CN113042107B - Noble metal catalyst with cation resin as carrier and preparation and application thereof - Google Patents

Noble metal catalyst with cation resin as carrier and preparation and application thereof Download PDF

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CN113042107B
CN113042107B CN202110256967.6A CN202110256967A CN113042107B CN 113042107 B CN113042107 B CN 113042107B CN 202110256967 A CN202110256967 A CN 202110256967A CN 113042107 B CN113042107 B CN 113042107B
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nitrate
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resin
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CN113042107A (en
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李保乐
左臣
郑卫芳
晏太红
朱浩玮
白杨
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China Institute of Atomic of Energy
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0201—Impregnation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention belongs to the technical field of nuclear power waste treatment and environmental protection, and particularly relates to a noble metal catalyst with ZSM-5 as a carrier, and a preparation method and application thereof. The invention aims to provide a noble metal catalyst taking cationic resin as a carrier, and preparation and application thereof, so as to solve the problem of safe removal of hydrazine nitrate and hydroxylamine nitrate in the existing spent fuel post-treatment waste liquid. A noble metal catalyst with cation resin as a carrier is characterized in that the catalyst carrier is cation exchange resin, an active component is metal ruthenium, and the mass fraction of the active component in the catalyst is 3-10%. The method adopts a catalytic decomposition mode to remove dangerous compounds such as hydrazine nitrate, hydroxylamine nitrate and the like in the nitric acid waste liquid, and compared with the traditional mode of adding the oxidant, the method is cleaner and more environment-friendly, has no potential safety hazard, and has better economical efficiency than the mode of adding the oxidant.

Description

Noble metal catalyst with cation resin as carrier and preparation and application thereof
Technical Field
The invention belongs to the technical field of nuclear power waste treatment and environmental protection, and particularly relates to a noble metal catalyst taking cationic resin as a carrier, and preparation and application thereof.
Background
Nuclear power is a green low-carbon clean energy, the technology is mature, and the nuclear power is one of the most practical and feasible technical ways for solving the energy problem. However, nuclear power generates a large amount of waste materials with strong radioactivity, namely spent fuel, and the safety problem of the nuclear power is one of the main factors restricting the large-scale popularization and application of the nuclear power.
As is well known, the nuclear fuel utilization rate of the current nuclear reactor is not high, spent fuel contains a large amount of unconverted uranium and value-added nuclides, and is an important nuclear element resource bank, nuclear fuel closed circulation routes are mostly adopted in various nuclear power countries including china, and physical and chemical methods are adopted to separate, purify and recycle useful nuclear elements such as uranium, plutonium, neptunium and the like in the spent fuel, and a typical post-processing process such as a PUREX process: firstly, nitric acid is used for dissolving spent fuel rods, and separation and purification of each nuclide are realized by methods such as extraction of tributyl phosphate and n-dodecane and other organic diluents, reduction and back extraction of hydrazine nitrate and/or hydroxylamine nitrate and other reducing agents.
A large amount of nitric acid waste liquid containing reducing agents of hydrazine nitrate and hydroxylamine nitrate is generated in the post-treatment process, according to the minimization principle of radioactive waste after spent fuel post-treatment, the acidic waste liquid is evaporated, concentrated, destroyed, decomposed and absorbed in the subsequent flow to realize the recycling of nitric acid, and the evaporated residue is subjected to deep burying treatment after vitrification and solidification. Hydrazine nitrate and hydroxylamine nitrate are known to have strong reducibility, are easily oxidized and explosive substances with high energy content, and in order to avoid explosion hazard in the concentration treatment process of waste liquid, the hydrazine nitrate and the hydroxylamine nitrate need to be destroyed and removed in advance.
At present, the method for removing hydrazine nitrate and hydroxylamine nitrate mainly comprises the steps of adding an oxidant such as sodium nitrite or introducing dinitrogen tetroxide gas and the like, and can oxidize the hydrazine nitrate, the hydroxylamine nitrate and the like into dinitrogen monoxide, nitrogen, water, nitric oxide, ammonium nitrate and the like, and has the following defects: the consumption of the oxidant is large, and the cost is high; the reaction is severe, and certain safety risk exists during engineering application; when sodium nitrite is used as an oxidant, new solid waste sodium nitrate which is not easy to treat is generated; the nitrogen dioxide enhances the corrosivity of the solution to equipment, has low primary utilization rate and has leakage risk.
Therefore, in order to solve the above problems in the waste liquid treatment process, it is necessary to develop a method for efficiently, safely, economically and environmentally removing hydrazine nitrate and hydroxylamine nitrate from nitric acid.
Disclosure of Invention
The invention aims to provide a noble metal catalyst taking cationic resin as a carrier, and preparation and application thereof, so as to solve the problem of safe removal of hydrazine nitrate and hydroxylamine nitrate in the existing spent fuel post-treatment waste liquid.
The technical scheme of the invention is as follows:
a noble metal catalyst with cation resin as a carrier is characterized in that the catalyst carrier is cation exchange resin, an active component is metal ruthenium, and the mass fraction of the active component in the catalyst is 3-10%.
The noble metal catalyst taking the cation resin as the carrier is D001 macroporous strong-acid styrene cation exchange resin.
A noble metal catalyst supported on a cation resin as described above, said cation exchange resin being an acid-resistant cation resin support having working conditions suitable for a nitric acid environment having an acidity of less than 2 mol/L.
The preparation method of the noble metal catalyst taking the cationic resin as the carrier comprises the following steps:
1) taking cation exchange resin with the mass of M1, adding saturated sodium chloride solution with the volume of L1, soaking for three days, filtering, transferring the filtered cation exchange resin into deionized water, and repeatedly washing with the deionized water until the concentration of chloride ions is not more than 100 ppm;
2) soaking the resin obtained in the step 1) for two days by using a nitric acid solution with the volume of L1 and the concentration of 0.1-0.3 mol/L, then washing for three times by using nitric acid with the volume of 0.5L1 and the concentration of 1.8-2.3 mol/L, filtering, transferring the filtered cationic resin into deionized water, and repeatedly washing until the pH test paper is neutral;
3) dispersing the resin obtained in the step 2) into deionized water with the volume of L1, and dropwise adding RuCl with the mass of M2 and the volume of 0.3L13·3H2O solution;
RuCl addition was completed3·3H2Soaking and adsorbing for 12 hours at room temperature after the O solution is obtained;
4) dropwise adding the mixture into ice bath until the volume is 08L1, NaBH containing mass M34And stirring the solution for 3 hours;
5) filtering, repeatedly washing with deionized water until the concentration of chloride ions is not more than 100ppm, and then putting the prepared catalyst into a vacuum drying oven for drying and standing to obtain the noble metal catalyst taking the cationic resin as the carrier.
In the method for preparing the noble metal catalyst using the cationic resin as the carrier, in the step 2), the judgment criterion for the neutral pH test paper is that the pH is 6.8-7.2.
Further, in the preparation method of the noble metal catalyst using the cationic resin as the carrier, in the step 5), the drying temperature of the vacuum drying oven is 50-70 ℃, and the standing time is 20-25 h.
Further, the preparation method of the noble metal catalyst taking the cation resin as the carrier as described above, M1: l1 ═ 15 g: 100 mL; m1: m2: m3 ═ 15: 1.94: 1.5.
the application of the noble metal catalyst taking the cationic resin as the carrier can be applied to the removal of hydrazine nitrate and hydroxylamine nitrate in the feed liquid to be treated.
In the application of the noble metal catalyst with the cationic resin as the carrier, the feed liquid to be treated is an aqueous solution containing 0.8-1.2 mol/L of nitric acid, 0.01-0.2 mol/L of hydrazine nitrate and 0.01-0.3 mol/L of hydroxylamine nitrate.
The application of the noble metal catalyst taking the cationic resin as the carrier is applied to removing hydrazine nitrate and hydroxylamine nitrate in a feed liquid to be treated, and the treatment is carried out by adopting a fixed bed continuous reaction mode, wherein the reaction temperature is 50-85 ℃.
The application of the noble metal catalyst taking the cationic resin as the carrier is applied to removing hydrazine nitrate and hydroxylamine nitrate in the feed liquid to be treated, the treatment is carried out by adopting a suspension slurry bed intermittent reaction mode, the reaction temperature is 80-85 ℃, the dosage of the catalyst is 6-7% of the mass of the feed liquid to be treated, and the reaction time is 40-60 min.
The technical scheme of the invention has the beneficial effects that:
(1) the method adopts a catalytic decomposition mode to remove dangerous compounds such as hydrazine nitrate, hydroxylamine nitrate and the like in the nitric acid waste liquid, and compared with the traditional mode of adding the oxidant, the method is cleaner and more environment-friendly, has no potential safety hazard, and has better economical efficiency than the mode of adding the oxidant.
(2) The catalyst disclosed by the invention is suitable for treating waste liquid in a fixed bed continuous mode or a reaction kettle intermittent mode, is simple to operate, is flexible and convenient, can be coupled with a subsequent treatment process, and improves the energy efficiency.
(3) The catalyst disclosed by the invention has high decomposition activity of hydrazine nitrate and hydroxylamine nitrate, has long service life, and is mild in reaction conditions, the feed liquid treated by the catalyst in unit mass in a fixed bed mode can be more than 800 times, and the feed liquid treated by the catalyst in unit mass in an intermittent reaction mode can be more than 300 times.
(4) The catalyst disclosed by the invention has high efficiency in catalytic decomposition of hydrazine nitrate and hydroxylamine nitrate.
Detailed Description
The present invention will be further described with reference to the following examples.
The feed liquid to be treated consists of aqueous solution containing 0.8-1.2 mol/L of nitric acid, 0.01-0.2 mol/L of hydrazine nitrate and 0.01-0.3 mol/L of hydroxylamine nitrate.
Because the feed liquid to be treated has stronger acidity and corrosivity, the noble metal catalyst taking the cation resin as the carrier is the cation exchange resin, the active component is metal ruthenium, and the mass fraction of the active component in the catalyst is 3-10%.
The cation exchange resin is D001 macroporous strong-acid styrene cation exchange resin, and also can be an acid-resistant cation resin carrier with working conditions suitable for a nitric acid environment with acidity less than 2 mol/L.
The preparation method of the noble metal catalyst taking the cationic resin as the carrier comprises the following steps:
1) taking cation exchange resin with the mass of M1, adding a saturated sodium chloride solution with the volume of L1, and soaking for three days, thereby removing organic micromolecular compounds in the resin;
filtering, transferring the filtered cationic resin into deionized water, and repeatedly washing with the deionized water until the concentration of chloride ions is not more than 100ppm, thereby avoiding the catalyst from being poisoned by the residual cationic resin;
2) soaking the resin obtained in the step 1) for two days by using a nitric acid solution with the volume of L1 and the concentration of 0.1-0.3 mol/L, and then washing for three times by using nitric acid with the volume of 0.5L1 and the concentration of 1.8-2.3 mol/L, thereby removing metal ion impurities in the resin;
filtering, transferring the filtered cationic resin into deionized water, and repeatedly washing until the pH test paper is neutral;
the judgment standard for the pH test paper to be neutral is that the pH value is 6.8-7.2.
3) Dispersing the resin obtained in the step 2) into deionized water with the volume of L1, and dropwise adding RuCl with the mass of M2 and the volume of 0.3L13·3H2O solution;
RuCl addition was completed3·3H2Soaking and adsorbing for 12 hours at room temperature after the O solution is obtained;
4) a volume of 0.8L1 of NaBH of mass M3 was added dropwise in an ice bath4And stirring the solution for 3 hours;
5) filtering, repeatedly washing with deionized water until the concentration of chloride ions is not more than 100ppm, and then putting the prepared catalyst into a vacuum drying oven for drying and standing to obtain the noble metal catalyst taking the cationic resin as the carrier.
In this series of operations, the carrier is first soaked in a solution containing the noble metal active precursor through step 3) to bring the noble metal into sufficient contact with the carrier to be adsorbed into the pores of the carrier. Subsequently adding NaBH dropwise thereto in the step 4)4The solution reduces trivalent ruthenium to metallic ruthenium. And finally, repeatedly washing and removing chloride ions in the catalyst in the step 5), thereby avoiding poisoning the catalyst after acidification in a nitric acid solution.
Specifically, in the step 5), the drying temperature of the vacuum drying oven is 50-70 ℃, and the standing time is 20-25 h.
As a preferable condition, the drying temperature of the vacuum drying oven is 60 ℃ and the standing time is 24 hours.
In the preparation method of the noble metal catalyst taking the cationic resin as the carrier, the ratio of M1: l1 ═ 15 g: 100 mL; m1: m2: m3 ═ 15: 1.94: 1.5.
the application of the noble metal catalyst taking the cationic resin as the carrier can be applied to the removal of hydrazine nitrate and hydroxylamine nitrate in the feed liquid to be treated.
The catalyst can be used for treating waste liquid containing hydrazine nitrate and hydroxylamine nitrate through an intermittent reaction, a certain mass of the catalyst is weighed and placed in a reaction bottle filled with the waste liquid containing hydrazine nitrate and hydroxylamine nitrate, and the reaction bottle is heated to the reaction temperature, so that the decomposition of the hydrazine nitrate and the hydroxylamine nitrate is realized; the method can also be used in column reaction, and the waste liquid containing the hydrazine nitrate and the hydroxylamine nitrate passes through a catalyst column with a heating system, and the proper flow rate is adjusted to realize the decomposition of the hydrazine nitrate. The residual hydrazine nitrate and hydroxylamine nitrate were determined spectrophotometrically.
The specific removing method comprises two methods:
firstly, a fixed bed continuous reaction mode is adopted for treatment, and the reaction temperature is 50-85 ℃. The waste liquid containing hydrazine nitrate and hydroxylamine nitrate is made to pass through a catalyst column with heating system, and the proper flow rate is regulated to decompose hydrazine nitrate. The residual hydrazine nitrate and hydroxylamine nitrate were determined spectrophotometrically.
Secondly, treating by adopting a suspension slurry bed intermittent reaction mode, weighing a certain mass of catalyst in a reaction bottle filled with hydrazine nitrate and hydroxylamine nitrate waste liquid, and heating to the reaction temperature of 80-85 ℃ to realize the decomposition of the hydrazine nitrate and the hydroxylamine nitrate; the dosage of the catalyst is 6-7% of the mass of the feed liquid to be treated, and the reaction time is 40-60 min. The residual hydrazine nitrate and hydroxylamine nitrate were determined spectrophotometrically.
The mechanism of catalytic decomposition of hydrazine nitrate and hydroxylamine nitrate by the catalyst is explained as follows:
the reaction process of Ru catalyzed decomposition of hydroxylamine nitrate first goes through a reaction induction period, followed by a rapid autocatalytic reaction process. Nitrous acid is generated in the reaction induction period, and has a catalytic effect on a rapid reaction process. The reaction mechanism is as follows (reaction formulas 1-5):
Figure BDA0002967847560000071
NH2OH+N2O4→HNO+N2O3+H2O (2)
HNO+N2O4→HNO2+N2O3 (3)
Figure BDA0002967847560000072
HNO2+NH2OH+→N2O+H2O+H3O+ (5)
the process of decomposing hydrazine in the Ru catalytic nitric acid solution is mainly realized by the oxidation-reduction reaction of the catalyst. The reaction process is as follows, Ru on the surface of the catalyst is oxidized by nitric acid to generate RuO2And HNO2(equation 6), followed by HNO2And N2H5 +Reaction to form HN3(reaction formula 7) with RuO2Is N in solution2H5 +Reduced to Ru (equation 8) and entered the next catalytic cycle.
Ru+2HNO3＝RuO2+2HNO2 (6)
N2H5 ++HNO2＝HN3+H++2H2O (7)
2RuO2+4N2H5NO3＝2Ru+N2O+4N2+2HNO3+9H2O (8)
Therefore, the hydrazine nitrate concentration in the solution at the initial stage of the reaction is high and functions as a nitrous acid scavenger, and the decomposition of the hydrazine nitrate is promoted by generating nitrous acid through the decomposition of hydroxylamine nitrate and the hydrazine nitrate concentration is reduced to 10 as the reaction proceeds-3And when the concentration of the nitric acid in the solution is less than M, the nitric acid begins to accumulate, and after the nitric acid reaches a certain concentration, the self-catalytic reaction process of hydroxylamine nitrate occurs.
Example 1
Taking 15g of cation exchange resin carrier, addingSoaking in 100mL saturated sodium chloride solution for three days, filtering, directly transferring the filtered cationic resin carrier into deionized water, and repeatedly washing until the concentration of chloride ions is not more than 100 ppm; soaking the resin in 100mL of 0.1mol/L nitric acid solution for two days, then washing the resin for three times by using 50mL of 1.8mol/L nitric acid, filtering, directly transferring the filtered cationic resin carrier into deionized water, and repeatedly washing until the pH test paper is detected to be neutral; dispersing the treated cation exchange resin in 100mL of deionized water, and adding 30mL of deionized water containing 1.94g of RuCl dropwise3·3H2O solution, which is soaked and adsorbed at room temperature for 12h, and then 80mL of solution containing 3.0g of NaBH is added dropwise in an ice bath4The solution is continuously stirred for 3 hours, filtered and repeatedly washed until the concentration of chloride ions is not more than 100ppm, and finally, the prepared catalyst is put into a vacuum drying oven to be dried for 20 hours at 50 ℃.
When the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in feed liquid to be treated, a fixed bed continuous reaction mode is adopted for treatment, 5g (dry weight) of catalyst is loaded into a glass transparent column reactor with the inner diameter of 10mm, the outer wall of the reactor is tapped to enable the catalyst layer to be tightly filled, and the reaction temperature is 50 ℃.
And (3) introducing the material liquid to be treated, reacting for 137h, wherein the pump flow is 0.5mL/min, the co-treatment material is 4.1kg, sampling and detecting the contents of hydrazine nitrate and hydroxylamine nitrate in the effluent liquid respectively in the morning and evening during the operation process of the device, and the catalyst treatment waste liquid is 0.82kg/g.cat (820 times).
The treated feed liquid has the hydrazine nitrate content lower than 10-4mol/L, hydroxylamine nitrate concentration less than 10-2mol/L。
Example 2
Taking 15g of cation exchange resin carrier, adding 100mL of saturated sodium chloride solution, soaking for three days, filtering, directly transferring the filtered cation exchange resin carrier into deionized water, and repeatedly washing until the concentration of chloride ions is not more than 100 ppm; soaking the resin in 100mL of 0.3mol/L nitric acid solution for two days, then washing the resin for three times by using 50mL of 2.3mol/L nitric acid, filtering, directly transferring the filtered cation resin carrier into deionized water, and repeatedly washing until pH test paper is detected to be neutral; will be processedThe cation exchange resin was dispersed in 100mL of deionized water, and 30mL of a solution containing 1.94g of RuCl was added dropwise3·3H2O solution, which is soaked and adsorbed at room temperature for 12h, and then 80mL of solution containing 1.5g of NaBH is added dropwise in an ice bath4The solution is continuously stirred for 3 hours, filtered and repeatedly washed until the concentration of chloride ions is not more than 100ppm, and finally, the prepared catalyst is put into a vacuum drying oven to be dried for 25 hours at 70 ℃.
When the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in feed liquid to be treated, a fixed bed continuous reaction mode is adopted for treatment, 5g (dry weight) of catalyst is loaded into a glass transparent column reactor with the inner diameter of 10mm, the outer wall of the reactor is tapped to enable the catalyst layer to be tightly filled, and the reaction temperature is 85 ℃.
And (3) introducing the material liquid to be treated, reacting for 125 hours, wherein the pump flow is 0.5mL/min, the co-treatment material is 3.75kg, sampling and detecting the contents of hydrazine nitrate and hydroxylamine nitrate in the effluent liquid respectively in the morning and evening during the operation of the device, and the catalyst treatment waste liquid is 0.75kg/g.cat (750 times).
The treated feed liquid has the hydrazine nitrate content lower than 10-4mol/L, hydroxylamine nitrate concentration less than 10-2mol/L。
Example 3
The catalyst preparation was carried out as in example 1.
When the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in a feed liquid to be treated, a suspension slurry bed batch reaction mode is adopted for treatment, 30mL of prepared reaction feed liquid is added into a 100mL three-necked bottle, a constant-temperature magnetic stirring water bath is started to preheat to 80 ℃, 1.8g of catalyst (dry product) is added, the reaction is timed, the reaction is stopped when no bubbles are generated in a reaction system, and the reaction time is recorded as 40 min.
And (3) recovering the catalyst for the next reaction by decompression and suction filtration, sampling a reaction solution to analyze the content of each component, recycling the catalyst for 24 times, treating the solution for 0.72kg, and treating the reaction solution by the catalyst for 0.35kg/g. The treated feed liquid has the hydrazine nitrate content lower than 10-4mol/L, hydroxylamine nitrate concentration less than 10-2mol/L。
Example 4
The catalyst preparation was carried out as in example 2.
When the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in a feed liquid to be treated, a suspension slurry bed batch reaction mode is adopted for treatment, 30mL of prepared reaction feed liquid is added into a 100mL three-necked bottle, a constant-temperature magnetic stirring water bath is started to preheat to 85 ℃, 2.1g of catalyst (dry product) is added, the reaction is timed, the reaction is stopped when no bubbles are generated in a reaction system, and the reaction time is recorded as 60 min.
The catalyst is recovered by vacuum filtration for the next reaction, the reaction liquid is sampled and analyzed for the content of each component, the catalyst is recycled for 19 times, the treatment solution is 0.57kg, and the capability of the catalyst for treating the reaction liquid is 0.28kg/g. The content of hydrazine nitrate in the treated feed liquid is less than 10-4mol/L, hydroxylamine nitrate concentration less than 10-2mol/L。
According to the catalyst for decomposing the hydrazine nitrate in the nitric acid solution, disclosed by the invention, the problem of safely removing the hydrazine nitrate in the existing spent fuel post-treatment waste liquid can be effectively solved, and the hydrazine nitrate and hydroxylamine nitrate in the waste liquid are efficiently decomposed into nitrous oxide, nitrogen, water, nitric oxide and ammonium nitrate under the catalytic action of the catalyst, so that the aim of elimination is fulfilled.

Claims (2)

1. The application of a noble metal catalyst taking cation resin as a carrier is characterized in that:
the catalyst carrier is cation exchange resin, the active component is metal ruthenium, and the mass fraction of the active component in the catalyst is 3-10%;
the cation exchange resin is D001 macroporous strong-acid styrene cation exchange resin;
the cation exchange resin is an acid-resistant cation resin carrier with working conditions suitable for a nitric acid environment with acidity less than 2 mol/L;
the noble metal catalyst taking the cationic resin as a carrier is applied to the removal of hydrazine nitrate and hydroxylamine nitrate in the feed liquid to be treated;
the feed liquid to be treated is an aqueous solution containing 0.8-1.2 mol/L of nitric acid, 0.01-0.2 mol/L of hydrazine nitrate and 0.01-0.3 mol/L of hydroxylamine nitrate;
when the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in feed liquid to be treated, a fixed bed continuous reaction mode is adopted for treatment, and the reaction temperature is 50-85 ℃;
or when the method is applied to removing hydrazine nitrate and hydroxylamine nitrate in the feed liquid to be treated, the treatment is carried out by adopting a suspension slurry bed intermittent reaction mode, the reaction temperature is 80-85 ℃, the dosage of the catalyst is 6-7% of the mass of the feed liquid to be treated, and the reaction time is 40-60 min.
2. The use of a cationic resin-supported noble metal catalyst according to claim 1, wherein: the preparation method of the noble metal catalyst with the cationic resin as the carrier comprises the following steps:
1) taking cation exchange resin with the mass of M1, adding saturated sodium chloride solution with the volume of L1, soaking for three days, filtering, transferring the filtered cation exchange resin into deionized water, and repeatedly washing with the deionized water until the concentration of chloride ions is not more than 100 ppm;
2) soaking the resin obtained in the step 1) for two days by using a nitric acid solution with the volume of L1 and the concentration of 0.1-0.3 mol/L, then washing for three times by using nitric acid with the volume of 0.5L1 and the concentration of 1.8-2.3 mol/L, filtering, transferring the filtered cationic resin into deionized water, and repeatedly washing until the pH test paper is neutral;
3) dispersing the resin obtained in the step 2) into deionized water with the volume of L1, and dropwise adding RuCl with the mass of M2 and the volume of 0.3L13·3H2O solution;
RuCl is added completely3·3H2Soaking and adsorbing for 12 hours at room temperature after the O solution is obtained;
4) a volume of 0.8L1 of NaBH of mass M3 was added dropwise in an ice bath4And continuously stirring the solution for 3 hours;
5) filtering, repeatedly washing with deionized water until the concentration of chloride ions is not more than 100ppm, and then putting the prepared catalyst into a vacuum drying oven for drying and standing to obtain a noble metal catalyst taking cationic resin as a carrier;
in the step 2), the judgment standard for the pH test paper to be neutral is that the pH is 6.8-7.2;
in the step 5), the drying temperature of the vacuum drying oven is 50-70 ℃, and the standing time is 20-25 h;
M1：L1＝15g：100mL；M1：M2：M3＝15：1.94：1.5。
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