CN107651959B - preparation of iron phosphide Fe under high temperature and high pressure2Method of P - Google Patents

preparation of iron phosphide Fe under high temperature and high pressure2Method of P Download PDF

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CN107651959B
CN107651959B CN201711066574.9A CN201711066574A CN107651959B CN 107651959 B CN107651959 B CN 107651959B CN 201711066574 A CN201711066574 A CN 201711066574A CN 107651959 B CN107651959 B CN 107651959B
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尹远
翟双猛
李泽明
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Institute of Geochemistry of CAS
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Abstract

The invention discloses a method for preparing ferrophosphorus under high temperature and high pressure, which comprises the steps of using analytically pure iron nano powder and red phosphorus powder as starting raw materials, fully grinding and mixing the raw materials in an agate mortar according to a molar ratio of 2: 1 by using alcohol, pressing the ground mixed powder into a cylindrical sample by using a tablet press, processing a boron nitride ceramic rod into a round pipe, drying the round pipe in an oven, putting the cylindrical sample into the boron nitride round pipe, sealing the upper part and the lower part of the boron nitride round pipe by using a boron nitride ceramic plate, putting the whole body into a cubic apparatus press for high temperature and high pressure reaction, taking out the reacted sample, and removing boron nitride outside the sample to obtain a pure ferrophosphorus blocky sample, and the technical problems that reaction variables are difficult to control, a quartz pipe is corroded, the reaction time is long, the product purity is low, the crystallinity is low, the product is powder or small particles and cannot be processed in a later period in the prior art are solved.

Description

preparation of iron phosphide Fe under high temperature and high pressure2Method of P
Technical Field
The invention belongs to the field of functional material synthesis, and particularly relates to methods for preparing iron phosphide Fe under high temperature and high pressure2And (P) is a method.
Background
Industrially, iron phosphide Fe2P is also called ferrous phosphide, a by-product of phosphorus chemical industry, is widely applied to the industries of metallurgy, smelting and chemical industry, ultrafine ferrophosphorus powder has the characteristics of electric conduction, heavy corrosion resistance, marine organism adsorption resistance, environmental protection and the like, is a new technological product in the industries of paint and coating, particularly has the advantages of environmental protection, protection of the health of electric welding workers, low price and heavy corrosion resistance on replacing zinc powderCan provide abundant experimental data for magnetic refrigeration technology.
The ferrophosphorus existing in the market at present is partially from industrial production, but the impure phase, such as ferrophosphorus , ferrophosphorus, ferrosilicon and the like, is more, and is difficult to control and purify a single-phase pure ferrophosphorus finished product, at present, methods for preparing ferrophosphorus mainly comprise a tube furnace heating method, a hydrothermal synthesis method and a temperature programmed reduction method in a TPR-hydrogen atmosphere, and a method for preparing ferrophosphorus under the protection of argon by using iron phosphate as a precursor potassium borohydride as a reducing agent in the publication No. CN 102442652A, wherein the main advantages and disadvantages of the methods are as follows:
the ferrophosphorus is prepared by a tubular furnace method, and has the following defects that red phosphorus which is an initial material of reaction is sublimated when being heated to about 400 ℃ to generate phosphorus vapor, so that the phosphorus content of the whole reaction is difficult to control, a large amount of excessive elemental phosphorus is needed, and in addition, the phosphorus vapor can react with a quartz tube under the high temperature condition to corrode the heating furnace.
The iron phosphide prepared by the hydrothermal synthesis method has poor catalytic performance as a catalyst, and the hydrothermal method has long time and long period.
The temperature programmed reduction method in TPR-hydrogen atmosphere uses transition metal phosphate as a precursor, has the advantages of low cost and high safety performance, the obtained product is relatively pure and is applied to , but the temperature and the reaction time of the method need to be strictly controlled, and the temperature rise time is relatively long.
The ferrophosphorus is prepared under the protection of argon by using iron phosphate as a precursor potassium borohydride as a reducing agent, and although a purer ferrophosphorus particle sample can be obtained, the production process is complex, the argon protection is needed, the vacuum drying time is too long, generally needs more than 12 hours, the production period is long, the obtained product particles are small, and the post-processing is difficult.
Disclosure of Invention
The technical problem to be solved by the invention is that kinds of iron phosphide Fe are prepared under high temperature and high pressure2The method of P is used for solving the technical problems that the operation process is complex, the aging of experimental equipment is accelerated, the reaction time is long, the obtained ferrophosphide product has low purity and low crystallinity, is powdery or granular, is difficult to process in later period and the like in the prior art.
The technical scheme of the invention is that kinds of iron phosphide Fe are prepared under high temperature and high pressure2P, which comprises:
step 1: analytically pure reduced iron powder and red phosphorus powder are used as starting materials;
step 2: mixing iron nano powder and red phosphorus powder according to a molar ratio of 2: 1, mixing, putting into a mortar, adding alcohol, and grinding until the liquid is completely volatilized;
and step 3: placing the ground mixed powder into a circular mold by using a tablet press for tabletting to obtain a cylindrical sample;
and 4, step 4: processing a boron nitride BN ceramic rod into a round tube, and drying in an oven;
and 5: putting the sample pre-pressed and molded in the step 3 into the boron nitride round tube in the step 4, and sealing the upper part and the lower part of the sample by using a boron nitride ceramic plate;
step 6: assembling the cylindrical sample prepared in the step 5 in a high-pressure synthesis assembly block and placing the cylindrical sample in a cubic apparatus large press for high-temperature high-pressure reaction;
and 7, taking out the reacted sample, and removing the boron nitride sleeve outside the sample to obtain a pure ferrophosphide blocky sample.
The specific preparation method in the step 5 comprises the following steps: and (3) machining the boron nitride ceramic rod into a circular tube with the length of 10mm, the outer diameter of 10mm and the inner diameter of 6mm by using a lathe, wherein the circular tube is used as a sleeve for wrapping the sample, then putting the cylindrical sample obtained in the step (3) into the circular tube, and sealing the upper part and the lower part of the circular tube by using a boron nitride ceramic plate.
The method for synthesizing the assembly block by high pressure in the step 6 comprises the following steps:
6.1, selecting pyrophyllite blocks, and punching circular through holes in the centers of the pyrophyllite blocks;
step 6.2, sleeving cylindrical graphite heating furnaces in the circular through holes;
6.3, placing a sample wrapped by a boron nitride tube in the middle of a graphite heating furnace;
and 6.4, sealing the upper end and the lower end of the circular graphite heating furnace by pyrophyllite plugs.
And a thermocouple is arranged in the high-pressure synthesis assembly block.
The temperature of the high-temperature high-pressure reaction in the step 6 is 800-1200 ℃, the pressure is 1-3GPa, and the reaction time is 1-5 hours.
The pure ferrophosphorus of step 7 is a single phase, has no impurity phase, has a hexagonal structure, has a space group of P-62m (No.189), and has lattice parameters
Figure BDA0001455914370000031
Has good metallic luster, and is typical alloy materials.
The invention has the beneficial effects that:
adopting analytically pure iron nano powder and red phosphorus powder as starting raw materials, and obtaining iron phosphide samples by a solid-phase reaction method at high temperature and high pressure, wherein the principle is as follows:
2Fe+P－Fe2P
1. the ferrophosphorus prepared by the invention is a single -phase sample with high purity, and the high-temperature high-pressure experimental sample is wrapped by high-density boron nitride ceramic and is carried out in a closed cavity, so that the volatilization loss of red phosphorus is avoided, the reaction can be strictly carried out according to the nominal proportion, and the pure ferrophosphorus is obtained.
2. Compared with the iron phosphide sintered by the normal-pressure synthesis method, the iron phosphide prepared by the CN 102442652A patent has small particles and is not easy to be processed later, so that the difficulty of resistivity test is caused.
3. The ferrophosphide prepared by the invention is a sample with good crystallinity, the decomposition temperature of the material can be increased under high pressure, so that the reaction temperature for synthesizing ferrophosphide at high temperature and high pressure is much higher than that of normal pressure sintering, therefore, the higher reaction temperature not only completes the high-temperature and high-pressure solid phase reaction, but also completes the recrystallization reaction of the sample, so that the crystallinity of the ferrophosphide sample is greatly improved, compared with ferrophosphide sample with large crystal grains, the crystallinity of ferrophosphide sintered by the normal pressure synthesis method is very poor, and the requirement of the spectral test of Raman scattering and the like on the crystallinity of the sample can not be met.
In conclusion, the method overcomes the problems that the phosphorus content of the whole reaction is difficult to control by a tube furnace heating method and phosphorus steam corrodes a heating tube furnace, the problems that ferrophosphide prepared by a hydrothermal synthesis method is poor in catalytic performance and long in hydrothermal method time, the problems that the temperature and the reaction time of a temperature-raising reduction method need to be strictly controlled in a TPR-hydrogen atmosphere and the temperature-raising time is long are solved, and the problems that the method disclosed in the publication No. CN 102442652A has a long production period and the obtained product has small particles and is difficult to process in a later period are solved.
Drawings
FIG. 1 is an XRD pattern of iron phosphide prepared in example 3 of the present invention;
FIG. 2 is a BSE plot of iron phosphide prepared in example 3 of the present invention;
FIG. 3 is a Raman plot of ferrophosphorus prepared in example 3 of the present invention.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments:
example 1
Analytically pure iron nano powder (Fe) and red phosphorus powder (P) were used as starting materials, which were mixed in a molar ratio of 2: 1, fully grinding and mixing the mixture in an agate mortar by using alcohol, taking 0.30g of iron-phosphorus mixed powder, pressing the iron-phosphorus mixed powder into a cylinder with the diameter of 6mm multiplied by 6mm by using a powder tablet press, processing a boron nitride ceramic rod into a boron nitride ceramic tube with the length of 10mm, the outer diameter of 10mm and the inner diameter of 6mm, drying the boron nitride ceramic tube in an oven at the temperature of 150 ℃ for 2 hours, putting the powder cylinder body into the boron nitride ceramic tube, and sealing the upper part and the lower part by using a 2mm boron nitride ceramic plate to finish the high-pressure assembly block. Assembling a high-pressure assembling block:
① 32mm by 32mm pyrophyllite cube center drilling circular through holes with diameter of 12 mm;
graphite sleeve heating furnaces with the outer diameter of 12mm and the inner diameter of 10mm are sleeved in the circular through hole of the ② pyrophyllite block;
③ A boron nitride cylinder containing iron-phosphorus mixed powder is placed in the middle of the graphite sleeve heating furnace, and the upper part and the lower part are plugged by pyrophyllite plugs with the diameter of 10 mm.
The invention has the advantages that ① uses a thermocouple to control temperature, a heating system adjusts heating power through the temperature fed back by the thermocouple so as to change the temperature, the method can realize instant monitoring of the temperature and is suitable for experiments with high temperature measurement precision, ② pyrophyllite is used as -grade pressure transmission medium and has good pressure transmission, machinability, heat resistance and insulation, boron nitride is ceramic materials with strong processability and is used as a secondary pressure transmission medium, so that the pressure in a cavity is uniform, the sealing performance is good, the boron nitride is stable, the quality of products cannot be polluted and damaged, the most suitable sealing material is prepared by ferrophosphorus, and a ③ graphite furnace is used as a heating furnace, and the temperature uniformity is high.
And (3) putting the assembled block into a cubic apparatus press for high-temperature high-pressure reaction, setting the temperature to be 800 ℃, the pressure to be 1GPa and the reaction time to be 5h, taking out the obtained sample after the high-temperature high-pressure reaction is finished, and removing boron nitride on the surface of the sample to obtain a pure ferrophosphide sample, wherein the result of X-ray diffraction electronic probe analysis shows that the ferrophosphide prepared by the preparation method is a single phase and has no impurity phase.
Example 2
Analytically pure iron nano powder (Fe) and red phosphorus powder (P) were used as starting materials, which were mixed in a molar ratio of 2: 1, fully grinding and mixing the mixture in an agate mortar by using alcohol, taking 0.30g of iron-phosphorus mixed powder, pressing the iron-phosphorus mixed powder into a cylinder with the diameter of 6mm multiplied by 6mm by using a powder tablet press, processing a boron nitride ceramic rod into a boron nitride ceramic tube with the length of 10mm, the outer diameter of 10mm and the inner diameter of 6mm, drying the boron nitride ceramic tube in an oven at the temperature of 150 ℃ for 2 hours, putting the powder cylinder body into the boron nitride ceramic tube, and sealing the upper part and the lower part by using a 2mm boron nitride ceramic plate to finish the high-pressure assembly block. Assembling a high-pressure assembling block:
① 32mm by 32mm pyrophyllite cube center drilling circular through holes with diameter of 12 mm;
graphite sleeve heating furnaces with the outer diameter of 12mm and the inner diameter of 10mm are sleeved in the circular through hole of the ② pyrophyllite block;
③ A boron nitride cylinder containing iron-phosphorus mixed powder is placed in the middle of the graphite sleeve heating furnace, and the upper part and the lower part are plugged by pyrophyllite plugs with the diameter of 10 mm.
The invention has the advantages that ① uses a thermocouple to control temperature, a heating system adjusts heating power through the temperature fed back by the thermocouple so as to change the temperature, the method can realize instant monitoring of the temperature and is suitable for experiments with high temperature measurement precision, ② pyrophyllite is used as -grade pressure transmission medium and has good pressure transmission, machinability, heat resistance and insulation, boron nitride is ceramic materials with strong processability and is used as a secondary pressure transmission medium, so that the pressure in a cavity is uniform, the sealing performance is good, the boron nitride is stable, the quality of products cannot be polluted and damaged, the most suitable sealing material is prepared by ferrophosphorus, and a ③ graphite furnace is used as a heating furnace, and the temperature uniformity is high.
And (2) putting the assembled block into a cubic apparatus press for high-temperature high-pressure reaction, setting the temperature at 1200 ℃, the pressure at 3GPa and the reaction time at 1h, taking out the obtained sample after the high-temperature high-pressure reaction is finished, and removing boron nitride on the surface of the sample to obtain a pure ferrophosphide sample, wherein the result of X-ray diffraction electronic probe analysis shows that the ferrophosphide prepared by the preparation method is a single phase and has no impurity phase.
Embodiment 3
Analytically pure iron nano powder (Fe) and red phosphorus powder (P) were used as starting materials, which were mixed in a molar ratio of 2: 1, fully grinding and mixing the mixture in an agate mortar by using alcohol, taking 0.30g of iron-phosphorus mixed powder, pressing the iron-phosphorus mixed powder into a cylinder with the diameter of 6mm multiplied by 6mm by using a powder tablet press, processing a boron nitride ceramic rod into a boron nitride ceramic tube with the length of 10mm, the outer diameter of 10mm and the inner diameter of 6mm, drying the boron nitride ceramic tube in an oven at the temperature of 150 ℃ for 2 hours, putting the powder cylinder body into the boron nitride ceramic tube, and sealing the upper part and the lower part by using a 2mm boron nitride ceramic plate to finish the high-pressure assembly block. Assembling a high-pressure assembling block:
① 32mm by 32mm pyrophyllite cube center drilling circular through holes with diameter of 12 mm;
graphite sleeve heating furnaces with the outer diameter of 12mm and the inner diameter of 10mm are sleeved in the circular through hole of the ② pyrophyllite block;
③ A boron nitride cylinder containing iron-phosphorus mixed powder is placed in the middle of the graphite sleeve heating furnace, and the upper part and the lower part are plugged by pyrophyllite plugs with the diameter of 10 mm.
The invention has the advantages that ① uses a thermocouple to control temperature, a heating system adjusts heating power through the temperature fed back by the thermocouple so as to change the temperature, the method can realize instant monitoring of the temperature and is suitable for experiments with high temperature measurement precision, ② pyrophyllite is used as -grade pressure transmission medium and has good pressure transmission, machinability, heat resistance and insulation, boron nitride is ceramic materials with strong processability and is used as a secondary pressure transmission medium, so that the pressure in a cavity is uniform, the sealing performance is good, the boron nitride is stable, the quality of products cannot be polluted and damaged, the most suitable sealing material is prepared by ferrophosphorus, and a ③ graphite furnace is used as a heating furnace, and the temperature uniformity is high.
The assembled block is placed in a cubic apparatus press to carry out high-temperature high-pressure reaction, the set temperature is 1000 ℃, the pressure is 2GPa, the reaction time is 3h, after the high-temperature high-pressure reaction is finished, the obtained sample is taken out, boron nitride on the surface of the sample is removed, and a pure ferrophosphide sample can be obtained.
It will be apparent to those skilled in the art that many more modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the following claims .

Claims (4)

  1. Preparation of iron phosphide Fe at high temperature and high pressure from 1, kinds2P, which comprises:
    step 1: analytically pure reduced iron powder and red phosphorus powder are used as starting materials;
    step 2: mixing iron nano powder and red phosphorus powder according to a molar ratio of 2: 1, mixing, putting into a mortar, adding alcohol, and grinding until the liquid is completely volatilized;
    and step 3: placing the ground mixed powder into a circular mold by using a tablet press for tabletting to obtain a cylindrical sample;
    and 4, step 4: processing a boron nitride BN ceramic rod into a round tube, and drying in an oven;
    and 5: putting the sample pre-pressed and molded in the step 3 into the boron nitride round tube in the step 4, and sealing the upper part and the lower part of the sample by using a boron nitride ceramic plate;
    step 6: assembling the cylindrical sample prepared in the step 5 in a high-pressure synthesis assembly block and placing the cylindrical sample in a cubic apparatus large press for high-temperature high-pressure reaction;
    the method for synthesizing the assembly block by high pressure in the step 6 comprises the following steps:
    6.1, selecting pyrophyllite blocks, and punching circular through holes in the centers of the pyrophyllite blocks;
    step 6.2, sleeving cylindrical graphite heating furnaces in the circular through holes;
    6.3, placing a sample wrapped by a boron nitride tube in the middle of a graphite heating furnace;
    step 6.4, sealing the upper end and the lower end of the round graphite heating furnace by pyrophyllite plugs;
    6, the temperature of the high-temperature high-pressure reaction is 800-1200 ℃, the pressure is 1-3GPa, and the reaction time is 1-5 hours;
    and 7, taking out the reacted sample, and removing the boron nitride sleeve outside the sample to obtain a pure ferrophosphide blocky sample.
  2. 2. kinds of the iron phosphide Fe prepared under high temperature and high pressure according to claim 12P, characterized in that: the specific preparation method in the step 5 comprises the following steps: and (3) machining the boron nitride ceramic rod into a circular tube with the length of 10mm, the outer diameter of 10mm and the inner diameter of 6mm by using a lathe, wherein the circular tube is used as a sleeve for wrapping the sample, then putting the cylindrical sample obtained in the step (3) into the circular tube, and sealing the upper part and the lower part of the circular tube by using a boron nitride ceramic plate.
  3. 3. kinds of the iron phosphide Fe prepared under high temperature and high pressure according to claim 12P, characterized in that: and a thermocouple is arranged in the high-pressure synthesis assembly block.
  4. 4. kinds of the iron phosphide Fe prepared under high temperature and high pressure according to claim 12The method for P is characterized in that the pure ferrophosphorus in the step 7 is a single phase, has no impurity phase, has a hexagonal structure, has a space group of P-62m (No.189), has a lattice parameter of a = 5.86 Å and a lattice parameter of c = 3.45 Å, has good metallic luster, and is typical alloy materials.
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CN108352230A (en) * 2015-10-30 2018-07-31 巴斯夫欧洲公司 Include the magneto-caloric material of manganese, iron, silicon, phosphorus and nitrogen
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