CN116692852A - Preparation method of coal-based diamond based on catalyst method - Google Patents
Preparation method of coal-based diamond based on catalyst method Download PDFInfo
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- CN116692852A CN116692852A CN202310653901.XA CN202310653901A CN116692852A CN 116692852 A CN116692852 A CN 116692852A CN 202310653901 A CN202310653901 A CN 202310653901A CN 116692852 A CN116692852 A CN 116692852A
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- 239000003245 coal Substances 0.000 title claims abstract description 64
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 50
- 239000010432 diamond Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 230000005484 gravity Effects 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012265 solid product Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000005539 carbonized material Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003830 anthracite Substances 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000012778 molding material Substances 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 229910002804 graphite Inorganic materials 0.000 abstract description 7
- 239000010439 graphite Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a preparation method of coal-based diamond based on a catalyst method, which comprises the following steps: the method sequentially comprises the steps of separation by a gravity separation method, alkali dissolution treatment, acid dissolution treatment, extraction treatment and carbonization treatment to improve the aromatic carbon rate of a coal structure, so that a high-quality carbon source required by diamond synthesis is obtained, then the high-quality carbon source is mixed with a catalyst, pre-pressed and molded, and finally diamond synthesis is carried out under certain temperature and pressure conditions. The invention successfully replaces graphite with coal to synthesize diamond, which can obviously reduce the cost. In addition, the utilization range of coal is enlarged, the coal is pushed to be converted from a single fuel property to a raw material direction, and the method has important social significance for the consumption upgrading and the clean and efficient utilization of the coal and brings a new opportunity for the diamond industry.
Description
Technical Field
The invention belongs to the field of diamond artificial synthesis, relates to high-value conversion and utilization of coal, and in particular relates to a preparation method of coal-based diamond based on a catalyst method.
Background
The diamond as super-hard material has excellent thermal, optical, chemical and mechanical properties, semiconductor and other excellent properties, has the effect of being difficult to replace in the aspects of industry, medical treatment, national defense, science and technology and the like, and particularly has great application potential in electronic product parts as a new-generation semiconductor. In addition, the demand for diamond micropowder in precision machining is also increasing.
One of the main methods used for artificially synthesizing diamond is a static pressure catalyst method (catalyst method) which mainly consists in mixing graphite with a catalyst, pressing Cheng Danmo column, and converting graphite into diamond under the catalysis of a metal catalyst at 5.5gpa at 1200-1500 ℃.
At present, the carbon sources of the synthetic diamond are mainly nano graphite, micron graphite, onion carbon and amorphous carbon, while the pure natural graphite has harsh forming conditions and the corresponding carbon source has high price. Therefore, the search for a carbon-rich material that replaces graphite is a current challenge.
The method has rich coal resources in China, develops coal as a low-cost and high-purity carbon source to prepare high-quality diamond, provides new raw materials and methods for the synthetic diamond industry, and has great application value for coal consumption upgrading and clean and efficient utilization.
Disclosure of Invention
The invention aims to provide a preparation method of coal-based diamond based on a catalyst method, so that coal is used for replacing graphite to prepare diamond as a raw material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing coal-based diamond based on a catalyst method, comprising the following steps:
(1) Separating the coal sample by adopting a gravity separation method to obtain a coal sample light product from which minerals are removed; then washing and drying;
(2) Alkali dissolution treatment is carried out on the product obtained in the step (1) by alkali liquor so as to remove alkali-soluble substances in the product, and an alkali leaching sample is obtained; then washing and drying;
(3) Acid solution is utilized to carry out acid dissolution treatment on the product obtained in the step (2) so as to remove acid-soluble substances in the product, thus obtaining an acid leaching sample; then washing and drying;
(4) Mixing the product obtained in the step (3) with an extraction solvent, and then placing the mixture in a reaction kettle, extracting under the protection of nitrogen at the extraction temperature of 350-400 ℃, and carrying out solid-liquid separation after the extraction is completed to obtain extraction residues and extraction liquid respectively; recovering the extraction solvent in the extract liquid by reduced pressure distillation, separating out solid products, and then cleaning the residual extraction solvent on the obtained solid products and drying; wherein the extraction solvent is N-methyl pyrrolidone;
(5) Carbonizing the product obtained in the step (4) to obtain carbonized material;
(6) Crushing the carbonized material and catalyst mixture obtained in the step (5), and pre-pressing and molding to obtain a molded material;
(7) And (3) placing the molding material obtained in the step (6) into a cavity of a press, increasing the pressure to 5GPa-6GPa, increasing the temperature to 1200 ℃ to 1500 ℃, and synthesizing the diamond under the condition of keeping the temperature and the pressure stable.
In the step (1) of the invention, a gravity separation method is adopted according to the density difference of organic matters and mineral matters in the coal to separate light products from heavy products, and the light products floating on the surface of the liquid are recovered. In a preferred embodiment, coal samples of particle size ranging from 0.5mm to 6mm, such as 1mm, 2mm or 4mm, are added to a density of 1.20kg/cm when the coal samples are separated by gravity 3 -1.40kg/cm 3 Such as 1.30kg/cm 3 Is stirred and separated in the heavy medium suspension. After separation, the coal sample may be repeatedly rinsed with hot water until the heavy liquid adsorbed on the sample surface is washed, and then the sample is dried in an oven.
Preferably, in step (2), the alkali solution used in the alkali-dissolution treatment is sodium hydroxide solution, and the alkali solution concentration is 6mol/L to 9mol/L, preferably 6.5mol/L to 8mol/L such as 7mol/L or 7.5mol/L, and the reaction temperature is 60 ℃ to 90 ℃, preferably 70 ℃ to 85 ℃ such as 80 ℃, so as to remove the alkali-soluble substances better. Those skilled in the art understand that the amount of alkali may be excessive in order to sufficiently remove the alkali-soluble substance therein; for cost reasons, it is preferable that the ratio of the molar amount of sodium hydroxide of the alkali liquor to the mass of the product obtained in the step (1) is 0.03mol/g to 0.06mol/g, preferably 0.035mol/g to 0.056mol/g, and the alkali dissolution reaction time is 0.5 to 3 hours, preferably 1 to 2.5 hours such as 2 hours.
Preferably, in the step (3), when the acid dissolution treatment is carried out, the acid solution is hydrochloric acid, the concentration of the acid solution is 8mol/L-10mol/L, preferably 9mol/L-10mol/L, the reaction temperature is 60 ℃ to 90 ℃, preferably 70 ℃ to 85 ℃ such as 80 ℃, so as to better remove acid-soluble substances; those skilled in the art understand that the amount of acid may be excessive in order to sufficiently remove the acid-soluble substances therein; to achieve a cost, it is preferred that the ratio of the molar amount of hydrogen chloride in the acid solution to the mass of the product obtained in step (2) is from 0.1mol/g to 0.2mol/g, preferably from 0.15mol/g to 0.18mol/g, and the acid dissolution reaction time is from 0.5 to 3 hours, preferably from 1 to 2.5 hours such as 2 hours.
In the step (4) of the invention, the components which are beneficial to the subsequent synthesis of diamond are successfully extracted from the coal treated in the steps (1) - (3) by particularly selecting N-methylpyrrolidone as an extracting agent. In the preferred embodiment, in the step (4), the extraction temperature is 360-390 ℃, the extraction is carried out in the presence of a rotating stirring paddle, and the solid-liquid ratio of the extraction is controlled to be 1: (7-12), preferably 1: (9-11) such as 1:10, the stirrer rotation speed is 180-250rpm, preferably 190-230rpm such as 200rpm, and the extraction time is 0.5-3h, preferably 1-2.5h.
Preferably, in the step (4), when the solid product is cleaned, the solid product is alternately cleaned by using alcohol and deionized water.
In a preferred embodiment, in step (5), the carbonization treatment is performed under nitrogen atmosphere to remove the heterocyclic atoms for subsequent synthesis, the carbonization temperature is 800-1000 ℃, preferably 850-950 ℃, and the carbonization time is 3-7min, preferably 5-7min.
In step (6) of the present invention, the catalyst may be a catalyst for synthesizing diamond, which is well known in the art,see catalysts used in CN115400691A or CN106591943A, e.g. iron-nickel alloys, e.g. Fe 75 Ni 25 Or Fe (Fe) 70 Ni 30 The dosage ratio of the alloy to the carbonized material is (1-3): 1 such as 1:1 or 2:1, a step of; preferably, the mixture of carbonized material and catalyst is crushed to below 200 mesh, preferably 200-400 mesh, and then pre-pressed to shape.
In step (7) of the present invention, diamond is synthesized by a catalyst method. In one embodiment, in step (7), the press may be a hinged hexahedral press, as is well known in the art; the pressure may be 5.2-5.5GPa, the temperature may be 1250-1450 ℃, and the reaction time may be 15-60 min, such as 25min, 30min or 40min, to synthesize diamond. Those skilled in the art will appreciate that the separation of the synthesized product, such as by gravity separation using a density difference followed by acid-leaching the catalyst, is well known in the art and will not be described in detail herein.
In the preparation method of the invention, the products after the heavy separation, the alkali treatment and the acid treatment in the steps (1) - (3) are respectively washed to remove heavy liquid, alkali liquor and acid liquor respectively, preferably hot water is used for washing, and the washing effect is better, and the temperature of the hot water can be 60-90 ℃, such as 70 ℃ or 80 ℃.
In the production method of the present invention, the kind of raw coal for producing the coal sample may be various, such as long flame coal, coking coal or anthracite, preferably coking coal or anthracite.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, a physical-chemical combination method is adopted to purify organic matters in coal, ash is firstly removed preliminarily through a gravity separation method, so that the subsequent alkali pickling and washing treatment efficiency is improved, then the structure of the coal is promoted to be changed to a certain extent through alkali pickling and washing, the content of hydroxyl functional groups of the coal is reduced, the ratio of carboxylic acid to phenolic hydroxyl is increased, the effects of destroying molecular hydrogen bonds in the coal and the like of an extraction solvent are facilitated, and the extraction effect of the coal is improved; finally, oxygen and hydrogen in the coal are directionally removed by a solvent extraction method and high-temperature carbonization, so that aromatization of an organic basic structural unit in the coal is realized, and a high-quality carbon source required by diamond synthesis is obtained.
2. According to the invention, the treated carbonized material and the catalyst are directly mixed and then pre-pressed and molded, and then the mixture is put into a hexahedral press, the synthesis of the diamond by coal is carried out based on the catalyst method, and the coal source is successfully used for replacing the traditional natural graphite as the carbon source, so that the aim of synthesizing the diamond by coal, which is expected to be realized in the field for a long time, is fulfilled, and the cost of diamond synthesis is obviously reduced. The diamond made of coal can expand the utilization range of coal, so that the diamond is not limited to the industries of coal-fired power generation and traditional coal chemical industry, the coal is pushed to be converted from single fuel property to raw material direction, and the diamond has important social significance for coal consumption upgrading and clean and efficient utilization and brings new opportunities for the diamond industry.
Drawings
Figure 1 is an XRD pattern of the product of example 1.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. It is to be understood that the embodiments described below may take on alternative variations and embodiments. It should also be understood that the specific articles, compositions, and/or methods described herein are exemplary and should not be considered limiting. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Unless explicitly stated otherwise, the term "substantially" such as "substantially the same" as used herein will be understood to encompass parameters having fluctuations within a suitable range, for example having ±10% or ±15% fluctuations of the parameter. In some embodiments, the range of fluctuation is within ±10%.
Unless otherwise indicated, all reagents used in the following examples were analytically pure.
Example 1
Diamond was synthesized by the following steps:
(1) A long flame coal sample in the particle size range of 0.5mm to 6mm was added to 1.30kg/cm 3 Uniformly stirring, fishing out light products floating on the surface of the liquid by adopting a fishing spoon, and then washing and drying by adopting hot water.
(2) The dried sample from the previous step is added into an excessive sodium hydroxide solution of 8mol/L, reacted for 2 hours at 80 ℃ to obtain an alkaline leaching sample, and then washed and dried by hot water.
(3) The alkali leached coal sample obtained in the last step is added into an excessive hydrochloric acid solution of 8mol/L, reacted for 2 hours at 80 ℃, and then washed by hot water and dried.
(4) And (3) controlling the solid-liquid ratio to be 1:10, mixing the coal sample obtained in the step (3) with an extraction solvent (N-methylpyrrolidone), and placing the mixture in a reaction kettle. Under the protection of nitrogen, the extraction temperature is controlled to be 380 ℃, the rotating speed of a stirring paddle is 200rpm, and the reaction is carried out for 1h. After the reaction is finished, solid-liquid separation is carried out through a filter element at the bottom of the reaction kettle, and extraction residues and extraction solution are respectively obtained. The extraction solvent in the extract was recovered by distillation under reduced pressure and solid product was precipitated. The solid product was repeatedly rinsed with alcohol and deionized water and dried in an oven.
(5) And (3) further placing the solid product into a carbonization device, and carbonizing at 900 ℃ for 6min under nitrogen atmosphere to remove part of heterocyclic atoms, so as to obtain the high-purity carbonized material required by diamond synthesis.
(6) The obtained carbonized material and catalyst Fe 70 Ni 30 The alloy comprises the following components in percentage by mass: 2, fully grinding the mixture to below 200 meshes after mixing the mixture in proportion, and prepressing and forming the mixture.
(7) The pre-pressed forming material is put into a domestic hinged hexahedral top press, then the pressure is increased to 5.5Gpa, the temperature is increased to 1400 ℃, and the temperature and the pressure are kept constant to react for 30min, so as to synthesize the diamond.
XRD detection was performed on diamond separated from the product obtained in example 1, and it was confirmed that it belongs to diamond as shown in FIG. 1.
Example 2
Diamond was synthesized by the following steps:
(1) Adding a coking coal sample with the granularity ranging from 0.5mm to 6mm into the mixture of 1.30kg/cm 3 Uniformly stirring, fishing out light products floating on the surface of the liquid by adopting a fishing spoon, and then washing and drying by adopting hot water.
(2) The dried sample from the previous step is added into 7mol/L of excessive sodium hydroxide solution, reacted for 2 hours at 90 ℃ to obtain an alkali leaching sample, and then washed and dried by adopting hot water.
(3) The alkali leached coal sample obtained in the last step is added into 9mol/L of excessive hydrochloric acid solution to react for 3 hours at 60 ℃, and then is washed by hot water and dried.
(4) And (3) controlling the solid-liquid ratio to be 1:7, mixing the coal sample obtained in the step (3) with an extraction solvent (N-methylpyrrolidone), and placing the mixture in a reaction kettle. Under the protection of nitrogen, the extraction temperature is controlled to be 390 ℃, the rotating speed of a stirring paddle is 250rpm, and the reaction is carried out for 1h. After the reaction is finished, solid-liquid separation is carried out through a filter element at the bottom of the reaction kettle, and extraction residues and extraction solution are respectively obtained. The extraction solvent in the extract was recovered by distillation under reduced pressure and solid product was precipitated. The solid product was repeatedly rinsed with alcohol and deionized water and dried in an oven.
(5) And (3) further placing the solid product into a carbonization device, and carbonizing at 850 ℃ for 7min under nitrogen atmosphere to remove part of heterocyclic atoms, thereby obtaining the high-purity carbonized material required by diamond synthesis.
(6) The obtained carbonized material and catalyst Fe 70 Ni 30 The alloy comprises the following components in percentage by mass: 3, fully grinding the mixture to below 200 meshes after mixing the mixture in proportion, and pre-pressing and forming the mixture.
(7) The pre-pressed forming material is put into a domestic hinged hexahedral top press, then the pressure is increased to 5.2Gpa, the temperature is increased to 1500 ℃, and the temperature and the pressure are kept constant to react for 25 minutes, so as to synthesize the diamond.
XRD detection was performed on the diamond obtained in example 2, and the XRD was substantially the same as that of FIG. 1, confirming that it belongs to diamond.
Example 3
Diamond was synthesized by the following steps:
(1) Anthracite coal samples in the particle size range of 0.5mm to 6mm were added to 1.30kg/cm 3 Uniformly stirring, fishing out light products floating on the surface of the liquid by adopting a fishing spoon, and then washing and drying by adopting hot water.
(2) The dried sample from the previous step is added into 10mol/L of excessive sodium hydroxide solution, reacted for 2 hours at 90 ℃ to obtain an alkali leaching sample, and then washed and dried by adopting hot water.
(3) The alkali leached coal sample obtained in the last step is added into 7mol/L of excessive hydrochloric acid solution to react for 3 hours at 85 ℃, and then washed by hot water and dried.
(4) And (3) controlling the solid-liquid ratio to be 1:12, mixing the coal sample obtained in the step (3) with an extraction solvent (N-methylpyrrolidone), and placing the mixture in a reaction kettle. Under the protection of nitrogen, the extraction temperature is controlled to be 360 ℃, the rotating speed of a stirring paddle is 250rpm, and the reaction is carried out for 1h. After the reaction is finished, solid-liquid separation is carried out through a filter element at the bottom of the reaction kettle, and extraction residues and extraction solution are respectively obtained. The extraction solvent in the extract was recovered by distillation under reduced pressure and solid product was precipitated. The solid product was repeatedly rinsed with alcohol and deionized water and dried in an oven.
(5) And (3) further placing the solid product into a carbonization device, and carbonizing at 950 ℃ for 5min under nitrogen atmosphere to remove part of heterocyclic atoms, thereby obtaining the high-purity carbonized material required by diamond synthesis.
(6) The obtained carbonized material and catalyst Fe 70 Ni 30 The alloy comprises the following components in percentage by mass: 3, fully grinding the mixture to below 200 meshes after mixing the mixture in proportion, and pre-pressing and forming the mixture.
(7) And (3) placing the pre-pressed molding material into a domestic hinged hexahedral top press, then raising the pressure to 5.2Gpa, further raising the temperature to 1500 ℃, and keeping the temperature and the pressure constantly for reaction for 15min to synthesize the diamond.
XRD detection was performed on the diamond obtained in example 3, and the XRD was substantially the same as that of FIG. 1, confirming that it belongs to diamond.
From the above examples, it is apparent that the technology of the present invention can be applied to successfully synthesize diamond by a catalytic method using coal.
Claims (10)
1. A method for preparing coal-based diamond based on a catalyst method, which is characterized by comprising the following steps:
(1) Separating the coal sample by adopting a gravity separation method to obtain a coal sample light product from which minerals are removed; then washing and drying;
(2) Alkali dissolution treatment is carried out on the product obtained in the step (1) by alkali liquor so as to remove alkali-soluble substances in the product, and an alkali leaching sample is obtained; then washing and drying;
(3) Acid solution is utilized to carry out acid dissolution treatment on the product obtained in the step (2) so as to remove acid-soluble substances in the product, thus obtaining an acid leaching sample; then washing and drying;
(4) Mixing the product obtained in the step (3) with an extraction solvent, and then placing the mixture in a reaction kettle, extracting under the protection of nitrogen at the extraction temperature of 350-400 ℃, and carrying out solid-liquid separation after the extraction is completed to obtain extraction residues and extraction liquid respectively; recovering the extraction solvent in the extract liquid by reduced pressure distillation, separating out solid products, and then cleaning the residual extraction solvent on the obtained solid products and drying; wherein the extraction solvent is N-methyl pyrrolidone;
(5) Carbonizing the product obtained in the step (4) to obtain carbonized material;
(6) Crushing the carbonized material and catalyst mixture obtained in the step (5), and pre-pressing and molding to obtain a molded material;
(7) And (3) placing the molding material obtained in the step (6) into a cavity of a press, increasing the pressure to 5GPa-6GPa, increasing the temperature to 1200 ℃ to 1500 ℃, and synthesizing the diamond under the condition of keeping the temperature and the pressure stable.
2. The method according to claim 1The preparation method is characterized in that in the step (1), when the coal sample is separated by adopting a gravity separation method, the coal sample with the granularity ranging from 0.5mm to 6mm is added into the coal sample with the density of 1.20kg/cm 3 -1.40kg/cm 3 Is stirred and separated in the heavy medium suspension.
3. The process according to claim 1 or 2, wherein in the step (2), alkali solution is sodium hydroxide solution, the alkali solution concentration is 6mol/L to 9mol/L, and the reaction temperature is 60 ℃ to 90 ℃.
4. The process according to any one of claims 1 to 3, wherein in the step (3), the acid solution used in the acid-dissolving treatment is hydrochloric acid, the acid solution concentration is 8mol/L to 10mol/L, and the reaction temperature is 60℃to 90 ℃.
5. The process according to any one of claims 1 to 4, wherein in step (4), extraction is performed in the presence of a rotating stirring paddle, and the extraction solid-to-liquid ratio is controlled to be 1: (7-12), the rotating speed of the stirring paddle is 180-250rpm, and the extraction time is 0.5-3 h.
6. The method according to any one of claims 1 to 5, wherein in the step (4), the solid product is alternately washed with alcohol and deionized water when the solid product is washed.
7. The method according to any one of claims 1 to 6, wherein in the step (5), the carbonization treatment is performed under a nitrogen atmosphere at 800 ℃ to 1000 ℃ for 3min to 7min.
8. The method according to any one of claims 1 to 7, wherein in the step (6), the catalyst is an iron-nickel alloy, and the ratio of the catalyst to the carbonized material is (1-3): 1, a step of; preferably, the mixture of carbonized material and catalyst is crushed to below 200 meshes and then pre-pressed to shape.
9. The method according to any one of claims 1 to 8, wherein in step (7), the press is a hinged hexahedral press, the pressure is 5.2GPa-5.5GPa, the temperature is 1250 ℃ -1450 ℃, and the reaction time is 15min-60min.
10. The production method according to any one of claims 1 to 9, wherein the kind of raw coal for producing the coal sample is long flame coal, coking coal or anthracite coal.
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