CN112934123A - Fixed bed reactor for preparing high-purity argon - Google Patents

Abstract

A fixed bed reactor for preparing high-purity argon gas comprises a reactor and an oxygen carrier arranged in the reactor, wherein the reactor comprises a reactor upper end enclosure, a first cylinder, a second cylinder and a reactor lower end enclosure, the reactor upper end enclosure, the first cylinder, the second cylinder and the reactor lower end enclosure are sequentially connected into a whole, the reactor upper end enclosure is provided with a feed inlet, and the first cylinder is provided with a first liquid inlet and a first liquid outlet₄Oxygen supply activity of (3), CO and H increase₂Reaction rate of impurity gas, Al₂O₃The addition of the double metals improves the activity of the oxygen carrier by utilizing the synergistic effect of the double metals，Al³⁺The addition of the oxygen carrier also improves the stability of the oxygen carrier, and has wide application prospect.

Description

Fixed bed reactor for preparing high-purity argon

Technical Field

The invention relates to a fixed bed reactor, in particular to a fixed bed reactor for preparing high-purity argon.

Background

In the production and preparation process of monocrystalline silicon, at present, a pure argon atmosphere crystal pulling process is mostly adopted. Argon is an inert gas which acts as a protective gas around the liquid level of the single crystal silicon and the polycrystalline silicon to protect the single crystal silicon and the polycrystalline silicon from oxidation. Moreover, since argon gas flows in the single crystal furnace, the argon gas can be volatilized, and the single crystal silicon or polycrystalline silicon liquid can be prevented from being polluted to influence the product quality of the single crystal silicon. In addition, the argon forms uniform laminar flow from top to bottom and sweeps across the surface of the crystal, so that the latent heat of crystallization can be taken away, and the normal growth of the monocrystalline silicon can be ensured.

However, the purity of the argon required by the production of the monocrystalline silicon reaches 99.999 percent, the consumption is large, and after the monocrystalline silicon is produced for one time, the argon can be subjected to CO and H₂And the impurity gas is polluted, so that the purity is reduced and the reuse is not realized. The one-time use of the high-purity argon in the production process of the monocrystalline silicon inevitably increases the production cost. If can be treated by CO and H₂And purifying the argon polluted by the impurity gas to obtain high-purity argon again, so that the production cost can be reduced inevitably, the industry development is promoted, and the existing reactor can not reach the standard.

Disclosure of Invention

A fixed bed reactor for preparing high-purity argon gas comprises a reactor and an oxygen carrier arranged in the reactor, wherein the reactor comprises a reactor upper head, a first barrel, a second barrel and a reactor lower head, the reactor upper head, the first barrel, the second barrel and the reactor lower head are sequentially connected into a whole, the reactor upper head is provided with a feed inlet, the first barrel is provided with a first liquid inlet and a first liquid outlet, the second barrel is provided with a second liquid inlet and a second liquid outlet, the lower part of the reactor lower head is provided with a discharge outlet, a first tube plate and a second tube plate are fixed in the first barrel, vertically arranged reaction tubes are fixed on the first tube plate and the second tube plate, the oxygen carrier is filled in the reaction tubes, a third tube plate and a fourth tube plate are fixed in the second barrel, a transversely arranged liquid passing tube is fixed between the third tube plate and the fourth tube plate, the interval part of the liquid passing pipe is filled with an oxygen carrier.

A plurality of baffle plates are also arranged in the first cylinder.

The temperature of the fixed bed reactor is 150-200 ℃.

The oxygen carrier is M-CuCoFeO₄/Al₂O₃An oxygen carrier.

And M is Ag or Pd.

And M is Pd.

The M-CuCoFeO₄/Al₂O₃The preparation method of the oxygen carrier comprises the following steps:

s1: adding inorganic copper salt, inorganic cobalt salt and inorganic iron salt into water, stirring and mixing uniformly to obtain uniform solution, adding polyethylene glycol, citric acid and porous Al₂O₃Stirring and heating to 80-95 ℃, and reacting for 10-15h to obtain gel;

s2: drying the gel at the temperature of 100-120 ℃ for 10-15 h;

s3: heating to 300-500 ℃ for calcination for 2-5h, heating to 700-900 ℃ for calcination for 2-5h, cooling, grinding and sieving to obtain a precursor;

s4: dispersing the precursor in methanol water solution containing palladium acetate or silver nitrate, performing ultrasonic treatment for 20-30min, filtering, irradiating under a high-pressure mercury lamp for 10-20h, washing with water, and drying.

The invention has the beneficial effects that:

the first cylinder is internally provided with a plurality of baffle plates so as to separate a plurality of catalytic reaction zones, thereby reducing the thickness of a single reaction zone, reducing the temperature rise of a catalyst bed layer, simultaneously reducing the pressure drop of the single bed layer, leading the reaction to be carried out under the condition of more uniform and stable, and when the second cylinder is further catalyzed, changing the second cylinder into a catalytic reaction zone which is transversely arranged, thereby improving the reaction efficiency under the condition of ensuring normal temperature rise;

Pd-CuCoFeO in the invention₄/Al₂O₃Oxygen carrier in CO and H₂When the impurity gas is combusted, oxygen required by combustion can be provided, and no additional oxygen is required to be added, so that oxygen pollution caused by insufficient combustion is avoided, namely CuCoFeO₄The oxygen migration energy barrier is low, the oxygen vacancy forming energy is low, the reaction can be carried out at low temperature, the reduction depth is high, and the addition of palladium atoms can further improve the CuCoFeO₄Oxygen supply activity of (3), CO and H increase₂Reaction rate of impurity gas, Al₂O₃While the activity of the oxygen carrier is improved by utilizing the synergistic effect of the bimetal, Al³⁺The addition of the oxygen carrier also improves the stability of the oxygen carrier, and has wide application prospect.

Drawings

Fig. 1 is an overall structural view of the present invention.

Reference numerals: 1. a feed inlet; 2. an upper end enclosure of the reactor; 3. a feed distributor; 4. a first tube sheet; 5. an oxygen carrier; 6. a reaction tube; 7. a first liquid inlet; 8. a first liquid outlet; 9. a first cylinder; 10. a second cylinder; 11. a second liquid outlet; 12. a second liquid inlet; 13. a third tube sheet; 14. a second tube sheet; 15. a fourth tube sheet; 16. a liquid passing pipe; 17. a support leg; 18. a discharge port; 19. a reactor lower end enclosure; 20. and (7) a baffle plate.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

Example (b):

referring to fig. 1, a fixed bed reactor for preparing high-purity argon gas comprises a reactor and an oxygen carrier 5 arranged inside the reactor, wherein the reactor comprises a reactor upper head 2, a first cylinder 9, a second cylinder 10 and a reactor lower head 19, the reactor upper head 2, the first cylinder 9, the second cylinder 10 and the reactor lower head 19 are connected in sequence, the reactor upper head 2 is provided with a feed inlet 1, the first cylinder 9 is provided with a first inlet 7 and a first outlet 8, the second cylinder 10 is provided with a second inlet 12 and a second outlet 11, the lower part of the reactor lower head 19 is provided with a discharge outlet 18, the first cylinder 9 is internally fixed with a first tube plate 4 and a second tube plate 14, the first tube plate 4 and the second tube plate 14 are fixedly provided with a reaction tube 6 which is vertically arranged, the reaction tube 6 is filled with the oxygen carrier 5, a third tube plate 13 and a fourth tube plate 15 are fixed in the second cylinder 10, a liquid passing tube 16 transversely arranged is fixed between the third tube plate 13 and the fourth tube plate 15, an oxygen carrier 5 is filled in the interval part of the liquid passing tube 16, and a support leg 17 is fixed at the lower part of the second cylinder 10.

A plurality of baffles 20 are also arranged in the first cylinder 9.

The temperature of the fixed bed reactor is 150-200 ℃.

The oxygen carrier 5 is M-CuCoFeO₄/Al₂O₃An oxygen carrier 5.

And M is Ag or Pd.

And M is Pd.

The M-CuCoFeO₄/Al₂O₃The preparation method of the oxygen carrier 5 comprises the following steps:

s1: adding inorganic copper salt, inorganic cobalt salt and inorganic iron salt into water, stirring and mixing uniformly to obtain uniform solution, adding polyethylene glycol, citric acid and porous Al₂O₃Stirring and heating to 80-95 ℃, and reacting for 10-15h to obtain gel;

s2: drying the gel at the temperature of 100-120 ℃ for 10-15 h;

s3: heating to 300-500 ℃ for calcination for 2-5h, heating to 700-900 ℃ for calcination for 2-5h, cooling, grinding and sieving to obtain a precursor;

s4: dispersing the precursor in methanol water solution containing palladium acetate or silver nitrate, performing ultrasonic treatment for 20-30min, filtering, irradiating under a high-pressure mercury lamp for 10-20h, washing with water, and drying.

The working principle of the invention is as follows: gas is introduced into the feed inlet 1, and respectively enters the reaction tube 6 to react with the oxygen carrier 5 after being uniformly distributed by the feed distributor 3, wherein the Pd-CuCoFeO in the invention₄/Al₂O₃Oxygen carrier 5 in CO, H₂When the impurity gas is combusted, oxygen required by combustion can be provided, and no additional oxygen is required to be added, so that oxygen pollution caused by insufficient combustion is avoided, namely CuCoFeO₄The oxygen migration energy barrier is low, the oxygen vacancy forming energy is low, the reaction can be carried out at low temperature, the reduction depth is high, and the addition of palladium atoms can further improve the CuCoFeO₄Oxygen supply activity of (3), CO and H increase₂Reaction rate of impurity gas, Al₂O₃While the activity of the oxygen carrier 5 is improved by utilizing the synergistic effect of the bimetal, Al³⁺Also improves the stability of the oxygen carrier 5, inside said first cylinder 9The plurality of baffle plates 20 are arranged to separate a plurality of catalytic reaction zones, so that the thickness of a single reaction zone is reduced, the temperature rise of a catalyst bed layer is reduced, and the pressure drop of the single bed layer is reduced, so that the reaction is carried out under the condition of more uniformity and stability;

when the second cylinder 10 is further catalyzed, the second cylinder is changed into a catalytic reaction zone which is transversely arranged, so that the reaction efficiency can be improved under the condition of normal temperature rise.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (7)

1. A fixed bed reactor for preparing high-purity argon gas is characterized in that: the reactor comprises a reactor and an oxygen carrier arranged in the reactor, wherein the reactor comprises a reactor upper end enclosure, a first cylinder, a second cylinder and a reactor lower end enclosure, the reactor upper end enclosure, the first cylinder, the second cylinder and the reactor lower end enclosure are sequentially connected into a whole, the reactor upper end enclosure is provided with a feed inlet, the first cylinder is provided with a first liquid inlet and a first liquid outlet, the second cylinder is provided with a second liquid inlet and a second liquid outlet, the lower part of the reactor lower end enclosure is provided with a discharge outlet, the first cylinder is internally fixed with a first tube plate and a second tube plate, the first tube plate and the second tube plate are fixedly provided with vertically arranged reaction tubes, the reaction tubes are filled with the oxygen carrier, the second cylinder is internally fixed with a third tube plate and a fourth tube plate, and a horizontally arranged liquid passing tube is fixed between the third tube plate and the fourth tube plate, the interval part of the liquid passing pipe is filled with an oxygen carrier.

2. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: a plurality of baffle plates are also arranged in the first cylinder.

3. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: the temperature of the fixed bed reactor is 150-200 ℃.

4. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: the oxygen carrier is M-CuCoFeO₄/Al₂O₃An oxygen carrier.

5. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: and M is Ag or Pd.

6. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: and M is Pd.

7. A fixed bed reactor for producing high purity argon as claimed in claim 1 wherein: the M-CuCoFeO₄/Al₂O₃The preparation method of the oxygen carrier comprises the following steps:

s1: adding inorganic copper salt, inorganic cobalt salt and inorganic iron salt into water, stirring and mixing uniformly to obtain uniform solution, adding polyethylene glycol, citric acid and porous Al₂O₃Stirring and heating to 80-95 ℃, and reacting for 10-15h to obtain gel;

s2: drying the gel at the temperature of 100-120 ℃ for 10-15 h;

s3: heating to 300-500 ℃ for calcination for 2-5h, heating to 700-900 ℃ for calcination for 2-5h, cooling, grinding and sieving to obtain a precursor;

s4: dispersing the precursor in methanol water solution containing palladium acetate or silver nitrate, performing ultrasonic treatment for 20-30min, filtering, irradiating under a high-pressure mercury lamp for 10-20h, washing with water, and drying.

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