as dangerous waste to discharge, and recycles the water after neutralization and filtration, but the salinity in the water after repeated recycling is higher and higher, and can not reach the discharge standard of environmental protection. Taking the clean treatment of the powder containing the hybrid diamond as an example, the acid consumption is the largest, the neutralization amount is large by using alkali, the direct cost of the acid is up to 10 yuan/kg, and the environmental-friendly operating cost can reach 7.5 yuan/kg.
By adopting the method provided by the embodiment of the application, the cost of treating the rust inhibitor and the rust remover of each kilogram of the powder containing the hybrid diamond is about 5 yuan; because the concentration of the weak acid contained in the concentration of the discharged waste gas and waste water is greatly lower than that of the strong acid treatment, the alkali consumption for neutralization treatment is greatly reduced by at least more than 5 times, and the environment-friendly operation cost can be reduced to 1.5 yuan/kg of diamond; the content of the extract of the solid waste discharged by neutralization, precipitation and filter pressing is greatly reduced, and the neutralized water does not contain nitrogen oxide and COD and can be directly discharged.
The features and properties of the present application are described in further detail below with reference to examples:
example 1
A method of processing a hybrid diamond-containing single crystal is provided. The rust agent is a two-component rust agent produced by Guangzhou mussel chemical engineering and comprises a component A and a component B. 300Kg of diamond containing impurities, a rusting agent and water are put into a container to be stirred and wetted evenly. Wherein, 30Kg of the component A of the rust agent is added with 60Kg of water with the ratio of 1:1, and the mixture is added into the materials, stirred evenly and stood for more than several minutes; 30Kg of the component B of the rust agent is added with 60Kg of water with the ratio of 1:1, and the mixture is added into the materials, stirred uniformly and kept stand for more than 30 minutes, and can be stirred for a plurality of times during the period, so that the components are oxidized and rusted uniformly; transferring the materials to a high-temperature roasting furnace in an aerobic atmosphere, roasting at 550 ℃ for 4 hours to further thoroughly oxidize the materials; transferring the materials into a heatable stirring container, such as a common reaction kettle; adding 45Kg of rust remover, namely adding water according to the proportion of 1:1.5, wherein the weight of the rust remover is about 112.5Kg, adding the rust remover into a reaction kettle, heating the material at 85 ℃ for 3 hours by taking the surface of the material submerged, stopping heating, and cooling; discharging the materials to a centrifugal dehydrator, and removing the derusting waste liquid; washing the material to neutrality, elutriating with pure water for more than 4 times, draining water, putting into a container, drying in a drying oven at below 200 deg.C. Wherein, the rust remover adopts the rust remover sold in the market by Zhengzhou Henan chemical industry company.
Example 2
A method for treating a hybrid diamond-containing powder is provided. The rust agent is a two-component rust agent produced by Guangzhou mussel chemical engineering and comprises a component A and a component B. Taking 100Kg of powder containing the hybrid diamond, and putting the powder into a container; adding 20Kg of the component A of the rusting agent into the material by adding 40Kg of water with the ratio of 1:1, uniformly stirring, and standing for more than 30 minutes; 20Kg of the component B of the rust agent is added with 40Kg of water with the ratio of 1:1, and the mixture is added into the materials and stirred evenly and stands for more than 60 minutes, and can be stirred for a plurality of times during the period to ensure that the components react evenly; firstly, transferring the materials into an acid-resistant and temperature-resistant vessel, and then transferring the materials into a high-temperature roasting furnace in an aerobic atmosphere, wherein the temperature is 500 ℃, and roasting is carried out for 4 hours; transferring the material into a reaction kettle capable of heating and stirring, adding 40Kg of rust remover, adding 120Kg of water according to a ratio of 1:2, adding into a container, wherein the surface of the material is submerged by the liquid surface of the rust remover, heating the material at 70 ℃ for 2 hours, stopping heating, and cooling; discharging reaction materials, and skimming the derusting waste liquid after the diamond powder is settled; washing the material to neutrality, and elutriating with pure water for more than 4 times, wherein the complete precipitation of the diamond powder is ensured during each elutriation, so as to avoid elutriation loss; then controlling the moisture, putting the mixture into a vessel, and drying the mixture at the temperature of below 150 ℃ by using drying equipment. Wherein, the rust remover adopts the rust remover sold in the market by Zhengzhou Henan chemical industry company.
Example 3
A method of processing a hybrid diamond-containing single crystal is provided. The rust agent is a single-component solid rust agent produced by Tengfenn chemical Co., Ltd, Luoyang, Henan province. Mixing 100Kg of diamond monocrystal containing a catalyst and graphite impurities with 3Kg of single-component solid-state rusting agent, adding water, stirring, putting into a vessel, reacting for more than 4 hours, then putting into a roasting furnace, heating to 550 ℃, preserving heat for 4 hours to ensure that residual catalyst and graphite in the material are sufficiently rusted and oxidized, then cooling to below 200 ℃ along with the furnace, discharging, and naturally cooling to room temperature; transferring the material into a reaction kettle, adding water according to the ratio of 1:2, adding 45Kg of rust remover into the reaction kettle, submerging the surface of the material, heating to 80 ℃, continuously reacting for 3 hours to remove the rust fully, stopping heating and cooling, discharging the material to a centrifugal dehydrator when the temperature is reduced to below 40 ℃, and separating out reaction waste liquid; the separated material was elutriated clean as in example 1.2 above and then oven dried in an oven below 200 ℃ to a clean product. Wherein, the rust remover adopts the rust remover sold in the market by Zhengzhou Henan chemical industry company.
Example 4
The steps of this example are the same as those of example 3, except that the diamond material is a diamond powder material, and the amount of the rust remover and the rust remover is doubled.
The method of examples 1 to 4 was examined for the effect of removing impurities by the following experimental examples.
Examples of the experiments
And (3) shooting by using a microscope, and testing the impurity removal effect in the diamond material removed by the method of the embodiment 1-4 from a macroscopic angle.
The results are shown in FIGS. 2 to 5. As can be seen from fig. 2 and 3, the cleanliness of the diamond single crystal after the treatment is significantly increased.
The purity of the diamond powder is judged by macroscopically observing the color after treatment, and further analyzing the impurity content of the diamond powder, wherein the impurity content is not impurities on the surfaces of the diamond powder and impurities with internal defects of the diamond powder. As can be seen from fig. 4 and 5, the color of the treated diamond powder changes from darker (dark brown) in fig. 4 to light color (light yellow, the picture is gray-scale-treated, and the actual color is light yellow), which indicates that the cleanliness of the diamond powder is obviously increased.
The impurity content of the diamond powders treated in examples 2 and 4 of the present application was determined according to standard JB/T10986-2010 and the results are shown in the following table:
as can be seen from the above table, the content of impurities in the diamond powder treated by the method of the embodiment of the present application is reduced to only 0.03%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (11)
1. A method for removing metal impurities and residual graphite in diamond material, which is characterized by comprising the following steps:
mixing and reacting a diamond material and a rusting agent until metal impurities are oxidized and rusted to obtain a first product;
roasting the first product in an oxygen atmosphere to continuously oxidize residual metal impurities and residual graphite to obtain a second product;
and mixing the second product with a neutral or weakly acidic rust remover for reaction, and removing rusted oxides to obtain the clean diamond.
2. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 1,
the step of mixing and reacting the diamond material and the rusting agent comprises the following steps:
and mixing the diamond material and the rusting agent, and reacting for at least 30 minutes.
3. A method of removing metallic impurities and residual graphite from a diamond mass according to claim 2, characterised in that the mixture of diamond mass, the rusting agent is stirred during the reaction.
4. The method of removing metallic impurities and residual graphite from a diamond mass according to claim 1 or 2,
when the rusting agent is mixed with the diamond material, the total mass ratio of the rusting agent to the diamond material is 8-40%.
5. The method of removing metallic impurities and residual graphite from a diamond mass according to claim 1 or 2,
the step of roasting and oxidizing the first product in an oxygen atmosphere comprises the following steps:
roasting at 450-600 ℃ for 0.5-5 hours.
6. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 1,
when the second product is mixed with the rust remover, the mass ratio of the rust remover to the second product is 10-30%.
7. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 6,
and mixing and reacting the second product with the rust remover and water at the temperature of below 100 ℃, wherein the reaction time is at least 1 hour.
8. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 7,
the reaction temperature is 60-90 ℃;
the reaction time is 1.5-5 hours.
9. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 1,
the rust remover and the rust remover are not used by adding water, or are used after being diluted by adding water;
wherein, when the water is added for dilution, the mass ratio is as follows:
the rust agent comprises: the water is within 1: 3; or
The rust remover comprises the following components: the water is within 1: 3.
10. The method of removing metallic impurities and residual graphite from a diamond mass according to claim 6, further comprising:
and cleaning a product obtained by mixing and reacting the second product with a rust remover and water.
11. The method for removing metallic impurities and residual graphite from a diamond mass according to claim 10,
and the cleaning step comprises removing waste liquid from the product to obtain a precipitate, cleaning the precipitate to be neutral, and drying at the temperature of below 200 ℃ to obtain a clean diamond product.
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| CN112551521B (en) * | 2020-11-09 | 2022-08-16 | 河南黄河旋风股份有限公司 | Environment-friendly diamond purification method based on high-temperature air |
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| RU2077476C1 (en) * | 1991-03-21 | 1997-04-20 | Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт технической физики | Method for cleaning ultradispersed diamonds |
| CN106276886A (en) * | 2015-05-22 | 2017-01-04 | 江苏益林金刚石工具有限公司 | A kind of method of purification of diamond |
| CN106587046A (en) * | 2016-12-30 | 2017-04-26 | 郑州大学 | Purification method of artificial diamond |
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| CN100396605C (en) * | 2005-07-29 | 2008-06-25 | 郑州人造金刚石及制品工程技术研究中心 | Purification technology of artificial diamond synthesis material |
| RU2007113361A (en) * | 2007-04-10 | 2008-10-27 | Ольга Алексеевна Козьменко (RU) | METHOD FOR DIAMOND CLEANING |
| CN100500560C (en) * | 2007-04-13 | 2009-06-17 | 中国地质大学（武汉） | Method of purifying ultra-fine diamond |
| JP2016094327A (en) * | 2014-11-11 | 2016-05-26 | 株式会社ダイセル | Method for manufacturing nanodiamond |
| KR101955445B1 (en) * | 2017-09-12 | 2019-03-08 | 한국기초과학지원연구원 | Method for the Chemical Purification of Nanodiamond |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2077476C1 (en) * | 1991-03-21 | 1997-04-20 | Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт технической физики | Method for cleaning ultradispersed diamonds |
| CN106276886A (en) * | 2015-05-22 | 2017-01-04 | 江苏益林金刚石工具有限公司 | A kind of method of purification of diamond |
| CN106587046A (en) * | 2016-12-30 | 2017-04-26 | 郑州大学 | Purification method of artificial diamond |
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Address after: 450000 No. 28, floor 3, building 1, No. 12, Dongqing street, high tech Industrial Development Zone, Zhengzhou, Henan Province Patentee after: Henan tianzuan crystal material Co.,Ltd. Patentee after: Zhecheng Xinrui Diamond Tools Co., Ltd Address before: 472000 2nd floor, No.6 standard workshop, Sanmenxia industrial agglomeration area, Sanmenxia City, Henan Province Patentee before: SANMENXIA TIANZUAN CRYSTAL MATERIALS Co.,Ltd. Patentee before: Zhecheng Xinrui Diamond Tools Co., Ltd |
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