CN112427648B - Preparation method and preparation device of metal molybdenum powder - Google Patents
Preparation method and preparation device of metal molybdenum powder Download PDFInfo
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- CN112427648B CN112427648B CN202011377293.7A CN202011377293A CN112427648B CN 112427648 B CN112427648 B CN 112427648B CN 202011377293 A CN202011377293 A CN 202011377293A CN 112427648 B CN112427648 B CN 112427648B
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- molybdenum powder
- metal molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
A method and a device for preparing metal molybdenum powder. The disclosed preparation method comprises mixing raw materials of molybdenum disulfide or molybdenite with a proper amount of auxiliary conductive material, and then pressing and forming the mixture into a blank, wherein the auxiliary conductive material is selected from materials which can assist in conducting electricity and do not react with metal molybdenum powder; and in an environment of 200-1300 ℃, directly electrifying the blank, carrying out decomposition reaction on the raw materials under the coupling action of a temperature field and an electric field, recovering sulfur released in the decomposition reaction process, and recovering the auxiliary conductive material in the metal molybdenum powder after the reaction is finished to obtain the metal molybdenum powder. The disclosed apparatus mainly comprises a decomposition furnace and an electrode provided in the decomposition furnace. The method for preparing the metal molybdenum powder has the advantages of simple process, energy conservation, consumption reduction and environmental protection.
Description
Technical Field
The invention relates to a production technology of metal molybdenum powder, in particular to a multi-field coupling preparation process of molybdenum powder.
Background
The metal molybdenum powder is an important raw material added in molybdenum materials, products and ferrous metallurgy, and the traditional production process is prepared from molybdenite through multiple processes.
The preparation of molybdenum powder and sulfur by direct decomposition of molybdenum disulfide or molybdenite has been an ideal production mode pursued by the metallurgical industry, and long-term research has been conducted by scholars at home and abroad. However, the existing vacuum decomposition temperature reaches 1750 ℃, the temperature is high, the decomposition time is long, and the equipment requirement is high, which is an important problem.
Disclosure of Invention
In order to overcome the defects or shortcomings of the prior art, the invention provides a method for preparing metal molybdenum powder.
Therefore, the preparation method of the metal molybdenum powder provided by the invention comprises the following steps:
mixing a raw material molybdenum disulfide or molybdenite with a proper amount of auxiliary conductive material, and then pressing the mixture to form a blank, wherein the auxiliary conductive material is selected from materials which can assist in conducting electricity and do not react with metal molybdenum powder;
and in an environment of 200-1300 ℃, directly electrifying the blank, carrying out decomposition reaction on the raw materials under the coupling action of a temperature field and an electric field, recovering sulfur released in the decomposition reaction process, and recovering the auxiliary conductive material in the metal molybdenum powder after the reaction is finished to obtain the metal molybdenum powder.
Optionally, the auxiliary conductive material is selected from one or a mixture of two of metal molybdenum powder or aluminum oxide, the added mass of the auxiliary conductive material accounts for 1 wt% -20 wt% of the mass of the raw materials, and the auxiliary conductive material is recovered according to the specific gravity difference between the auxiliary conductive material and the metal molybdenum powder after the reaction is finished.
Optionally, the environmental pressure is a vacuum state less than 200Pa, and sulfur is recovered under vacuum conditions.
Optionally, the blank is directly electrified at 1300 ℃, under normal pressure and hydrogen environment, the raw materials are subjected to decomposition reaction under the coupling action of a temperature field, an electric field and hydrogen to prepare metal molybdenum powder and hydrogen sulfide, the hydrogen sulfide generated in the decomposition reaction process is recovered, and the auxiliary conductive material in the metal molybdenum powder is recovered after the reaction is finished to obtain the metal molybdenum powder.
Further, the hydrogen sulfide is decomposed to prepare sulfur and hydrogen, and the hydrogen is used as a gas source of the hydrogen.
Further optionally, the section current density of the blank is 0.5-20A/mm 2 The electrifying time is 0.1-2 hours.
The invention also provides a device for preparing the metal molybdenum powder.
Therefore, the device provided by the invention comprises a decomposition furnace, wherein a first electrode and a second electrode which are opposite to each other are arranged in the decomposition furnace, a blank placing space is formed between the two electrodes, power connectors are arranged on the first electrode and the second electrode, and a gas inlet and a gas outlet are arranged on the decomposition furnace.
Further, the gas inlet and outlet are connected with a sulfur cooling collector through a vacuum pump.
Furthermore, a first gas inlet and a second gas outlet are arranged on the decomposing furnace, the first gas inlet and the second gas outlet are connected with a hydrogen sulfide decomposing device, the hydrogen sulfide grading device is connected with a hydrogen source through a circulating pump, and the hydrogen source is connected with the second gas inlet and the second gas outlet.
The method and the device have the advantages of low vacuum decomposition temperature, short time period and low equipment requirement, and are easy to popularize and use.
Drawings
FIG. 1 is a schematic structural diagram of a device for preparing molybdenum powder according to the present invention;
FIG. 2 is another schematic structural diagram of a molybdenum powder preparing apparatus according to the present invention;
fig. 3 is a phase XRD pattern of the metal molybdenum powder prepared in example.
Detailed Description
Unless otherwise indicated, the pertinent terms in the present invention are to be understood according to conventional knowledge of those skilled in the art.
It should be explained that:
the raw materials used in the preparation process of the invention can be selected and determined according to the prior art. The auxiliary conductive material is selected in principle to play a conductive role in the decomposition reaction process so as to overcome the skin effect generated when the raw materials are directly electrified, and the auxiliary conductive material does not react with the metal molybdenum powder. Auxiliary conductive materials suitable for use in the present invention include, but are not limited to, metal molybdenum powder or/and aluminum oxide.
The forming shape of the blank can be determined according to the actual processing environment and conditions, for example, the blank can be formed into a cubic shape or a cylindrical shape generally, and can also be directly used by being directly compacted in a decomposing furnace. The section of the blank is a section perpendicular to the current direction.
In the preparation method, the prepared metal molybdenum powder and the auxiliary conductive material are separated, and a proper separation means can be selected according to the physical and chemical properties of the materials, including but not limited to centrifugal separation according to the specific gravity difference of the materials.
The hydrogen sulfide decomposition of the present invention may employ a method capable of decomposing hydrogen sulfide into hydrogen and sulfur, including but not limited to an electrochemical decomposition hydrogen production method.
The skilled in the art can optimize and select the values of the preparation process parameters on the basis of the concept of the invention. The amount of the auxiliary conductive material is determined according to actual yield and process parameters. The result of the optimization selection is within the protection scope of the present invention as long as the result does not depart from or exceed the inventive concept of the present invention.
The materials of the two electrodes in the device can be high-temperature-resistant electrode materials such as metal molybdenum or molybdenum silicide and the like simultaneously or respectively.
The following are specific examples provided by the inventors to further explain the technical solutions of the present invention. The input yield of the raw materials of the following examples is about 50 g + -2, and the raw materials are pressed into cylindrical samples with the diameter of 18 mm + -1, the invention is not limited to the output and the size of the green body, and the skilled person can process the green body with the proper size according to the actual production conditions by using the scheme of the invention as the guide. The starting materials used in the following examples are commercially available products.
Example 1:
in the embodiment, 10 wt% molybdenum powder is added into high-purity molybdenum disulfide as a raw material, the mixture is placed in a vacuum decomposition furnace, compacted under the pressure of 1Mpa and heated to 1200 ℃, a blank is electrified, and the section current of the blank is 3A/mm 2 Decomposing for 2 hours at the voltage of 30V/mm, collecting sulfur generated by decomposition through a vacuum condensation system, separating metal molybdenum powder and alumina powder by adopting a rotary centrifugal method, wherein the material slag after the decomposition is a mixture of the metal molybdenum powder and the alumina powder. Calculated, the raw material decomposition rate is 84 percent (the raw material decomposition rate is the sum of the mass of the prepared metal molybdenum powder and the mass of the sulfurPercentage of material mass); the product phase of this example was measured by X-ray diffraction and the results are shown in FIG. 3.
Example 2:
in the embodiment, 15 wt% of alumina powder is added into the high-purity molybdenum disulfide as the raw material, the mixture is placed in a vacuum decomposition furnace, the mixture is compacted under the pressure of 10Mpa and then heated to 1300 ℃, then the blank is electrified, and the section current is 3A/mm 2 Decomposing for 1 hour at the voltage of 30V/mm, collecting sulfur generated by decomposition through a vacuum condensation system, wherein the decomposed material slag is a mixture of metal molybdenum powder and alumina powder, and separating the metal molybdenum powder and the alumina powder by adopting a rotary centrifugal method. The material decomposition rate of this example was calculated to be 73% and the product phase XRD is shown in figure 3.
Example 3:
in the embodiment, 5 wt% molybdenum powder is added into high-purity molybdenum disulfide as a raw material, the mixture is placed in a decomposing furnace, the mixture is compacted under the pressure of 20Mpa and then heated to 800 ℃, hydrogen is introduced, a blank is electrified, and the section current of the blank is 15A/mm 2 Decomposing at 30V/mm for 0.1 hr to obtain molybdenum powder with material decomposing rate of 49%.
In a further scheme, hydrogen sulfide generated in the process is recovered, and then the hydrogen is decomposed by adopting an electrochemical method to generate hydrogen as a gas source required by the decomposing furnace.
Example 4:
in the embodiment, high-purity molybdenum disulfide is used as a raw material, 1 wt% of alumina powder is added, the mixture is placed in a decomposing furnace, after the mixture is compacted under the pressure of 200Mpa and heated to 200 ℃, a blank is electrified, and the section current of the blank is 9A/mm 2 Decomposing for 2 hours at the voltage of 30V/mm, collecting sulfur generated by decomposition through a vacuum condensation system, separating metal molybdenum powder and alumina powder by adopting a rotary centrifugal method after the decomposition is finished, and calculating to obtain the raw material decomposition rate of 94%.
Example 5:
in the embodiment, 20 wt% molybdenum powder is added into high-purity molybdenum disulfide as a raw material, the mixture is placed in a vacuum decomposition furnace, compacted under the pressure of 30Mpa and heated to 1000 ℃, a blank body is electrified, and the section current is 11A ^ and/or greater than or equal to the standardmm 2 And decomposing for 4 hours at the voltage of 30V/mm, collecting sulfur generated by decomposition through a vacuum condensation system, wherein the decomposed material slag is a mixture of metal molybdenum powder and alumina powder, and separating the metal molybdenum powder and the alumina powder by adopting a rotary centrifugal method. The raw material decomposition rate was calculated to be 99%.
Example 6:
as shown in FIG. 1, the apparatus of this embodiment comprises a decomposing furnace 3, a heating device 6 such as an electric furnace heating body is arranged outside the decomposing furnace 3, two opposite electrodes 5 are arranged in the decomposing furnace 3, and two electrodes 5 are externally connected with a power supply 7; the top of the decomposing furnace 3 is provided with a gas inlet and outlet which is connected with a sulfur cooler 2 through a vacuum pump 1.
During production, under a reasonable vacuum condition, the blank 4 is heated to a required temperature in the decomposing furnace 3 by using the heating device 6 as a heat source, required current and voltage are applied to the electrodes 5 at two sides of the raw material through the power supply 7, decomposed sulfur gas is condensed and collected in the sulfur cooler 2, and molybdenum powder is left in a sagger of the decomposing furnace; the vacuum pump 1 is arranged in front of the sulfur cooler and provides vacuum conditions for pyrolyzing molybdenum sulfide in the vacuum furnace.
Example 7:
as shown in fig. 2, the apparatus of this embodiment includes a decomposition furnace 8, a heating device 12 is provided outside the decomposition furnace 8, two opposite electrodes 10 are provided inside the decomposition furnace 8, and the two electrodes 10 are externally connected with a power supply 11; the top of the decomposing furnace 8 is provided with two gas inlets and outlets, one of the gas inlets and outlets is connected with an electrochemical decomposing device 13, the electrochemical decomposing device 13 is communicated with a gas source 16 through a circulating pump 14 and a pipeline 15, and the gas source 16 is connected with the other gas inlet and outlet in a return mode.
During production, in a normal pressure state, the blank 9 is heated to a required temperature between two electrodes of the decomposing furnace 8 by using the heating device 12 as a heat source, required current and voltage are applied to the electrodes 10 on two sides of the raw material through the power supply 11, decomposed hydrogen sulfide gas is decomposed into sulfur in the electrochemical decomposing device 13 to be condensed and collected, the hydrogen gas is recycled after passing through the circulating pump, the pipeline and the gas source 16, and molybdenum powder is remained in the decomposing furnace.
Claims (3)
1. A method for preparing metal molybdenum powder is characterized by comprising the following steps:
mixing a raw material molybdenum disulfide or molybdenite with a proper amount of auxiliary conductive material, and then pressing the mixture to form a blank, wherein the auxiliary conductive material is selected from materials which can assist in conducting electricity and do not react with metal molybdenum powder;
in an environment of 200-;
the auxiliary conductive material is selected from alumina, the addition mass of the auxiliary conductive material accounts for 1-20 wt% of the mass of the raw materials, and the alumina is recovered according to the specific gravity difference between the alumina and the metal molybdenum powder after the reaction is finished;
the pressure in the environment is a vacuum state of less than 200Pa, and sulfur is recovered under the vacuum condition;
the section current density of the blank is 0.5-20A/mm 2 The electrifying time is 0.1-2 hours.
2. The method as claimed in claim 1, wherein the blank is directly electrified at 1300 ℃ under normal pressure and hydrogen atmosphere, the decomposition reaction is carried out on the raw materials under the coupling action of the temperature field, the electric field and the hydrogen to obtain the metal molybdenum powder and the hydrogen sulfide, the hydrogen sulfide generated in the decomposition reaction is recovered, and the auxiliary conductive material in the metal molybdenum powder is recovered to obtain the metal molybdenum powder after the reaction.
3. The method for preparing molybdenum metal powder as claimed in claim 1, wherein the hydrogen sulfide is decomposed to produce sulfur and hydrogen, and the obtained hydrogen is used as a source of hydrogen required for the hydrogen environment.
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