A hydrogen selenide purification apparatus and method

Abstract

The application provides a hydrogen selenide purification device and method, in particular to removal of trace oxygen, hydrogen and water impurities in hydrogen selenide, and relates to the technical field of electronic special gas purification. In the variable-temperature purifier A, hydrogen and oxygen impurities in the hydrogen selenide react to generate water under the action of a catalyst, so that the hydrogen and part of the oxygen are removed, and the reaction principle is: H2+1 / 2O2 Catalyst The oxygen impurities in the hydrogen selenide are removed in the variable-temperature purifier B, and the principle is: 2H2Se+O2=2H2O+Se.When the impurity water in the hydrogen selenide is overproof, the purification device further comprises a normal-temperature purifier C, and the second adsorbent in the normal-temperature purifier C is used to remove the water generated in the variable-temperature purifier and the impurity water carried by the hydrogen selenide itself. The method provided by the application can remove the oxygen, hydrogen and water impurities without rectification and low-temperature evacuation, and the process is safe and simple to operate.

Description

Technical Field

[0001] This invention relates to the field of electronic specialty gas purification technology, and in particular to a purification apparatus and method for hydrogen selenide. Background Technology

[0002] Hydrogen selenide is a crucial electronic gas widely used in optoelectronics and microelectronics. It serves as an important raw material and reducing gas in the production of semiconductor materials, and can also form PN protective and isolation layers on semiconductor surfaces. It is also a vital electronic gas for advanced defense and aerospace applications. The purity of the gas significantly impacts the integration density, reliability, yield, and various optoelectronic properties of semiconductor devices and integrated circuits, thereby affecting the performance, quality, and overall performance of military electronic information technology and equipment. With the rapid development of my country's semiconductor industry, the market demand for high-purity hydrogen selenide is increasing.

[0003] Patent CN 101041425A discloses a method for purifying hydrogen selenide using aluminum selenide for dehydration. The advantage is that aluminum selenide maintains a good dehydration depth, but the disadvantage is that the preparation and storage conditions for aluminum selenide are demanding, limiting its market potential and making practical application difficult. Patent CN 112142015A discloses a method for purifying hydrogen selenide, using secondary distillation to remove impurities such as water and oxygen, but does not mention a method for removing hydrogen impurities. Patent CN 108726492A discloses a method for purifying hydrogen selenide, first removing organic and metallic impurities under low-temperature vacuum conditions, and then removing gaseous impurities such as nitrogen and hydrogen under low-temperature vacuum conditions. The above patents either require secondary distillation or low-temperature vacuuming, making the processes complex. Summary of the Invention

[0004] The purpose of this invention is to provide a purification device and method for hydrogen selenide. This invention has good purification effect and can remove trace oxygen, hydrogen and water impurities without distillation or low-temperature evacuation. The process is safe and simple to operate.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a hydrogen selenide purification device, including a temperature-controlled purifier;

[0007] The variable temperature purifier includes variable temperature purifier A and / or variable temperature purifier B; both variable temperature purifier A and variable temperature purifier B are equipped with heaters on the outside of their main bodies to control the main body temperature.

[0008] The variable temperature purifier A is internally filled with a carrier and a catalyst; the catalyst is palladium or platinum.

[0009] The variable temperature purifier B is filled with a first adsorbent.

[0010] Preferably, the variable temperature purifier includes both variable temperature purifier A and variable temperature purifier B, with variable temperature purifier A and variable temperature purifier B connected in series.

[0011] Preferably, it also includes a room temperature purifier C, which is connected in series with a variable temperature purifier;

[0012] The ambient temperature purifier C is filled with a second adsorbent.

[0013] Preferably, the first adsorbent and the second adsorbent independently comprise one or more of molecular sieves, activated carbon, silica gel, and activated alumina.

[0014] Preferably, the carrier is one or more of activated alumina, titanium dioxide, and carbon black.

[0015] Preferably, the mass of the catalyst is 0.01 to 4% of the total mass of the catalyst and the support.

[0016] This invention provides a method for purifying hydrogen selenide, which removes trace amounts of oxygen, hydrogen, and water impurities from hydrogen selenide using the purification device described above. Specifically, it employs a combination of chemical reaction and physical adsorption, and includes the following steps:

[0017] The crude hydrogen selenide is passed into a temperature-controlled purifier to remove hydrogen and / or remove oxygen in temperature-controlled purifier B.

[0018] The temperature of the variable temperature purifier A is controlled between 20 and 40°C;

[0019] The temperature of the variable temperature purifier B is controlled between 200 and 500°C.

[0020] Preferably, the purification device further includes a room temperature purifier C, and after treatment by the variable temperature purifier, the intermediate purified gas is further passed into the room temperature purifier C to remove impurity water.

[0021] Preferably, the flow rate of the crude hydrogen selenide is below 15 kg / h.

[0022] Preferably, the reaction pressure in the variable temperature purifier A is below 0.2 MPa; the pressure in the variable temperature purifier B is below 0.2 MPa; and the pressure in the ambient temperature purifier C is below 0.4 MPa.

[0023] This invention provides a hydrogen selenide purification device, wherein the temperature-switching purifier includes a temperature-switching purifier A and / or a temperature-switching purifier B; both temperature-switching purifier A and temperature-switching purifier B are equipped with heaters to control the temperature of the main body; the temperature-switching purifier A is filled with a carrier and a catalyst; the catalyst is palladium or platinum; and the temperature-switching purifier B is filled with a first adsorbent.

[0024] In temperature-controlled purifier A, hydrogen and oxygen impurities in hydrogen selenide react to form water under the action of a catalyst, thereby removing hydrogen and some oxygen. The reaction principle is: H₂ + 1 / 2O₂ H2O; Oxygen impurities in hydrogen selenide are removed in temperature-controlled purifier B, the principle of which is: 2H2Se + O2 = 2H2O + Se.

[0025] The purification device also includes a room-temperature purifier C. This invention utilizes a second adsorbent in the room-temperature purifier C to remove the water generated in the temperature-variable-temperature purifier, as well as the impurity water inherent in the hydrogen selenide itself. The method of this invention does not require distillation or low-temperature evacuation to remove oxygen, hydrogen, and impurity water; the process is safe and simple to operate.

[0026] Moreover, the present invention can adopt different combinations and arrangements of purifiers according to the different impurity contents in the hydrogen selenide product. The three purification modules can be used individually or connected in combination, which is flexible and not limited to a fixed device structure. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of one possible structure of the purification device of the present invention.

[0028] Among them, 1-purifier A, 2-purifier B, 3-purifier C, 4-raw material tank, 5-product bottle. Detailed Implementation

[0029] The present invention provides a hydrogen selenide purification device, including a temperature-switching purifier; the temperature-switching purifier includes temperature-switching purifier A and / or temperature-switching purifier B; both temperature-switching purifier A and temperature-switching purifier B are provided with heaters on the outside of their main bodies to control the main body temperature.

[0030] The variable temperature purifier A is internally filled with a carrier and a catalyst; the catalyst is palladium or platinum.

[0031] The variable temperature purifier B is filled with a first adsorbent.

[0032] The purification apparatus provided by this invention includes a temperature-switching purifier, which comprises temperature-switching purifier A and / or temperature-switching purifier B; both temperature-switching purifier A and temperature-switching purifier B are equipped with heaters to control the temperature of the main body. This invention does not impose special requirements on the specific structure and specifications of the components in temperature-switching purifier A and temperature-switching purifier B; reactors and heaters well-known in the art can be used.

[0033] In this invention, the variable-temperature purifier A is internally filled with a support and a catalyst; the catalyst is palladium or platinum; the particle size of the catalyst is preferably 1.5–4 nm, more preferably 1.5–3.5 nm. In this invention, the support is preferably one or more of activated alumina, titanium dioxide, and carbon black. In this invention, the mass of the catalyst is preferably 0.01–4% of the total mass of the catalyst and support, more preferably 0.01–3.5%, and even more preferably 0.02–2.5%. The variable-temperature purifier A of this invention removes hydrogen and oxygen impurities; the reaction principle is: H₂ + 1 / 2O₂ H2O.

[0034] In this invention, the variable-temperature purifier B is filled with a first adsorbent. Preferably, the first adsorbent comprises one or more of molecular sieves, activated carbon, silica gel, and activated alumina. The variable-temperature purifier B removes oxygen impurities, and its principle is as follows: under conditions of 200–500°C, 2H₂Se + O₂ = 2H₂O + Se, with Se being recyclable in the later stages.

[0035] Those skilled in the art can determine, based on the impurity content in hydrogen selenide, whether to select temperature-variable purifier A alone or temperature-variable purifier B, or to select both simultaneously.

[0036] For example, when the oxygen content in hydrogen selenide is low and the hydrogen content is high, and the oxygen and hydrogen content can be met by using only temperature-controlled purifier A, then only temperature-controlled purifier A needs to be installed. If the hydrogen content is already within the acceptable range, but the oxygen content is not, then temperature-controlled purifier A can be omitted, and only temperature-controlled purifier B needs to be installed. When both the hydrogen and oxygen content in hydrogen selenide are not within the acceptable range, this invention preferably uses both temperature-controlled purifier A and temperature-controlled purifier B simultaneously.

[0037] In this invention, when the variable temperature purifier includes both variable temperature purifier A and variable temperature purifier B, it is preferable that variable temperature purifier A and variable temperature purifier B are connected in series.

[0038] The purification device provided by the present invention includes a room temperature purifier C, which is connected in series with a variable temperature purifier. Its function is to remove water impurities contained in the raw material and those generated after passing through the variable temperature purifier A and the variable temperature purifier B.

[0039] In this invention, the ambient temperature purifier C is filled with a second adsorbent; the second adsorbent preferably includes one or more of molecular sieves, activated carbon, silica gel, and activated alumina. This invention does not impose special requirements on the specific structure and specifications of the ambient temperature purifier C; any adsorbent well-known in the art can be used.

[0040] The present invention does not impose any special restrictions on the selection method and arrangement order of the three purification modules in the device, and can make corresponding adjustments according to the impurity content of the hydrogen selenide raw material and the technical indicators required by the product.

[0041] In this invention, the purification device preferably further includes a raw material tank; the raw material tank is used to hold crude hydrogen selenide; the raw material tank is connected to the inlet of the temperature-variable purifier.

[0042] In this invention, the purification device preferably further includes a product bottle; the product bottle is used to collect purified hydrogen selenide, and the product bottle is connected to the outlet of the ambient temperature purifier C.

[0043] Figure 1 This is a schematic diagram of one structure of the purification device of the present invention, wherein 1-purifier A, 2-purifier B, 3-purifier C, 4-raw material tank, and 5-product bottle.

[0044] This invention provides a method for purifying hydrogen selenide, which utilizes the purification device described above to remove trace amounts of oxygen, hydrogen, and water impurities from hydrogen selenide. Specifically, it employs a combination of chemical reaction and physical adsorption, and includes the following steps:

[0045] The crude hydrogen selenide is passed into a temperature-controlled purifier to remove hydrogen and / or remove oxygen in temperature-controlled purifier B.

[0046] The temperature of the variable temperature purifier A is controlled between 20 and 40°C;

[0047] The temperature of the variable temperature purifier B is controlled between 200 and 500°C.

[0048] The present invention does not have any special requirements for the crude hydrogen selenide product; any crude hydrogen selenide product with a purity of 99.9% known in the art is acceptable.

[0049] In this invention, when the temperature-switching purifier is temperature-switching purifier A, crude hydrogen selenide is introduced into temperature-switching purifier A to remove hydrogen and some oxygen. In this invention, the temperature of temperature-switching purifier A is controlled at 20–40°C, preferably 25–35°C; the reaction pressure is preferably below 0.2 MPa, more preferably 0.1–0.15 MPa. This invention preferably controls the reaction pressure by controlling the flow rate of crude hydrogen selenide, which is preferably below 15 kg / h, more preferably 2–12 kg / h, and even more preferably 5–10 kg / h. In this invention, the following chemical reaction occurs in temperature-switching purifier A: H₂ + 1 / 2O₂ catalyst H2O.

[0050] In this invention, when the temperature-switching purifier is temperature-switching purifier B, crude hydrogen selenide is introduced into temperature-switching purifier B to remove oxygen. In this invention, the temperature of temperature-switching purifier B is controlled at 200–500°C, preferably 250–500°C, more preferably 350–480°C; the reaction pressure is preferably below 0.2 MPa, more preferably 0.1–0.15 MPa. This invention preferably controls the reaction pressure by controlling the feed flow rate of crude hydrogen selenide, which is preferably below 15 kg / h, more preferably 2–12 kg / h, and more preferably 5–10 kg / h. In this invention, the following chemical reaction occurs in temperature-switching purifier B: 2H₂Se + O₂ = 2H₂O + Se.

[0051] In this invention, when the temperature-switching purifier includes temperature-switching purifier A and temperature-switching purifier B, it is preferable to first pass the crude hydrogen selenide into temperature-switching purifier A, and then into temperature-switching purifier B. Specific reaction conditions have been discussed previously and will not be repeated here.

[0052] When the purification apparatus includes a room-temperature purifier C, the present invention further includes removing impurity water in the room-temperature purifier C by physical adsorption. In the present invention, the pressure inside the room-temperature purifier C is preferably below 0.4 MPa, more preferably 0.05–0.4 MPa, and even more preferably 0.2–0.4 MPa. The present invention preferably controls the pressure inside the room-temperature purifier C by controlling the feed flow rate. In the present invention, the room-temperature purifier C is filled with a second adsorbent, which can remove water generated in the temperature-variable-temperature purifier and impurity water inherent in the crude hydrogen selenide product.

[0053] The following detailed description of the hydrogen selenide purification apparatus and method provided by the present invention, in conjunction with embodiments, should not be construed as limiting the scope of protection of the present invention.

[0054] Example 1

[0055] An apparatus and method for purifying hydrogen selenide, employing... Figure 1 The apparatus shown is used in the following steps:

[0056] The crude hydrogen selenide (99.9% purity) first enters purifier A at a flow rate of 10 kg / h. Purifier A is a fixed-bed reactor packed with a palladium catalyst, supported by titanium dioxide. The palladium catalyst dosage is 0.02%, and the catalyst particle size is 2 nm. The heater controls the reaction temperature to be constant at 25℃. Hydrogen and oxygen impurities in the hydrogen selenide react in purifier A to produce water. Subsequently, the product gas enters purifier B, which is packed with molecular sieve adsorbent. The heater controls the temperature in purifier B to be 450℃. Trace oxygen impurities in the hydrogen selenide react with the hydrogen selenide product to produce water and elemental selenium. The product gas containing impurity water is then passed into purifier C, which contains activated carbon, for physical adsorption at room temperature. Finally, it is filled into a product bottle with a purity of 99.99%.

[0057] Example 2

[0058] use Figure 1 The apparatus shown is used to purify crude hydrogen selenide.

[0059] The crude hydrogen selenide product first enters purifier A at a flow rate of 5 kg / h. Purifier A is a fixed-bed reactor packed with a platinum catalyst, using carbon black as the support, with a platinum catalyst dosage of 0.1% and a catalyst particle size of 2.5 nm. The heater maintains a constant reaction temperature of 20°C. Hydrogen and oxygen impurities in the hydrogen selenide react in purifier A to produce water. Subsequently, the product gas enters purifier B, which is packed with activated carbon adsorbent. The heater maintains a temperature of 370°C in purifier B. Trace oxygen impurities in the hydrogen selenide react with the hydrogen selenide product to produce water and elemental selenium. The product gas containing impurities and water is then passed into purifier C, which is equipped with molecular sieves, for physical adsorption at room temperature. Finally, the product gas is filled into a product bottle.

[0060] Example 3

[0061] The purification unit consists of only purifiers A and C for purifying the crude hydrogen selenide product. The crude hydrogen selenide product first enters purifier C at a flow rate of 8 kg / h; purifier C is an adsorber filled with silica gel. The crudely dehydrated hydrogen selenide gas then enters purifier A, a fixed-bed reactor filled with a palladium catalyst. The support is activated alumina, the palladium catalyst dosage is 0.03%, and the catalyst particle size is 1.6 nm. The heater maintains a constant reaction temperature of 22°C. Hydrogen and oxygen impurities in the hydrogen selenide react in purifier A to produce water. The product passing through purifier A undergoes online analysis; if the oxygen and hydrogen content meets the standards, the product gas containing water impurities is then passed into purifier C, which is equipped with molecular sieves, for physical adsorption at room temperature. The finely dehydrated hydrogen selenide product is then filled into product bottles.

[0062] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for purifying hydrogen selenide, characterized in that, The purification device is used to remove trace oxygen, hydrogen, and water impurities from hydrogen selenide, specifically by a combination of chemical reaction and physical adsorption. The purification device includes a temperature-controlled purifier. The variable temperature purifier includes variable temperature purifier A and variable temperature purifier B, which are connected in series. Both variable temperature purifier A and variable temperature purifier B are equipped with heaters on the outside of their main bodies to control the main body temperature. The variable temperature purifier A is internally filled with a carrier and a catalyst; the catalyst is palladium or platinum. The variable-temperature purifier B is filled with a first adsorbent; Includes the following steps: The crude hydrogen selenide is passed into a temperature-variable temperature purifier. First, hydrogen is removed in temperature-variable temperature purifier A, and then oxygen is removed in temperature-variable temperature purifier B. The temperature of the variable-temperature purifier A is controlled at 20~40℃; The temperature of the variable temperature purifier B is controlled between 200 and 500°C.

2. The purification method according to claim 1, characterized in that, It also includes a room temperature purifier C, which is connected in series with a variable temperature purifier; The ambient temperature purifier C is filled with a second adsorbent.

3. The purification method according to claim 2, characterized in that, The first adsorbent and the second adsorbent independently include one or more of molecular sieves, activated carbon, silica gel and activated alumina.

4. The purification method according to claim 1, characterized in that, The carrier is one or more of activated alumina, titanium dioxide, and carbon black.

5. The purification method according to claim 1, characterized in that, The mass of the catalyst is 0.01 to 4% of the total mass of the catalyst and the support.

6. The purification method according to claim 2, characterized in that, The purification device further includes a room temperature purifier C, and after being processed by a variable temperature purifier, the intermediate purified gas is passed into the room temperature purifier C to remove impurity water.

7. The purification method according to claim 1, characterized in that, The flow rate of the crude hydrogen selenide is below 15 kg / h.

8. The purification method according to claim 6, characterized in that, The reaction pressure in the variable temperature purifier A is below 0.2 MPa; the pressure in the variable temperature purifier B is below 0.2 MPa; and the pressure in the ambient temperature purifier C is below 0.4 MPa.

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