Cuprous ion modified adsorbent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of polycrystalline silicon production, in particular to a cuprous ion modified adsorbent as well as a preparation method and application thereof. The cuprous ion modified adsorbent comprises an inorganic carrier containing a nitrogen element and Cu < + > loaded on the inorganic carrier. The low-valence Cu < + > ions are used as key active components, the dispersity of Cu < + > species is improved by means of rich pore channels and structural nitrogen sites in the activated carrier, the utilization efficiency of active metal is greatly improved, then the adsorbability of the adsorbent is improved, and the adsorbent has certain regeneration capacity.

Description

Technical Field

[0001] The present invention relates to the technical field of polysilicon production, and particularly relates to a cuprous ion modified adsorbent, a preparation method thereof, and an application thereof. Background Art

[0002] High-purity polysilicon is the key to supporting the technological iteration of photovoltaic products. The contents of various impurities (donors, acceptors, metals, etc.) in polysilicon products must be limited to lower levels. Phosphorus, as a donor impurity in polysilicon battery products, is introduced through phosphorus-containing compounds in the feedstock chlorosilane and reduction hydrogen. At present, the removal of phosphorus impurities in chlorosilane is mainly achieved by adsorption in a material adsorption column, and additional light-component removal and heavy-component removal processes in the rectification section are used to remove light phosphorus and heavy phosphorus impurities. In addition, the disproportionation fixed bed is also an important outlet for phosphorus impurities. In the process of recovering reduction hydrogen, impurities with higher boiling points such as phosphorus trichloride and phosphorus pentachloride can be removed through processes such as pressurized condensation and chlorosilane rinsing absorption. However, light phosphorus impurities represented by phosphine are restricted by the adsorption equilibrium, and the adsorption effect of conventional adsorbents is not good, resulting in the cyclic accumulation of phosphorus impurities in the system, which in turn affects the purity of polysilicon products.

[0003] Regarding the removal scheme of phosphine, at present, metal oxides with oxidizing properties are mostly used as the active components on the surface of the active carrier, with divalent copper metal compounds as typical representatives. For example, patent document CN110449121A reports a copper oxide and zinc oxide modified zeolite molecular sieve adsorbent, which can adsorb hydride gases such as phosphine, arsine, and silane at room temperature without adding heavy metals or precious metals; patent document CN103736455A reports a copper and iron oxide modified organic metal framework as an adsorbent for low-concentration phosphine adsorption; patent document CN114870803A reports an arsine and phosphine special gas adsorbent, which is composed of active copper oxide and active alumina, and also adds auxiliaries such as manganese acetate, nickel oxide, silylated graphene, and sodium persulfate.

[0004] However, the adsorbents reported in the above patent documents have problems such as poor adsorption performance, difficulty in regeneration under the current polysilicon hydrogen recovery adsorption process, and short service life. Summary of the Invention

[0005] The purpose of the present invention is to overcome the problems existing in the prior art, such as poor adsorption performance of the adsorbent and short service life, and to provide a cuprous ion modified adsorbent, a preparation method thereof, and an application thereof. The cuprous ion modified adsorbent has better adsorption performance and is easy to regenerate under the current polysilicon hydrogen recovery adsorption process.

[0006] To achieve the above object, on the one hand, the present invention provides a cuprous ion-modified adsorbent, which comprises an inorganic carrier containing nitrogen element and Cu supported on the inorganic carrier. + ;

[0007] Wherein, in the modified adsorbent, the molar ratio of the content of Cu + to the nitrogen element is 1:0.3 - 1; the existing form of the nitrogen element is selected from at least one of pyridine-type nitrogen, pyrrole-type nitrogen, and graphite-type nitrogen.

[0008] On the second aspect, the present invention provides a preparation method of the cuprous ion-modified adsorbent, which comprises:

[0009] S1: In the presence of a solvent, the inorganic carrier is subjected to a first contact reaction with a composite modifier, and the obtained solid material I is subjected to an activation treatment at a temperature not lower than 400 °C to obtain a modified inorganic carrier;

[0010] S2: The modified inorganic carrier is subjected to a second contact reaction with a copper salt compound, and the obtained solid material II is subjected to a heat treatment in an acidic atmosphere and a reducing atmosphere to obtain the cuprous ion-modified adsorbent;

[0011] Wherein, the composite modifier is an ammonium salt and / or an iron salt; and, the mass ratio of the dosage of the composite modifier to the copper salt compound is 1:0.1 - 3.

[0012] On the third aspect, the present invention provides a cuprous ion-modified adsorbent prepared by the preparation method described in the second aspect.

[0013] On the fourth aspect, the present invention provides an application of the cuprous ion-modified adsorbent described in the first aspect in the purification of hydrogen recovered from polysilicon.

[0014] Through the above technical solution, taking low-cost Cu + ions as the key active component, the dispersion of Cu + species is improved by means of the rich pore channels and structural nitrogen sites in the activated carrier, the utilization efficiency of the active metal is greatly improved, and thus the adsorption property of the adsorbent is improved, and the adsorbent has a certain regeneration ability. Detailed Embodiments

[0015] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values and individual point values of each range, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0016] On the one hand, the present invention provides a cuprous ion-modified adsorbent, which comprises an inorganic carrier containing nitrogen element and Cu supported on the inorganic carrier. + ;

[0017] Wherein, in the modified adsorbent, the molar ratio of the content of Cu + to the nitrogen element is 1:0.3 - 1; the existing form of the nitrogen element is selected from at least one of pyridine-type nitrogen, pyrrole-type nitrogen and graphite-type nitrogen.

[0018] In the present invention, in order to further improve the cooperative effect of Cu + and the nitrogen element, preferably, in the modified adsorbent, the molar ratio of the content of Cu + to the nitrogen element is 1:0.4 - 6.

[0019] In the present invention, preferably, the nitrogen element exists in the forms of pyridine-type nitrogen, pyrrole-type nitrogen and graphite-type nitrogen.

[0020] In the present invention, in order to improve the adsorption performance of the cuprous ion-modified adsorbent, preferably, the inorganic carrier is selected from at least one of activated carbon, activated alumina, molecular sieve and silica gel.

[0021] In the present invention, preferably, the pore diameter of the inorganic carrier is 0.1 - 15 nm, preferably 0.2 - 12 nm.

[0022] In the present invention, preferably, the specific surface area of the inorganic carrier is 200 - 2000 m 2 / g, preferably 300 - 1500 m 2 / g.

[0023] On the second aspect, the present invention provides a preparation method of a cuprous ion-modified adsorbent, which comprises:

[0024] S1: In the presence of a solvent, the inorganic carrier is subjected to a first contact reaction with a composite modifier, and the obtained solid material I is subjected to activation treatment under the condition of not less than 400 °C to obtain a modified inorganic carrier;

[0025] S2: The modified inorganic carrier is subjected to a second contact reaction with a copper salt compound, and the obtained solid material II is subjected to heat treatment under an acidic atmosphere and a reducing atmosphere to obtain the cuprous ion-modified adsorbent;

[0026] Wherein, the composite modifier is an ammonium salt and / or an iron salt; and, the mass ratio of the dosage of the composite modifier to the copper salt compound is 1:0.1 - 3.

[0027] In the present invention, to enhance the coordination effect between the composite modifier and the copper salt compound, preferably, the mass ratio of the dosage of the composite modifier to the copper salt compound is 1:0.5 - 2.

[0028] In the present invention, preferably, in step S1, the solvent is selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran. More preferably, based on the mass of the inorganic carrier, the dosage of the solvent is 30 - 60 wt%, preferably 40 - 50 wt%, for example, it can be values such as 40 wt%, 45 wt%, 47 wt%, 50 wt% and the range between any values.

[0029] In the present invention, preferably, in step S1, the first contact reaction includes impregnating the inorganic carrier in a solution containing the composite modifier, and the conditions of the first contact reaction include: the temperature is 20 - 40 °C, and the time is 12 - 24 h.

[0030] In the present invention, preferably, step S1 further includes: performing a first drying treatment on the product obtained after the first contact reaction to obtain solid material I. More preferably, the conditions of the first drying treatment include: the temperature is 60 - 100 °C, and the time is 8 - 12 h.

[0031] In the present invention, preferably, step S1 further includes: sequentially washing and performing a second drying treatment on the product after the activation treatment to prepare a modified inorganic carrier. More preferably, the detergent used in the washing treatment is selected from acid agents and / or deionized water; the concentration of the acid agent is preferably 0.5 - 2 mol / L.

[0032] In the present invention, preferably, the conditions of the second drying treatment include: the temperature is 80 - 110 °C, and the time is 6 - 9 h.

[0033] According to a preferred embodiment, in step S1, the dosage of the composite modifier is 3 - 30 wt% of the mass of the inorganic carrier, preferably 12 - 18 wt%, for example, it can be values such as 12 wt%, 14 wt%, 15 wt%, 16 wt%, 18 wt% and the range between any values thereof.

[0034] To improve the modification effect of the composite modifier, according to another preferred embodiment, in the composite modifier, the mass ratio of the ammonium salt to the iron salt dosage is 1:0.2 - 3, preferably 1:0.4 - 1.

[0035] In the present invention, in order to further improve the cooperation of the composite modifier and thus enhance its modification effect, preferably, the ammonium salt is selected from at least one of tributylammonium nitrate, butyltriethylammonium hexafluorophosphate, trimethylbutylammonium nitrate, triethylpropylammonium acetate, tetraethylammonium acetate, tetrapropylammonium phosphate, and propyltributylammonium phosphate; the iron salt is selected from at least one of iron nitrate, iron acetate, and iron sulfate.

[0036] In the present invention, preferably, in step S1, the conditions for the activation treatment include: a temperature of 400 - 600 °C and a time of 1 - 4 h. More preferably, the conditions for the activation treatment include: a temperature of 450 - 550 °C and a time of 1.5 - 3.5 h.

[0037] In the present invention, preferably, step S2 includes: subjecting the modified inorganic support to a second contact reaction with a mixture of a copper salt compound and a metal chloride, and subjecting the obtained solid material II to heat treatment in an acidic atmosphere to obtain the cuprous ion-modified adsorbent.

[0038] In the present invention, preferably, step S2 further includes: continuously purging the product after the heat treatment with argon for 2 - 4 h to obtain the cuprous ion-modified adsorbent.

[0039] In the present invention, preferably, the metal chloride is selected from calcium salt chloride and / or cerium salt chloride, and may be, for example, calcium chloride or cerium chloride. More preferably, based on the weight of the copper salt compound, the dosage of the metal chloride is 10 - 45 wt%, preferably 15 - 40 wt%.

[0040] In the present invention, preferably, the second contact reaction includes: immersing the modified inorganic support in a solution containing a copper salt compound and a metal chloride, and then performing a third drying treatment.

[0041] In the present invention, preferably, the conditions for the second contact reaction include: a temperature of 20 - 40 °C and a time of 3 - 10 h.

[0042] In the present invention, preferably, the conditions for the third drying treatment include: a temperature of 60 - 80 °C and a time of 12 - 18 h.

[0043] In the present invention, by enhancing the coordination effect between the structural nitrogen sites and Cu + preferably, in step S2, the copper salt compound is selected from at least one of copper nitrate, cuprous nitrate, copper sulfate, cuprous sulfate, copper bromide, cuprous bromide, copper chloride, cuprous chloride, copper formate, copper acetate, and copper acetylacetonate.

[0044] In the present invention, preferably, the copper salt compound is copper formate and copper bromide. More preferably, the mass ratio of the amounts of copper formate and copper bromide used is 1:0.5 - 2.

[0045] In the present invention, to improve the efficiency of the heat treatment reaction, preferably, in step S2, the acidic atmosphere is hydrogen chloride and / or hydrogen bromide; the reducing atmosphere is selected from at least one of hydrogen, formaldehyde, acetaldehyde, ethylene, acetylene, and propyne. More preferably, the volume ratio of the acidic atmosphere to the reducing atmosphere is 1:0.1 - 0.3.

[0046] In the present invention, to further improve the efficiency of the heat treatment reaction, preferably, the conditions of the heat treatment include: the temperature is 80 - 150 °C and the time is 0.15 - 3 h.

[0047] The third aspect of the present invention provides a cuprous ion-modified adsorbent prepared by the preparation method described in the second aspect.

[0048] The cuprous ion-modified adsorbent prepared by using the preparation method described in the second aspect of the present invention has the same technical features as the cuprous ion-modified adsorbent described in the first aspect of the present invention, and will not be elaborated herein.

[0049] The fourth aspect of the present invention provides an application of the cuprous ion-modified adsorbent described in the first aspect or the third aspect in the purification of hydrogen recovered from polysilicon.

[0050] The cuprous ion-modified adsorbent obtained by adopting the above technical scheme has better adsorption performance and is easy to regenerate under the current hydrogen adsorption process for polysilicon recovery. According to some preferred embodiments, the PH3 adsorption removal rate of the cuprous ion-modified adsorbent prepared in the present invention is higher than 90%.

[0051] The present invention will be described in detail below through examples. The specific sources of the raw materials involved in the following examples are shown in Tables 1 and 2.

[0052] Table 1

[0053] Serial number Raw material Source Brand 1 Tributylammonium nitrate Macklin 33850-87-2 2 Cerium(III) chloride heptahydrate Macklin 18618-55-8 3 Butyltriethylammonium hexafluorophosphate Macklin 384347-46-0 4 Copper(II) acetylacetonate Macklin 13395-16-9 5 Trimethylammonium chloride Macklin 593-81-7

[0054] Table 2

[0055]

[0056] Example 1

[0057] S1: At room temperature (25 °C, the same below), 2 g of tributylammonium nitrate and 1 g of iron nitrate are dissolved in 10 ml of N,N-dimethylformamide, and then 20 g of activated carbon is added for the first contact reaction for 18 h, and then the first drying treatment is carried out at 80 °C for 12 h to obtain solid material I;

[0058] The above solid material I is subjected to activation treatment at 500 °C for 2 h, then washed successively with 1 mol / L dilute hydrochloric acid and deionized water, and then subjected to a second drying treatment at 90 °C for 8 h to obtain a modified inorganic support a1;

[0059] S2: At room temperature, 1.77 g of copper formate tetrahydrate, 1.78 g of anhydrous copper bromide, 0.42 g of anhydrous calcium chloride, and 0.39 g of cerium chloride heptahydrate are dissolved in 10 ml of deionized water, and then subjected to a second contact reaction with the modified inorganic support a1 for 5 h, and then subjected to a third drying treatment at 80 °C for 12 h to prepare a solid material II;

[0060] In a hydrogen bromide + formaldehyde (volume ratio 90:10) mixed atmosphere, the above solid material II is subjected to heat treatment at 100 °C for 0.5 h, and then purged with argon for 3 h to prepare a cuprous ion-modified adsorbent IA1.

[0061] Example 2

[0062] S1: At room temperature (25 °C, the same below), 2 g of butyltriethylammonium hexafluorophosphate and 1 g of iron acetate are dissolved in 15 ml of N,N-dimethylformamide, and then 25 g of activated carbon is added for a first contact reaction for 24 h, and then subjected to a first drying treatment at 90 °C for 10 h to obtain a solid material I;

[0063] The above solid material I is subjected to activation treatment at 550 °C for 2.5 h, then washed successively with 1.2 mol / L dilute hydrochloric acid and deionized water, and then subjected to a second drying treatment for 7.5 h to obtain a modified inorganic support a2;

[0064] S2: At room temperature, 1.90 g of copper formate tetrahydrate, 1.65 g of anhydrous copper bromide, 0.5 g of anhydrous calcium chloride, and 0.45 g of cerium chloride heptahydrate are dissolved in deionized water, and then subjected to a second contact reaction with the modified inorganic support a2 for 6 h, and then subjected to a third drying treatment at 70 °C for 14 h to prepare a solid material II;

[0065] In a hydrogen bromide + formaldehyde (volume ratio 90:10) mixed atmosphere, the above solid material II is subjected to heat treatment at 100 °C for 0.5 h, and then purged with argon for 3 h to prepare a cuprous ion-modified adsorbent IA2.

[0066] Example 3

[0067] According to the method similar to Example 1, the difference is that in step S1, 1.6 g of tributylammonium nitrate is used to replace 2 g of tributylammonium nitrate, and 1.2 g of iron nitrate is used to replace 1 g of iron nitrate, and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA3 is prepared.

[0068] Example 4

[0069] According to the method similar to Example 1, the difference is that in step S2, 2.11 g of anhydrous copper chloride is used to replace "1.77 g of copper formate tetrahydrate + 1.78 g of anhydrous copper bromide", and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA4 is prepared.

[0070] Example 5

[0071] According to the method similar to Example 1, the difference is that in step S2, 3.14 g of copper acetate monohydrate is used to replace "1.77 g of copper formate tetrahydrate + 1.78 g of anhydrous copper bromide", and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA5 is prepared.

[0072] Example 6

[0073] According to the method similar to Example 1, the difference is that step S2 is: at room temperature, 4.12 g of copper acetylacetonate, 0.42 g of anhydrous calcium chloride, and 0.39 g of cerium chloride heptahydrate are dissolved in 20 ml of N-methylpyrrolidone, and then second contact reaction is carried out with the modified inorganic support a1 for 10 h, and then third drying treatment is carried out at 60 °C for 18 h to prepare solid material II;

[0074] The remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA6 is prepared.

[0075] Example 7

[0076] According to the method similar to Example 1, the difference is that in step S2, a mixed atmosphere of hydrogen bromide + acetylene (volume ratio 85:15) is used to replace the mixed atmosphere of hydrogen bromide + formaldehyde (volume ratio 90:10), and the cuprous ion-modified adsorbent IA7 is prepared.

[0077] Example 8

[0078] According to the method similar to Example 1, the difference is that in step S1, 4 g of tributylammonium nitrate is used to replace 2 g of tributylammonium nitrate, and 2 g of iron nitrate is used to replace 1 g of iron nitrate;

[0079] In step S2, 1.5 g of copper formate tetrahydrate is used to replace 1.77 g of copper formate tetrahydrate, and 1.2 g of anhydrous copper bromide is used to replace 1.78 g of anhydrous copper bromide;

[0080] The remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA8 is prepared.

[0081] Example 9

[0082] According to a method similar to that in Example 1, the difference is that in step S2, 3 g of copper formate tetrahydrate is used to replace 1.77 g of copper formate tetrahydrate, and 3.5 g of cupric bromide anhydrous is used to replace 1.78 g of cupric bromide anhydrous; the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA9 is prepared.

[0083] Example 10

[0084] According to a method similar to that in Example 1, the difference is that 20 g of activated alumina is used to replace 20 g of activated carbon, and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA10 is prepared.

[0085] Example 11

[0086] According to a method similar to that in Example 1, the difference is that in step S2, anhydrous calcium chloride and cerium chloride heptahydrate are not used, and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IA11 is prepared.

[0087] Example 12

[0088] According to a method similar to that in Example 1, the difference is that in step S2, a mixed atmosphere of hydrogen bromide + acetylene (volume ratio 10:90) is used to replace the mixed atmosphere of hydrogen bromide + formaldehyde (volume ratio 90:10), and the cuprous ion-modified adsorbent IA12 is prepared.

[0089] Comparative Example 1

[0090] According to a method similar to that in Example 1, the difference is that in step S1, 0.6 g of tributylammonium nitrate is used to replace 2 g of tributylammonium nitrate, and 0.3 g of iron nitrate is used to replace 1 g of iron nitrate, and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IB1 is prepared.

[0091] Comparative Example 2

[0092] According to a method similar to that in Example 1, the difference is that in step S2, 2.08 g of anhydrous zinc chloride is used to replace "1.77 g of copper formate tetrahydrate + 1.78 g of cupric bromide anhydrous", and the remaining steps are the same as those in Example 1, and the cuprous ion-modified adsorbent IB2 is prepared.

[0093] Test Example 1

[0094] Test Example 1 is used to illustrate the molar contents of Cu + and nitrogen element in the cuprous ion-modified adsorbents prepared in the examples and comparative examples, as specifically shown in Table 3;

[0095] Test method: X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) were used to qualitatively and quantitatively analyze the content and species of Cu metal and nitrogen species in the adsorbent. The results are shown in Table 3.

[0096] Table 3

[0097] Adsorbent number <![CDATA[Cu + / mol]]> Pyridine-type nitrogen / mol Pyrrole-type nitrogen / mol Graphite-type nitrogen / mol IA1 0.0154 0.0053 0.0018 0.0012 IA2 0.0155 0.0043 0.0014 0.0005 IA3 0.0153 0.0043 0.0015 0.0011 IA4 0.0152 0.0055 0.0017 0.0013 IA5 0.0157 0.0051 0.0013 0.0011 IA6 0.0153 0.0059 0.0015 0.0009 IA7 0.0152 0.0055 0.0016 0.0015 IA8 0.0118 0.0098 0.0035 0.0023 IA9 0.0289 0.0056 0.0016 0.0017 IA10 0.0143 0.0032 0.0011 0.0008 IA11 0.0141 0.0055 0.0019 0.0016 IA12 0.0046 0.0045 0.0014 0.0008 IB1 0.0151 0.0015 0.0006 0.0003 IB2 / 0.0051 0.0017 0.0013

[0098] Test Example 2

[0099] Test Example 2 was used to test the adsorption performance of the cuprous ion-modified adsorbents prepared in the examples and comparative examples for PH3 impurities in the adsorption gas mixture. The specific results are shown in Table 4.

[0100] Test method:

[0101] Stage Y1: A certain amount of cuprous ion-modified adsorbent was loaded. After the airtightness check, a PH3 gas mixture was introduced for the adsorption experiment, and the concentration of phosphine at the tail gas end was detected at 2 h of the experiment.

[0102] Stage Y2: After the experiment in Stage Y1 was completed, the gas mixture was switched to high-purity hydrogen, heated to 160 °C and purged for 3 hours. After purging, the temperature was lowered to room temperature, and the PH3 gas mixture was re-introduced. The concentration of phosphine at the tail gas end was detected at 2 h of the experiment.

[0103] The detection method was spectrophotometry; the PH3 gas mixture was a PH3 / H2 gas mixture with a PH3 concentration of 100 ppm (mole fraction), a PH3 mixed gas space velocity of 300 ml (gas) / min·ml (adsorbent), and the adsorption experiment temperature was controlled at 30 °C. The data at 2 h of the adsorption experiment were compared. The data on the removal of PH3 impurities in the gas mixture by different cuprous ion-modified adsorbents are shown in Table 4. Each group of data was tested in parallel 3 times and the average value was taken. The calculation formula for the PH3 adsorption removal rate was: impurity adsorption rate Y = [(initial content of impurities in the gas mixture before adsorption - content of impurities in the gas mixture after adsorption) / (initial content of impurities in the gas mixture before adsorption)] * 100%.

[0104] Table 4

[0105] Adsorbent number <![CDATA[PH3 adsorption rate (%), Y1]]> <![CDATA[PH3 adsorption rate (%), Y2]]> IA1 96.3 93.2 IA2 94.2 92.0 IA3 95.6 92.4 IA4 95.8 91.6 IA5 92.7 90.2 IA6 93.9 90.5 IA7 94.3 90.8 IA8 89.0 88.2 IA9 89.6 86.1 IA10 90.3 88.9 IA11 88.4 84.6 IA12 79.6 75.3 IB1 65.9 63.3 IB2 61.7 54.9

[0106] From the results in Table 1, it can be seen that compared with Comparative Examples 1-2, the cuprous ion-modified adsorbents prepared in Examples 1-12 of the present invention have significantly better adsorption performance. In particular, the cuprous ion-modified adsorbents prepared in Examples 1-7 have better adsorption performance, and the PH3 adsorption removal rates in both Stages Y1 and Y2 are higher than 90%.

[0107] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A cuprous ion modified adsorbent, characterized in that, The modified adsorbent includes an inorganic carrier containing nitrogen element and Cu supported on the inorganic carrier + ; Among them, in the modified adsorbent, the molar ratio of Cu + to the content of nitrogen element is 1:0.3 - 1; the existing form of nitrogen element is selected from at least one of pyridine-type nitrogen, pyrrole-type nitrogen and graphite-type nitrogen.

2. The cuprous ion-modified adsorbent according to claim 1, wherein In the modified adsorbent, Cu + has a molar ratio of the content of nitrogen element of 1:0.4 - 0.6; Preferably, the nitrogen element exists in the forms of pyridine-type nitrogen, pyrrole-type nitrogen, and graphitic nitrogen.

3. The cuprous ion-modified adsorbent according to claim 1 or 2, wherein The inorganic carrier is selected from at least one of activated carbon, activated alumina, molecular sieve, and silica gel; Preferably, the pore diameter of the inorganic carrier is 0.1 - 15 nm, preferably 0.2 - 12 nm; More preferably, the specific surface area of the inorganic carrier is 200-2000 m 2 / g, preferably 300-1500 m 2 / g.

4. A preparation method of a cuprous ion-modified adsorbent, characterized in that, This method includes: S1: In the presence of a solvent, the inorganic carrier is subjected to a first contact reaction with a composite modifier, and the obtained solid material I is activated at a temperature not lower than 400 °C to obtain a modified inorganic carrier; S2: The modified inorganic carrier is subjected to a second contact reaction with a copper salt compound, and the obtained solid material II is heat-treated in an acidic atmosphere and a reducing atmosphere to obtain the cuprous ion-modified adsorbent; Wherein, the composite modifier is an ammonium salt and / or an iron salt; and, the mass ratio of the dosage of the composite modifier to the copper salt compound is 1:0.1 - 3.

5. The preparation method according to claim 4, wherein, The mass ratio of the dosage of the composite modifier to the copper salt compound is 1:0.5 - 2.

6. The preparation method according to claim 4 or 5, wherein In step S1, the dosage of the composite modifier is 3 - 30 wt% of the mass of the inorganic carrier, preferably 12 - 18 wt%; Preferably, in the composite modifier, the mass ratio of the dosage of the ammonium salt to the iron salt is 1:0.2 - 3, preferably 1:0.4 - 1; More preferably, the ammonium salt is selected from at least one of tributylammonium nitrate, butyltriethylammonium hexafluorophosphate, trimethylbutylammonium nitrate, triethylpropylammonium acetate, tetraethylammonium acetate, tetrapropylammonium phosphate, and propyltributylammonium phosphate; the iron salt is selected from at least one of iron nitrate, iron acetate, and iron sulfate.

7. The preparation method according to any one of claims 4-6, wherein The conditions of the first contact reaction include: temperature is 20 - 40 °C, time is 12 - 24 h; And / or, the conditions of the activation treatment include: temperature is 400 - 600 °C, preferably 450 - 550 °C, time is 1 - 4 h, preferably 1.5 - 3.5 h; And / or, the conditions of the second contact reaction include: temperature is 20 - 40 °C, time is 3 - 10 h; And / or, the conditions of the heat treatment include: temperature is 80 - 150 °C, time is 0.15 - 3 h.

8. The preparation method according to any one of claims 4-7, wherein, In step S2, the copper salt compound is selected from at least one of copper nitrate, cuprous nitrate, copper sulfate, cuprous sulfate, copper bromide, cuprous bromide, copper chloride, cuprous chloride, copper formate, copper acetate, and copper acetylacetonate; Preferably, the copper salt compound is copper formate and copper bromide; More preferably, the mass ratio of the dosage of copper formate to copper bromide is 1:0.5 - 2.

9. The preparation method according to any one of claims 4-8, wherein, In step S2, the acidic atmosphere is hydrogen chloride and / or hydrogen bromide; the reducing atmosphere is selected from at least one of hydrogen, formaldehyde, acetaldehyde, ethylene, acetylene, and propyne; Preferably, the volume ratio of the acidic atmosphere to the reducing atmosphere is 1:0.1 - 0.

3.

10. The cuprous ion-modified adsorbent prepared by the preparation method according to any one of claims 4 - 9.

11. Use of the cuprous ion-modified adsorbent according to any one of claims 1 - 3, 10 in the purification of hydrogen for polysilicon recovery.

Images