CN115072680A - Method and device for continuously producing ultrapure phosphane - Google Patents

Method and device for continuously producing ultrapure phosphane Download PDF

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Publication number
CN115072680A
CN115072680A CN202210379458.7A CN202210379458A CN115072680A CN 115072680 A CN115072680 A CN 115072680A CN 202210379458 A CN202210379458 A CN 202210379458A CN 115072680 A CN115072680 A CN 115072680A
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phosphane
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周桂明
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Cangzhou Bohai New Area Shengtai Chemical Co ltd
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Cangzhou Bohai New Area Shengtai Chemical Co ltd
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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
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/06—Hydrogen phosphides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1856—Stationary reactors having moving elements inside placed in parallel

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Abstract

The invention relates to a method and a device for continuously producing ultrapure phosphane. Under water environment, adding sodium hydroxide solution into yellow phosphorus and lime by flow control of a flow meter, connecting a plurality of reaction kettles in parallel, and alternately feeding, producing and discharging reaction salt solution; obtaining a crude phosphane; freezing high-boiling-point impurities in a condenser by two-stage low-temperature freezing of the crude phosphane; feeding the frozen and impurity-removed crude phosphane into a constant-pressure buffer tank to supply gas to a rectification and adsorption device; removing impurities with high and low boiling points from the crude phosphane provided by the constant-pressure buffer tank through a two-stage low-temperature low-pressure rectifying tower; adsorbing the rectified phosphane; obtaining an ultrapure phosphane product with the purity of more than or equal to 99.99999; the invention adopts three reaction kettles connected in parallel and alternately fed materials to continuously produce the phosphane, is easy to realize industrial large-scale production, and has the advantages of large volume of the reactor, large yield and the like.

Description

Method and device for continuously producing ultrapure phosphane
Technical Field
The invention belongs to the technical field of preparation, purification and filling of phosphane, and particularly relates to a method and a device for continuously producing ultrapure phosphane.
Background
The high-purity phosphane is applied to the production industries of electronics, semiconductor materials, solar photovoltaic cells, novel lighting materials and the like. With the improvement of global energy-saving and environmental protection requirements and the progress of science and technology, high-purity and even ultra-pure phosphine becomes an essential raw material for the manufacturing industries of crystalline silicon (microcrystalline silicon and amorphous silicon) solar photovoltaic cells, ultra-large scale integrated circuits, liquid crystal displays, semiconductor light-emitting devices and semiconductor materials. At present, the main domestic production processes of high-purity phosphane are phosphorous acid pyrolysis and the reaction of metal phosphide and strong acid for preparation, for example: reacting aluminum phosphide with sulfuric acid to prepare phosphine; the implemented purification process is an adsorption method in domestic production at present, and impurity components are removed one by adopting a multi-stage adsorption device. The above processes have many disadvantages in the large-scale production process, such as: low production efficiency, large product quality fluctuation, incapability of realizing the production of ultrapure products, high danger degree and the like. In addition, some scientific achievements published domestically have many disadvantages, which are as follows:
chinese patent CN201510336886.1 proposes a device and a method for synthesizing and purifying electronic grade phosphane, which adopts the reaction of sulfuric acid and zinc phosphide to prepare the phosphane, and prepares a 6N phosphane product by rectifying, lightness removing and multi-stage adsorption impurity removing methods. Firstly, the metal phosphide is seriously polluted in the production process of the metal phosphide, and the production of the metal phosphide (aluminum phosphide and zinc phosphide) is a production process and a product which are eliminated by the nation, so that the metal phosphide can not be purchased for use in the subsequent production possibly in the market.
Chinese patent CN201810909843.1 proposes a purification system and a treatment method of electronic grade phosphane, wherein the method uses phosphane with the purity of 98 wt% as a raw material, and adopts a spray absorption process to remove H in the raw material gas 2 S and CO 2 After partial impurities are removed by adopting a high-pressure adsorption process, the mixture enters a rectifying tower to remove light and heavy. The process route has the problems that 98 percent of low-purity phosphane by weight cannot be purchased at all at home, dangerous factors exist in the collection and filling of the crude phosphane, enterprises try to collect and fill the crude phosphane at home, casualty events finally occur, and no enterprises and individuals are engaged in the work and research at home.
Chinese patent CN201210522061.5 proposes a method for preparing phosphine, which comprises the steps of firstly adding yellow phosphorus and low carbon alcohol with carbon number of 1-5 into a reactor, then adding sodium hydroxide solution, adding inorganic acid after the reaction is finished, then adding low carbon alcohol with carbon number of 1-5 to continue the reaction to obtain mixed acid of phosphoric acid and phosphorous acid, and finally electrolyzing the mixed acid at the temperature of 200-250 ℃ to prepare the phosphine. The method for preparing phosphine has complex process, overhigh operation temperature and high process risk, and leads to the introduction of C-H compounds by using polyalcohol, thereby bringing fatal damage to the production of semiconductor materials. And the high-temperature pyrolysis of phosphoric acid and phosphorous acid has extremely high requirements on the corrosion resistance of a production device, according to the experience of the original process (phosphorous acid is pyrolyzed at 250-300 ℃ to prepare phosphine) of a factory, the reaction kettle of the method can only use pure imported Ha B alloy, and the corrosion is serious only within the service life of equipment for less than one year.
Chinese patent CN201810929863.5 proposes liquefying phosphorous acid under oxygen-free conditions, adding into a reaction kettle, gasifying at high temperature to obtain crude phosphane, introducing the crude phosphane gas into a condensing tower to condense and remove impurities, filtering through a molecular sieve, and then introducing into a cold trap to obtain the phosphane. The method has the same defect of strong corrosivity to a reactor as the CN201210522061.5 patent, and the quality of the product is unstable and has large fluctuation by using the purification method, so that qualified high-purity products are not easy to obtain.
Disclosure of Invention
According to the characteristics of the problems in the prior art, the invention provides a method and a device for continuously producing ultrapure phosphane. The method adopts yellow phosphorus, lime and sodium hydroxide to react in water environment to prepare the phosphane, and has the following specific reaction formula:
P 4 +3NaOH+3H 2 O＝3NaH 2 PO 2 +PH 3 ↑
however, side reactions are generated simultaneously in the reaction process, and the side reactions mainly comprise:
P 4 +4NaOH+4H 2 O＝4NaH 2 PO 2 +2H 2 ↑
P 4 +4Ca(OH) 2 +4H 2 O＝4CaHPO 3 +6H 2 ↑
therefore, when yellow phosphorus, sodium hydroxide and calcium hydroxide are used for reaction, the yellow phosphorus, the sodium hydroxide and the calcium hydroxide cannot be completely converted into phosphine along with the progress of side reaction, and the yield of the phosphine is about 20-30%.
The continuous large-scale stable production of the crude phosphane is realized by optimizing the material ratio and alternately producing a plurality of reaction kettles; simultaneously, removing impurities in the crude product by adopting a combination mode of low-temperature freezing, two-stage low-temperature low-pressure rectification and multi-stage adsorption to obtain the ultrapure phosphane; the low-temperature steel cylinder group is adopted for negative pressure filling, so that the large-scale filling of the ultrapure phosphane is realized.
The technical scheme of the invention is as follows:
a method for the continuous production of ultrapure phosphanes; the method comprises the following steps:
(1) controlling the temperature of yellow phosphorus and lime to be 80-95 ℃ in water environment; controlling the flow by a flow meter, adding a sodium hydroxide solution, wherein the reaction pressure is 0-0.25 MPa, and the reaction time is 1-6 h; a plurality of reaction kettles are connected in parallel, and the reaction salt solution is alternately fed for production and discharged; obtaining a crude phosphane;
(2) freezing high-boiling-point impurities in a condenser by two-stage low-temperature freezing of the crude phosphane; the temperature of the freezing unit is controlled to be-70 to-30 ℃; feeding the frozen and impurity-removed crude phosphane into a constant-pressure buffer tank to supply gas to a rectification and adsorption device;
(3) removing impurities with high and low boiling points from the crude phosphane provided by the constant-pressure buffer tank through a two-stage low-temperature low-pressure rectifying tower; the operating pressure is 0-0.25 MPa, and the operating temperature is-89 to-68 ℃;
(4) adsorbing the rectified phosphane; obtaining an ultrapure phosphane product with the purity of more than or equal to 99.99999;
(5) filling an ultrapure phosphine product into a low-temperature negative-pressure steel cylinder group through a mass flow meter; the steel cylinder group is arranged in the liquid nitrogen tank, and the liquid level height of the liquid nitrogen tank is controlled to be 1/4-1/2 of the bottle height; the filling pressure is 0-0.25 MPa.
The weight ratio of the yellow phosphorus and the calcium hydroxide in the step (1) is 1: 0.8 to 1.2.
The weight ratio of the yellow phosphorus and water in the step (1) is 1: 5 to 7.
The step (4) adopts a multi-stage adsorption method, and the adsorbent for adsorption is one or more of activated carbon, soda lime, a molecular sieve and a high-temperature trap.
2. A device for continuously producing ultrapure phosphane comprises a first reaction kettle A, a second reaction kettle B, a third reaction kettle, a C first-stage condenser D, a second-stage condenser E, a constant-pressure buffer tank F, a first-stage rectifying tower H, a second-stage rectifying tower I, a first-stage adsorption column K, a second-stage adsorption column L, a third-stage adsorption column M, a steel cylinder group P and a liquid nitrogen tank Q; the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel, and the materials are alternately fed for production and the reaction salt solution is discharged; the upper parts of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are provided with inlets of calcium hydroxide, sodium hydroxide, water and yellow phosphorus, the top part of the first reaction kettle A is provided with a reaction gas outlet, the bottom part of the first reaction kettle B is provided with a salt solution outlet, and the reaction gas outlet is connected with a primary condenser D; the first-stage condenser D is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first reaction kettle A, the second reaction kettle B and the third reaction kettle C, and the material outlet is connected with the second-stage condenser E; the second-stage condenser E is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage condenser D, and the material outlet is connected with the constant-pressure buffer tank F; the constant-pressure buffer tank F is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary condenser E, and the material outlet is connected with the primary rectifying tower H; a material inlet is arranged in the middle of the primary rectifying tower H, a tower top extraction outlet is arranged at the top of the primary rectifying tower H, a tower kettle extraction outlet is arranged at the bottom of the primary rectifying tower H, the material inlet is connected with a constant-pressure buffer tank F, a tower top extraction outlet extracts low-boiling-point impurities, and a tower kettle extraction outlet is connected with the secondary rectifying tower I; the middle part of the second-stage rectifying tower I is provided with a material inlet, the top part of the second-stage rectifying tower I is provided with a tower top extraction outlet, the bottom part of the second-stage rectifying tower I is provided with a tower bottom extraction outlet, the material inlet is connected with the first-stage rectifying tower H, a tower bottom extraction outlet extracts high-boiling-point impurities, and the tower top extraction outlet is connected with the first-stage adsorption column K; the adsorption column K is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary rectifying tower I, and the material outlet is connected with the secondary adsorption column L; the second-stage adsorption column L is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage adsorption column K, and the material outlet is connected with the third-stage adsorption column M; the third-stage adsorption column M is provided with a material inlet and a material outlet, wherein the material inlet is connected with the second-stage adsorption column L, and the material outlet is connected with the steel cylinder group P; the steel bottle group P is placed in a liquid nitrogen tank Q.
The method for continuously producing the ultrapure phosphane by utilizing the device comprises the following steps:
the reaction pressure of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is 0-0.25 MPa, and the reaction temperature is 80-95 ℃.
The temperature of the primary condenser D is-50 to-30 ℃, and the temperature fluctuation is not more than +/-2 ℃; the temperature of the secondary condenser E is-70 to-60 ℃, and the temperature fluctuation is not more than +/-2 ℃.
The pressure of the constant-pressure buffer tank F is 0-0.25 MPa.
The operating pressure of the primary rectifying tower H is 0-0.25 MPa, the operating temperature is-89 to-72 ℃, and the temperature fluctuation is not more than +/-1 ℃; the operating pressure of the second-stage rectifying tower I is 0-0.25 MPa, the operating temperature is-85 to-68 ℃, and the temperature fluctuation is not more than +/-1 ℃.
The liquid nitrogen height of the liquid nitrogen tank Q is 1/4-1/2 of the height of the steel cylinder group M; the steel cylinder group P is formed by connecting 4-16 steel cylinders in parallel, and the inlet pressure is 0-0.25 MPa.
The concrete description is as follows:
(1) purging and replacing the first reaction kettle A by using nitrogen or helium, vacuumizing, sequentially adding yellow phosphorus and calcium hydroxide into the first reaction kettle A, heating, controlling a flow meter to add a sodium hydroxide solution, fully reacting the yellow phosphorus and mixed alkali in the first reaction kettle A to obtain a phosphine crude gas, extracting the phosphine crude gas to a primary condenser D, and allowing a salt solution generated by the reaction to enter a subsequent salt solution treatment process. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel, and the materials are alternately fed for production and the reaction salt solution is discharged. When the system is started for the first time, the production can be continued after the balance of the system to be rectified is established.
The weight ratio of the yellow phosphorus to the calcium hydroxide is 1: 0.8 to 1.2.
The weight ratio of the yellow phosphorus to the sodium hydroxide is 1: 0.75 to 0.85.
The weight ratio of the yellow phosphorus to the water is 1: 5 to 7.
The preparation weight ratio of the calcium hydroxide and the water in the lime milk is 1: 1.
(2) and the phosphine crude gas after impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the phosphine crude gas after deep impurity removal by the secondary condenser E enters a constant-pressure buffer tank F, and the constant-pressure buffer tank F supplies gas to the primary rectifying tower H at constant pressure.
The temperature of the primary condenser D is between 50 ℃ below zero and 30 ℃ below zero, and the temperature fluctuation is not more than +/-2 ℃.
The temperature of the secondary condenser E is-70 to-60 ℃, and the temperature fluctuation is not more than +/-2 ℃.
The pressure of the constant-pressure buffer tank F is 0-0.25 MPa.
(3) Extracting low-boiling impurities from the top of the first-stage rectifying tower H, and feeding the materials extracted from the tower kettle into a second-stage rectifying tower I; high boiling point impurities are extracted from the tower kettle of the second-stage rectifying tower I, and materials extracted from the tower top enter an adsorption column.
The operating pressure of the primary rectifying tower H is 0-0.25 MPa, the operating temperature is-89 to-72 ℃, and the temperature fluctuation is not more than +/-1 ℃.
The operating pressure of the secondary rectifying tower I is 0-0.25 MPa, the operating temperature is-85 to-68 ℃, and the temperature fluctuation is not more than +/-1 ℃.
(4) The first-stage adsorption column K, the second-stage adsorption column L and the third-stage adsorption column M are connected in series, the rectified and impurity-removed phosphine gas sequentially enters the first-stage adsorption column K, the second-stage adsorption column L and the third-stage adsorption column M, and the obtained ultrapure phosphine is filled at a low temperature.
The first-stage adsorption column K, the second-stage adsorption column L and the third-stage adsorption column M are filled with one or more of soda lime, activated carbon, molecular sieves and high-temperature traps.
(5) 4-16 steel cylinders are connected in parallel by pipelines and valves in advance to form a steel cylinder group P, and the steel cylinder group P is connected to a filling pipeline after being pre-vacuumized and replaced. And (3) placing the steel cylinder group P in a liquid nitrogen tank Q, controlling the liquid level of the liquid nitrogen tank Q, and controlling the flow of the phosphine by a flowmeter to fill the steel cylinders one by one.
The steel cylinder group P is formed by connecting 4-16 steel cylinders in parallel, and the inlet pressure is 0-0.25 MPa.
The liquid level height of the liquid nitrogen tank Q is 1/4-1/2 of bottle height.
The beneficial results of the invention are:
the reaction process adopts low-temperature reaction in water environment, has low risk and is the most safe one of all the existing phosphane production processes.
And the byproduct tail salt produced by the reaction process is sodium hypophosphite, so that the product has high added value, and brings great benefits for reducing the cost and increasing the profit of enterprises.
And thirdly, three reaction kettles are connected in parallel and alternately fed, so that the phosphane can be continuously produced, the industrial large-scale production is easy to realize, and the reactor has the advantages of large volume, large yield and the like.
And fourthly, the impurities are frozen in the condenser through two-stage condensation, so that part of high-boiling-point impurities which influence the rectification quality and the operation safety are removed in the process, and the possibility that the later process flow and the product quality are influenced by the untight closing of a valve, the wall hanging of the inner wall of the pipeline and the like caused by the pollution and the blockage of the pipeline and the valve in the later process link is avoided.
The arrangement of the constant pressure buffer tank in the production and the refining of the phosphane also belongs to the first time. Aims to improve and ensure the constant-pressure stable operation of the feeding of the subsequent rectification process and further improve the product quality.
And sixthly, refining the phosphane obtained by the reaction by using liquid nitrogen as a refrigerant source and controlling the temperature of the two-stage low-temperature low-pressure rectification tower to obtain the ultrapure phosphane with the purity of more than or equal to 99.99999 percent, wherein the yield of the phosphane in the refining process is more than or equal to 90 percent, and compared with the traditional process, the energy saving of the two-stage low-temperature low-pressure rectification process is more than or equal to 25 percent.
And the low-temperature steel cylinder assembly and filling can greatly improve the filling efficiency and realize large-scale filling on the premise of ensuring the stability of products.
Drawings
FIG. 1 is a schematic diagram of a method and apparatus for continuously producing ultrapure phosphane.
A: first reaction vessel, B: a second reaction kettle, C: third reaction kettle, D: first-stage condenser, E: secondary condenser, F: constant-pressure buffer tank, H: a first-stage rectifying tower, I: second-stage rectification column, K: first-order adsorption column, L: second-stage adsorption column, M: tertiary adsorption column, P: cylinder group, Q: and a liquid nitrogen tank.
Detailed Description
As shown in fig. 1, a device for continuously producing ultrapure phosphane comprises a first reaction kettle A, a second reaction kettle B, a third reaction kettle C, a first-stage condenser D, a second-stage condenser E, a constant-pressure buffer tank F, a first-stage rectifying tower H, a second-stage rectifying tower I, a first-stage adsorption column K, a second-stage adsorption column L, a third-stage adsorption column M, a steel cylinder group P and a liquid nitrogen tank Q; the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel, and the reaction salt solution is alternately fed for production and discharged; the upper parts of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are provided with inlets of calcium hydroxide, sodium hydroxide, water and yellow phosphorus, the top part of the first reaction kettle A is provided with a reaction gas outlet, the bottom part of the second reaction kettle B is provided with a salt solution outlet, and the reaction gas outlet is connected with a primary condenser D; the first-stage condenser D is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first reaction kettle A, the second reaction kettle B and the third reaction kettle C, and the material outlet is connected with the second-stage condenser E; the second-stage condenser E is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage condenser D, and the material outlet is connected with the constant-pressure buffer tank F; the constant-pressure buffer tank F is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary condenser E, and the material outlet is connected with the primary rectifying tower H; a material inlet is arranged in the middle of the primary rectifying tower H, a tower top extraction outlet is arranged at the top of the primary rectifying tower H, a tower kettle extraction outlet is arranged at the bottom of the primary rectifying tower H, the material inlet is connected with a constant-pressure buffer tank F, a tower top extraction outlet extracts low-boiling-point impurities, and a tower kettle extraction outlet is connected with the secondary rectifying tower I; the middle part of the second-stage rectifying tower I is provided with a material inlet, the top part of the second-stage rectifying tower I is provided with a tower top extraction outlet, the bottom part of the second-stage rectifying tower I is provided with a tower bottom extraction outlet, the material inlet is connected with the first-stage rectifying tower H, a tower bottom extraction outlet extracts high-boiling-point impurities, and the tower top extraction outlet is connected with the first-stage adsorption column K; the adsorption column K is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary rectifying tower I, and the material outlet is connected with the secondary adsorption column L; the second-stage adsorption column L is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage adsorption column K, and the material outlet is connected with the third-stage adsorption column M; the third-stage adsorption column M is provided with a material inlet and a material outlet, wherein the material inlet is connected with the second-stage adsorption column L, and the material outlet is connected with the steel cylinder group P; the steel bottle group P is placed in a liquid nitrogen tank Q.
The specific implementation method and steps are as follows:
(1) purging and replacing the first reaction kettle A, the second reaction kettle B and the third reaction kettle C by using nitrogen or helium, and vacuumizing; adding yellow phosphorus and calcium hydroxide into the first reaction kettle A, the second reaction kettle B and the third reaction kettle C, starting a stirring device of the reaction kettles, and stirring at a constant speed of 90-120 r/min; controlling the temperature to be 80-95 ℃; and then, controlling the flow by a flow meter and adding a sodium hydroxide solution, wherein the reaction pressure is 0-0.25 MPa, and the reaction time is 1-5 h. Three reaction kettles are connected in parallel, and the reaction salt solution is alternately fed and discharged. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time. When the system is started for the first time, the production can be continued after the balance of the rectification system is established.
The weight ratio of the yellow phosphorus to the calcium hydroxide is 1: 0.8 to 1.2.
The weight ratio of the yellow phosphorus to the sodium hydroxide is 1: 0.75-0.85.
The weight ratio of the yellow phosphorus to the water is 1: 5 to 7.
The preparation weight ratio of the calcium hydroxide and the water in the lime milk is 1: 1.
(2) and the crude phosphane generated by the reaction passes through a primary condenser D and a secondary condenser E and then enters a constant-pressure buffer tank F. Controlling the temperature of the primary condenser D to be-50 to-30 ℃, wherein the temperature fluctuation is not more than +/-2 ℃; the temperature of the secondary condenser E is controlled to be-70 to-60 ℃, and the temperature fluctuation is not more than +/-1 ℃. High boiling impurities are initially removed by two-stage cryogenic freezing.
(3) Feeding the crude phosphane in the constant-pressure buffer tank F into a primary rectifying tower H, controlling the temperature of the primary rectifying tower H to be-89 to-72 ℃ by using liquid nitrogen as a refrigerant, controlling the temperature fluctuation to be not more than +/-1 ℃ and controlling the pressure to be 0 to 0.25MPa, extracting low-boiling-point impurities from the top of the tower, and feeding the materials extracted from the bottom of the tower into a secondary rectifying tower I; the temperature of the secondary rectifying tower I is controlled to be-85 to-68 ℃ by using liquid nitrogen as a refrigerant, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0 to 0.25MPa, high-boiling-point impurities are extracted from a tower kettle, and materials extracted from the tower top enter an adsorption column. The rectification system establishes a total reflux system, and when the supply of the crude phosphane is not in time or the pressure flow of the system is reduced, the system automatically switches to a total reflux mode to carry out self-circulation so as to ensure the purity of the product.
The adsorbent filled in the adsorption column K, the adsorption column L and the adsorption column M is one or a combination of more of soda lime, activated carbon and molecular sieves.
(4) The material after the absorption fills the dress, connects in parallel with pipeline and valve with 4 ~ 16 steel bottles in advance and constitutes steel bottle group P to connect in filling the pipeline after the replacement of evacuation in advance. And (3) placing the steel bottle group P in a liquid nitrogen tank Q, controlling the liquid level height of the liquid nitrogen tank Q to be 1/4-1/2 of the bottle height, controlling the inlet pressure to be 0-0.25 MPa, and controlling the flow meters to fill the bottles one by one.
Example 1
After the nitrogen replacement system is vacuumized, 600Kg of lime milk is sequentially added into a first reaction kettle A, a second reaction kettle B and a third reaction kettle C, 1500Kg of deionized water is added, the temperature of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is raised to 60 ℃, 300Kg of yellow phosphorus is added, 743Kg of sodium hydroxide solution with the mass fraction of 32% is gradually added, the yellow phosphorus and mixed alkali react to release heat, the adding speed of sodium hydroxide is controlled, the temperature of a reaction salt solution is kept at 80 ℃, the rotating speed is kept at 120r/min, the system pressure is kept at 0.2MPa, and the generated phosphine crude gas is extracted. After 4h of reaction, no gas is generated, and the reaction salt solution is discharged after the reaction is finished. And a small amount of reaction salt solution is remained to play a liquid seal role when the reaction salt solution is discharged, so that the phosphine gas is prevented from being discharged. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel and alternately fed to produce and discharge a reaction salt solution. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time.
The salt solution generated by the reaction enters a subsequent treatment process, and the crude phosphane generated by the reaction is extracted to a primary condenser D, the temperature of the primary condenser D is controlled to be-30 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane subjected to impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the temperature of the secondary condenser E is-65 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane after impurity removal by the secondary condenser E enters a constant-pressure buffer tank F, and the pressure of the constant-pressure buffer tank F is 0.2 MPa; the phosphane passing through the constant-pressure buffer tank F enters a primary rectifying tower H, the temperature of the primary rectifying tower H is-72 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.2MPa, and low-boiling-point impurities are extracted from the top of the tower; the phosphane passing through the primary rectifying tower H enters a secondary rectifying tower I, the temperature of the secondary rectifying tower I is-68 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.2MPa, and high-boiling-point impurities are extracted from a tower kettle; allowing the phosphane to enter an adsorption column through a second-stage rectifying tower I, filling a first-stage adsorption column K, a second-stage adsorption column L and a third-stage adsorption column M with activated carbon and molecular sieve combined adsorbent, and performing low-temperature filling on the ultrapure phosphane obtained after adsorption; the steel cylinder group P is formed by connecting 16 steel cylinders in parallel, the inlet pressure of the steel cylinder group P is 0.16MPa, and the liquid level height of the liquid nitrogen tank Q is 1/3 of the cylinder height.
Three reaction kettles are alternately used for production to ensure that the phosphine with stable flow is generated. In the experiment, the total feeding amount of the yellow phosphorus is 1200Kg, and the recovery rates of the rectifying towers are all set at 94%. 288Kg of ultrapure phosphane product with a purity of 99.99995% is finally obtained.
Example 2
After the nitrogen replacement system is vacuumized, 480Kg of lime milk is sequentially added into a first reaction kettle A, a second reaction kettle B and a third reaction kettle C, 2100Kg of deionized water is added, the temperature of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is raised to 60 ℃, 300Kg of yellow phosphorus is added, 720Kg of sodium hydroxide solution with the mass fraction of 32 percent is gradually added, the yellow phosphorus and mixed alkali react to release heat, the adding speed of sodium hydroxide is controlled, the temperature of a reaction salt solution is kept at 90 ℃, the rotating speed is kept at 90r/min, the system pressure is kept at 0.25MPa, and the generated phosphine crude product gas is extracted. After 4h of reaction, no gas is generated, and the reaction salt solution is discharged after the reaction is finished. And a small amount of reaction salt solution is remained to play a liquid seal role when the reaction salt solution is discharged, so that the phosphine gas is prevented from being discharged. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel and alternately fed to produce and discharge a reaction salt solution. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time.
The salt solution generated by the reaction enters a subsequent treatment process, and the crude phosphane generated by the reaction is extracted to a primary condenser D, the temperature of the primary condenser D is controlled to be-40 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane subjected to impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the temperature of the secondary condenser E is-60 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane after impurity removal by the secondary condenser E enters a constant-pressure buffer tank F, and the pressure of the constant-pressure buffer tank F is 0.25 MPa; the phosphane passing through the constant-pressure buffer tank F enters a primary rectifying tower H, the temperature of the primary rectifying tower H is-76 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.25MPa, and low-boiling-point impurities are extracted from the top of the tower; the phosphane passing through the primary rectifying tower H enters a secondary rectifying tower I, the temperature of the secondary rectifying tower I is-72 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.25MPa, and high-boiling-point impurities are extracted from a tower kettle; allowing the phosphane to enter an adsorption column through a second-stage rectifying tower I, filling a first-stage adsorption column K, a second-stage adsorption column L and a third-stage adsorption column M with activated carbon and molecular sieve combined adsorbent, and performing low-temperature filling on the ultrapure phosphane obtained after adsorption; the steel cylinder group P is formed by connecting 16 steel cylinders in parallel, the inlet pressure of the steel cylinder group P is 0.20MPa, and the liquid level height of the liquid nitrogen tank Q is 1/2 of the height of the cylinder.
Three reaction kettles are alternately used for production to ensure that the phosphine with stable flow is generated. In the experiment, the total feeding amount of the yellow phosphorus is 1200Kg, and the recovery rate of the rectifying tower is set at 90 percent. 258Kg of ultrapure phosphane product with the purity of 99.999995 percent is finally obtained.
Embodiment 3
After the nitrogen replacement system is vacuumized, 720Kg of lime milk is sequentially added into a first reaction kettle A, a second reaction kettle B and a third reaction kettle C, 1800Kg of deionized water is added, the temperature of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is raised to 60 ℃, 300Kg of yellow phosphorus is added, 797Kg of sodium hydroxide solution with the mass fraction of 32% is gradually added, the yellow phosphorus and mixed alkali react to release heat, the adding speed of the sodium hydroxide is controlled, the temperature of the reaction salt solution is kept at 95 ℃, the rotating speed is kept at 90r/min, the system pressure is kept at 0.1MPa, and the generated phosphine crude product gas is extracted. After 3h of reaction, no gas is generated, and the reaction salt solution is discharged after the reaction is finished. And a small amount of reaction salt solution is remained to play a liquid seal role when the reaction salt solution is discharged, so that the phosphine gas is prevented from being discharged. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel and alternately fed to produce and discharge a reaction salt solution. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time.
The salt solution generated by the reaction enters a subsequent treatment process, and the crude phosphane generated by the reaction is extracted to a primary condenser D, the temperature of the primary condenser D is controlled to be-30 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane subjected to impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the temperature of the secondary condenser E is-70 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane after impurity removal by the secondary condenser E enters a constant-pressure buffer tank F, and the pressure of the constant-pressure buffer tank F is 0.1 MPa; the phosphane passing through the constant-pressure buffer tank F enters a primary rectifying tower H, the temperature of the primary rectifying tower H is-80 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.1MPa, and low-boiling-point impurities are extracted from the top of the tower; the phosphane passing through the primary rectifying tower H enters a secondary rectifying tower I, the temperature of the secondary rectifying tower I is-76 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.1MPa, and high-boiling-point impurities are extracted from a tower kettle; allowing the phosphane to enter an adsorption column through a second-stage rectifying tower I, filling a soda lime and molecular sieve combined adsorbent into a first-stage adsorption column K, a second-stage adsorption column L and a third-stage adsorption column M, and filling the ultrapure phosphane obtained after adsorption at a low temperature; the steel cylinder group P is formed by connecting 16 steel cylinders in parallel, the inlet pressure of the steel cylinder group P is 0.06MPa, and the liquid level height of the liquid nitrogen tank Q is 1/2 of the height of the cylinder.
Three reaction kettles are alternately used for production to ensure that the phosphine with stable flow is generated. In the experiment, the total feeding amount of the yellow phosphorus is 1200Kg, and the recovery rate of the rectifying tower is set at 95 percent. 292Kg of ultrapure phosphane product with a purity of 99.99995% is finally obtained.
Example 4
After the nitrogen replacement system is vacuumized, 600Kg of lime milk is sequentially added into a first reaction kettle A, a second reaction kettle B and a third reaction kettle C, 1500Kg of deionized water is added, the temperature of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is raised to 60 ℃, 300Kg of yellow phosphorus is added, 743Kg of sodium hydroxide solution with the mass fraction of 32% is gradually added, the yellow phosphorus and mixed alkali react to release heat, the adding speed of sodium hydroxide is controlled, the temperature of a reaction salt solution is kept at 95 ℃, the rotating speed is kept at 90r/min, the system pressure is kept at 0.05MPa, and the generated phosphine crude gas is extracted. After 5h of reaction, no gas is generated, and the reaction salt solution is discharged after the reaction is finished. And a small amount of reaction salt solution is remained to play a liquid seal role when the reaction salt solution is discharged, so that the phosphine gas is prevented from being discharged. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel and alternately fed to produce and discharge a reaction salt solution. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time.
The salt solution generated by the reaction enters a subsequent treatment process, and the crude phosphane generated by the reaction is extracted to a primary condenser D, the temperature of the primary condenser D is controlled to be 50 ℃ below zero, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane subjected to impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the temperature of the secondary condenser E is-70 ℃, and the temperature fluctuation is not more than +/-2 ℃; feeding the crude phosphane subjected to impurity removal by the secondary condenser E into a constant-pressure buffer tank F, wherein the pressure of the constant-pressure buffer tank F is 0.05 MPa; the phosphane passing through the constant-pressure buffer tank F enters a primary rectifying tower H, the temperature of the primary rectifying tower H is-89 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.05MPa, and low-boiling-point impurities are extracted from the top of the tower; the phosphane passing through the primary rectifying tower H enters a secondary rectifying tower I, the temperature of the secondary rectifying tower I is-85 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.05MPa, and high-boiling-point impurities are extracted from a tower kettle; the phosphane passing through the secondary rectifying tower I is directly filled at low temperature, a steel cylinder group P is formed by connecting 16 steel cylinders in parallel, the inlet pressure of the steel cylinder group P is 0.05MPa, and the liquid level height of a liquid nitrogen tank Q is 1/2 of the height of the cylinder.
Three reaction kettles are alternately used for production to ensure that the phosphine with stable flow is generated. In the experiment, the total feeding amount of the yellow phosphorus is 1200Kg, and the recovery rates of the rectifying towers are all set at 92%. Finally, 278.5Kg of ultrapure phosphane product with the purity of 99.99995 percent is obtained.
Example 5
After the nitrogen replacement system is vacuumized, 600Kg of lime milk is sequentially added into a first reaction kettle A, a second reaction kettle B and a third reaction kettle C, 1800Kg of deionized water is added, the temperature of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C is raised to 60 ℃, 300Kg of yellow phosphorus is added, 743Kg of sodium hydroxide solution with the mass fraction of 32% is gradually added, the yellow phosphorus and mixed alkali react to release heat, the adding speed of sodium hydroxide is controlled, the temperature of the reaction salt solution is kept at 80 ℃, the rotating speed is kept at 100r/min, the system pressure is kept at 0.15MPa, and the generated phosphine crude gas is extracted. After 5h of reaction, no gas is generated, and the reaction salt solution is discharged after the reaction is finished. And a small amount of reaction salt solution is remained to play a liquid seal role when the reaction salt solution is discharged, so that the phosphine gas is prevented from being discharged. The first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel and alternately fed to produce and discharge a reaction salt solution. The three reaction kettles do not discharge the reaction salt solution at the same time, so that at least one reaction kettle can be used for feeding production at any time.
The salt solution generated by the reaction enters a subsequent treatment process, and the crude phosphine generated by the reaction is extracted to a first-stage condenser D, the temperature of the first-stage condenser D is controlled to be-40 ℃, and the temperature fluctuation is not more than +/-2 ℃; the crude phosphane subjected to impurity removal by the primary condenser D enters a secondary condenser E for deep impurity removal, the temperature of the secondary condenser E is-60 ℃, and the temperature fluctuation is not more than +/-1 ℃; the crude phosphane after impurity removal by the secondary condenser E enters a constant-pressure buffer tank F, and the pressure of the constant-pressure buffer tank F is 0.15 MPa; the phosphane passing through the constant-pressure buffer tank F enters a primary rectifying tower H, the temperature of the primary rectifying tower H is-85 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.15MPa, and low-boiling-point impurities are extracted from the top of the tower; the phosphane passing through the primary rectifying tower H enters a secondary rectifying tower I, the temperature of the secondary rectifying tower I is-81 ℃, the temperature fluctuation is not more than +/-1 ℃, the pressure is 0.15MPa, and high-boiling-point impurities are extracted from a tower kettle; the phosphane passing through the secondary rectifying tower I is directly filled at low temperature, a steel cylinder group P is formed by connecting 16 steel cylinders in parallel, the inlet pressure of the steel cylinder group P is 0.15MPa, and the liquid level height of a liquid nitrogen tank Q is 1/3 of the height of the cylinder.
Three reaction kettles are alternately used for production to ensure that the phosphine with stable flow is generated. In the experiment, the total feeding amount of the yellow phosphorus is 1200Kg, and the recovery rate of the rectifying tower is set at 90 percent. 268.3Kg of ultrapure phosphane product with a purity of 99.99995% is finally obtained.

Claims (10)

1. A method for the continuous production of ultrapure phosphanes; the method is characterized by comprising the following steps:
(1) controlling the temperature of yellow phosphorus and lime to be 80-95 ℃ in water environment; controlling the flow of a flowmeter, adding a sodium hydroxide solution, wherein the reaction pressure is 0-0.25 MPa, and the reaction time is 1-6 h; a plurality of reaction kettles are connected in parallel, and reaction liquid is alternately fed, produced and discharged; obtaining a crude phosphane;
(2) freezing high-boiling-point impurities in a condenser by two-stage low-temperature freezing of the crude phosphane; the temperature of the freezing unit is controlled to be-70 to-30 ℃; feeding the frozen and impurity-removed crude phosphane into a constant-pressure buffer tank to supply gas to a rectification and adsorption device;
(3) removing impurities with high and low boiling points from the crude phosphane provided by the constant-pressure buffer tank through a two-stage low-temperature low-pressure rectifying tower; the operating pressure is 0-0.25 MPa, and the operating temperature is-89 to-68 ℃;
(4) adsorbing the rectified phosphane; obtaining an ultrapure phosphane product with the purity of more than or equal to 99.99999;
(5) filling an ultrapure phosphine product into a low-temperature negative-pressure steel cylinder group through a mass flow meter; the steel cylinder group is arranged in the liquid nitrogen tank, and the liquid level height of the liquid nitrogen tank is controlled to be 1/4-1/2 of the bottle height; the filling pressure is 0-0.25 MPa.
2. The method according to claim 1, wherein in step (1), the ratio of the yellow phosphorus to the calcium hydroxide is 1: 0.8 to 1.2; the weight ratio of the yellow phosphorus to the sodium hydroxide is 1: 0.75 to 0.85; the weight ratio of the yellow phosphorus to the water is 1: 5-7; the preparation weight ratio of the calcium hydroxide and the water in the lime milk is 1: 1.
3. the method of claim 1, wherein the step (4) adopts a multi-stage adsorption method, and the adsorbent for adsorption is one or more of activated carbon, soda lime, molecular sieve and high-temperature trap.
4. A device for continuously producing ultrapure phosphane comprises a first reaction kettle A, a second reaction kettle B, a third reaction kettle C, a first-stage condenser D, a second-stage condenser E, a constant-pressure buffer tank F, a first-stage rectifying tower H, a second-stage rectifying tower I, a first-stage adsorption column K, a second-stage adsorption column L, a third-stage adsorption column M, a steel cylinder group P and a liquid nitrogen tank Q; the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are connected in parallel, and the materials are alternately fed for production and reaction liquid is discharged; the upper parts of the first reaction kettle A, the second reaction kettle B and the third reaction kettle C are provided with inlets of calcium hydroxide, sodium hydroxide, water and yellow phosphorus, the top part of the first reaction kettle A is provided with a reaction gas outlet, the bottom part of the first reaction kettle B is provided with a salt solution outlet, and the reaction gas outlet is connected with a primary condenser D; the first-stage condenser D is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first reaction kettle A, the second reaction kettle B and the third reaction kettle C, and the material outlet is connected with the second-stage condenser E; the second-stage condenser E is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage condenser D, and the material outlet is connected with the constant-pressure buffer tank F; the constant-pressure buffer tank F is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary condenser E, and the material outlet is connected with the primary rectifying tower H; a material inlet is arranged in the middle of the primary rectifying tower H, a tower top extraction outlet is arranged at the top of the primary rectifying tower H, a tower kettle extraction outlet is arranged at the bottom of the primary rectifying tower H, the material inlet is connected with a constant-pressure buffer tank F, a tower top extraction outlet extracts low-boiling-point impurities, and a tower kettle extraction outlet is connected with the secondary rectifying tower I; the middle part of the second-stage rectifying tower I is provided with a material inlet, the top part of the second-stage rectifying tower I is provided with a tower top extraction outlet, the bottom part of the second-stage rectifying tower I is provided with a tower bottom extraction outlet, the material inlet is connected with the first-stage rectifying tower H, a tower bottom extraction outlet extracts high-boiling-point impurities, and the tower top extraction outlet is connected with the first-stage adsorption column K; the adsorption column K is provided with a material inlet and a material outlet, wherein the material inlet is connected with the secondary rectifying tower I, and the material outlet is connected with the secondary adsorption column L; the second-stage adsorption column L is provided with a material inlet and a material outlet, wherein the material inlet is connected with the first-stage adsorption column K, and the material outlet is connected with the third-stage adsorption column M; the third-stage adsorption column M is provided with a material inlet and a material outlet, wherein the material inlet is connected with the second-stage adsorption column L, and the material outlet is connected with the steel cylinder group P; the steel bottle group P is placed in a liquid nitrogen tank Q.
5. The apparatus as set forth in claim 4, wherein the first reactor A, the second reactor B and the third reactor C are connected in parallel at a reaction temperature of 80-95 ℃ and a reaction pressure of 0-0.25 MPa, and are alternately charged to produce and discharge the reaction solution.
6. The apparatus as claimed in claim 4, wherein the temperature of the primary condenser D is-50 to-30 ℃, and the temperature fluctuation is not more than +/-2 ℃; the temperature E of the secondary condenser is-70 to-60 ℃, and the temperature fluctuation is not more than +/-2 ℃.
7. The apparatus of claim 4, wherein the ratio of the volume of the constant pressure buffer tank F to the volume of the reaction vessel is 5-20: 1, and a constant pressure device is arranged.
8. The apparatus as claimed in claim 4, wherein the rectification column H is operated at a pressure of 0 to 0.25MPa, an operating temperature of-89 to-72 ℃ and a temperature fluctuation of not more than. + -. 1 ℃; the operating pressure of the rectifying tower I is 0-0.25 MPa, the operating temperature is-85 to-68 ℃, and the temperature fluctuation is not more than +/-1 ℃; the cold energy source of the rectifying tower H and the rectifying tower I is liquid nitrogen.
9. The apparatus of claim 4, wherein the cylinder group P comprises 4 to 16 cylinders connected in parallel.
10. The device as claimed in claim 4, wherein the steel bottle group P is filled by low-temperature negative pressure, liquid nitrogen is used as a refrigerant for freezing and filling the bottles, and the immersion height of the liquid nitrogen in the liquid nitrogen pool Q is 1/4-1/2 of the bottle height; the filling weight control mode adopted by the steel bottle group P is the mass flowmeter control; the pressure of the inlet P of the steel cylinder group is 0-0.25 MPa.
CN202210379458.7A 2022-04-12 2022-04-12 Method and device for continuously producing ultrapure phosphane Pending CN115072680A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111453708A (en) * 2020-05-21 2020-07-28 天津中科拓新科技有限公司 Method and device for synthesizing and refining electronic grade phosphane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111453708A (en) * 2020-05-21 2020-07-28 天津中科拓新科技有限公司 Method and device for synthesizing and refining electronic grade phosphane

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