CN112755953A - Adsorbent for removing nitrogen oxide in fluid, preparation method and application - Google Patents

Adsorbent for removing nitrogen oxide in fluid, preparation method and application Download PDF

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CN112755953A
CN112755953A CN201911001142.9A CN201911001142A CN112755953A CN 112755953 A CN112755953 A CN 112755953A CN 201911001142 A CN201911001142 A CN 201911001142A CN 112755953 A CN112755953 A CN 112755953A
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solution
adsorbent
preparation
fluid
mixture
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CN112755953B (en
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吴江
邹薇
任淑
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/402—Dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Abstract

The invention discloses an adsorbent for removing nitrogen oxides in fluid and a preparation method and application thereof. The composition of the adsorbent comprises: nixMg6‑xFe2O9Or NixMg6‑xAl2O9Wherein x is 1-6. The preparation method of the adsorbent comprises the following steps: and dropwise adding the alkaline solution into a solution containing nickel, magnesium, iron or aluminum to perform a precipitation reaction, and then performing hydrothermal crystallization, drying, roasting and the like to obtain the adsorbent. The adsorbent has high efficiency of removing nitrogen oxides in fluid and simple and convenient preparation methodThe production process is environment-friendly and pollution-free, and the operation is simple and convenient.

Description

Adsorbent for removing nitrogen oxide in fluid, preparation method and application
Technical Field
The invention relates to an adsorbent for removing nitrogen oxides (NOx) in fluid and a preparation method thereof.
Background
Among the challenges facing human society, global warming due to greenhouse effect is one of the most serious topics, and has seriously threatened the survival and continuation of human beings and other species. Although N is2The greenhouse effect of O is only about 6% of the total, but the potential greenhouse effect is about 310 times that of carbon dioxide and 4-21 times that of methane due to the fact that the O can be reserved in the atmosphere for as long as 120 years. N is a radical of2O is a greenhouse gas having a greenhouse effect and increasing global warming, N2O has a long residence time in the atmosphere and can be transported to the stratosphere, causing ozone depletion, creating ozone holes that can cause damage to the skin, eyes, and immune system of humans and other living beings by exposure to solar ultraviolet radiation. N is a radical of2The main sources of O are hydrocarbon combustion and partial oxidation thereof, industrial emissions, automobile exhaust, exhaust from domestic gas ranges and water heaters, etc. Nitrous oxide and nitric oxide have long been used medicinally as inhalation anesthetics. Inhalation of nitrous oxide and a mixture of nitric oxide and air, which can be asphyxiated when the oxygen concentration therein is low; inhalation of 80% nitrous oxide and a mixture of nitric oxide and oxygen results in deep anesthesia, resulting in hypoxia after entering the blood, which may cause hypertension, syncope, and even heart attack after long-term ingestion. In addition, prolonged exposure to such gases can cause anemia and central nervous system damage. Thus, remediation or purification of N in a fluid2O is necessary and critical.
The technology for removing nitrous oxide and nitric oxide by an adsorption method has attracted more and more attention due to the characteristics of high efficiency, rapidness, no secondary pollution, easy operation and the like. The selection of an adsorbent which is low in price, easy in material acquisition, simple in preparation, large in adsorption capacity and easy in regeneration is the key point of attention of researchers.
At present, the used adsorbent mainly comprises porous materials such as activated carbon, molecular sieve, alumina and the like, the adsorption of nitrous oxide and nitric oxide mainly comprises physical adsorption, and the removal efficiency of nitrous oxide and nitric oxide is low in the actual environment.
CN201611237320.4 discloses a nitrogen oxide adsorbent and a preparation method thereof. The nitrogen oxide adsorbent consists of the following raw materials in parts by weight: 26-34 parts of nano convex-concave bar soil, 9-17 parts of catechin, 5-13 parts of malondialdehyde and 1-5 parts of triethanolamine. The method is characterized in that the adsorbent is prepared by mixing and grinding nano attapulgite and triethanolamine, treating by catechin and malondialdehyde, and performing ultrasonic action. The adsorption effect of the adsorbent on nitrogen oxides still needs to be further improved.
CN201711323661.8 discloses a preparation method of a composite adsorbing material for treating nitrogen oxide waste gas. The method comprises the steps of drying the activated carbon fiber in an oven, impregnating the activated carbon fiber with potassium sulfate serving as a pre-soaking agent, and heating and carbonizing the impregnated activated carbon fiber to obtain modified activated carbon fiber; mixing and ball-milling silicon dioxide ceramic powder and a sintering aid boric acid, drying to obtain mixed powder, spraying a polyvinyl alcohol powder adhesive solution on the surface of a urea ball, then coating the mixed powder to obtain a hollow ball precursor, drying, and sintering at a high temperature to obtain a silicon dioxide hollow ceramic ball; adding a modifier solution of cetyl trimethyl ammonium bromide into the expanded graphite, carrying out immersion modification treatment in a constant-temperature water bath, taking out, washing with water, and drying to constant weight to obtain modified expanded graphite; drying, crushing and sieving the tea stalks, mixing and stirring the tea stalks with active carbon, mechanically extruding the tea stalks into strips, drying and sieving the tea stalks to obtain a tea-based adsorbing material; mixing the composite adsorbent with modified activated carbon fibers, silicon dioxide hollow ceramic balls and modified expanded graphite, and performing ball milling to obtain the composite adsorbent. The preparation method of the adsorbent is complex, and the adsorption effect still needs to be further improved.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a new adsorbent for removing nitrogen oxides from a fluid, a preparation method thereof and a use thereof, in order to overcome the problem of low removal efficiency of nitrogen oxides from an industrial fluid in the prior art. The adsorbent has the characteristics of high efficiency of removing nitrogen oxides (such as nitrous oxide and nitric oxide) in fluid, simple and convenient preparation method, environmental-friendly and pollution-free production process, simple and convenient operation and the like.
The invention provides an adsorbent for removing nitrogen oxides in fluid, which comprises the following components: nixMg6- xFe2O9Or NixMg6-xAl2O9Wherein x is 1 to 6, preferably 1 to 5.
In the technical scheme, the adsorbent has a hydrotalcite-like structure.
In the above technical solution, the adsorbent may further contain a binder, and the content of the binder is 25% or less, preferably 1% to 25% based on the weight of the adsorbent. The binder may be selected from silica and/or alumina.
The second aspect of the present invention provides a method for preparing the above adsorbent, comprising:
preparing a solution containing nickel, magnesium, iron or aluminum, and marking as a solution A; preparing an alkaline solution, and marking as a solution B;
dripping the solution B into the solution A, and continuing stirring for 2-4 hours when the pH value of the solution reaches 7-11 to obtain a mixture C;
carrying out hydrothermal crystallization on the mixture C obtained in the step II, and drying to obtain a dried material;
fourthly, roasting the dried material obtained in the third step to obtain the adsorbent; or adding a binder into the dried material obtained in the step three, mixing and molding, and drying and roasting to obtain the adsorbent.
In the above technical solution, preferably, a dispersant is added to the solution a and/or the mixture C.
In the above technical scheme, the dispersant is at least one selected from urea, polyvinylpyrrolidone (PVP) and polyethylene glycol. The dispersing agent is preferably added in a solution mode, and the mass concentration of the dispersing agent is 5-35%. The addition amount of the dispersant solution is calculated by the solid volume of nickel, magnesium and iron or aluminum precursor used for preparing the solution A, and the solid-liquid volume ratio is 1: 20 to 100.
In the above technical scheme, the solution containing nickel, magnesium, iron or aluminum prepared in step (i) is an acidic solution, and can be prepared by dissolving a water-soluble nickel, magnesium, iron or aluminum precursor (such as a water-soluble salt) in water.
In the above technical solution, the nickel salt may be at least one of nickel nitrate or nickel chloride.
In the above technical solution, the magnesium salt may be at least one of magnesium acetate, magnesium nitrate or magnesium chloride.
In the above technical solution, the iron salt may be at least one of ferric nitrate or ferric chloride.
In the above technical solution, the aluminum salt may be at least one of aluminum nitrate or aluminum chloride.
In the above technical solution, the alkaline solution in the step (i) may be prepared by using an alkaline source, and the alkaline source may be at least one of sodium hydroxide, potassium hydroxide or ammonia water.
In the above technical scheme, the pH value in the step (II) is further preferably 7-10.
In the above technical scheme, the hydrothermal crystallization conditions in the third step are as follows: the crystallization temperature is 70-150 ℃, the treatment time is 4-36 h, and the preferable conditions are as follows: the crystallization temperature is 75-120 ℃, and the treatment time is 4-15 h.
In the technical scheme, the crystallized product obtained in the third step can be subjected to conventional post-treatment steps such as filtering, washing and the like according to needs, and then is dried and roasted to obtain the adsorbent product. The drying and roasting conditions are as follows: drying at 80-150 ℃ for 4-24 h, and roasting at 300-600 ℃ for 4-24 h.
In the technical scheme, the crystallized product obtained in the third step can be subjected to conventional post-treatment steps such as filtering, washing and the like according to requirements, and after drying, a binder is selectively added, and after mixing and forming, drying and roasting are carried out, so as to obtain the adsorbent product. The drying and roasting conditions are as follows: drying at 80-150 ℃ for 4-24 h, and roasting at 300-600 ℃ for 4-24 h. The molding may be carried out by a conventional molding method such as a tablet method, an extrusion method, or the like. The shape may be a conventional shape such as granular, bar, sheet, etc.
In a third aspect, the present invention provides a method for removing nitrogen oxides from a fluid by using the adsorbent of the present invention, comprising: and contacting the adsorbent with a fluid containing nitrogen oxides to remove the nitrogen oxides to obtain a purified fluid. The nitrogen oxide is nitric oxide and/or nitrous oxide.
In the above technical solution, the fluid containing the nitrogen oxide may be in a gas phase or a liquid phase.
In the technical scheme, the adsorbent is contacted with the fluid containing the nitrogen oxide under the following conditions, wherein the contact temperature is 10-45 ℃, and the contact time is 10-50 min.
The technical scheme can adopt continuous operation or intermittent operation, and can adopt at least one process of a fixed bed, a fluidized bed, a moving bed or a suspended bed.
In the technical scheme, when continuous operation is adopted and the fluid containing the nitrogen oxide is in a gas phase, the airspeed of the fluid containing the nitrogen oxide is 1-50000 h-1Preferably 200 to 30000h-1。
In the technical scheme, when continuous operation is adopted and the fluid containing the nitrogen oxide is in a liquid phase, the airspeed of the raw material liquid containing the nitrogen oxide is 1-3000 h-1Preferably 200 to 1000 hours-1。
In the above technical solution, when the intermittent operation is adopted and the fluid containing nitrogen oxide is in a liquid phase, the mass ratio of the adsorbent to the fluid containing nitrogen oxide is 1: 20 to 100.
In the above technical scheme, the raw gas containing nitrogen oxides may be at least one of air, industrial waste gas, hydrogen-rich gas or automobile exhaust. The liquid phase may be at least one of an experimental waste liquid, an industrial waste water, a waste aqueous solution containing nitrogen oxides, and the like. The volume concentration of nitrogen oxides in the raw material fluid is 10 to 1000ppm, and more preferably 50 to 800 ppm.
Compared with the prior art, the adsorbent has the following advantages:
1. when the adsorbent is used for adsorbing and removing the nitrogen oxides in the raw material fluid containing the nitrogen oxides, the specific expression is that the dosage of the adsorbent is small, the adsorption speed is high, and the efficiency of removing the nitrogen oxides is high.
2. The adsorbent is prepared by coprecipitation and hydrothermal treatment, and the component of the adsorbent is NixMg6-xFe2O9Or NixMg6- xAl2O9The adsorbent prepared by the method has a layered structure, and nitrogen oxides can be adsorbed between layers, so that the adsorbent shows good adsorption performance on nitrogen oxides.
3. According to the invention, by optimizing and controlling the preparation process parameters of the adsorbent, the crystal form, the pore structure and the like can be effectively controlled, the efficiency of selectively removing nitric oxide can be optimized, and a better technical effect is obtained. Particularly, in the preparation process of the adsorbent, after the dispersing agent is added, the effective active component content of the adsorbent prepared by the invention is high, and the adsorbent has stronger performance of selectively adsorbing nitrogen oxides.
Drawings
Fig. 1 is an XRD pattern of the adsorbent prepared in example 1. As can be seen from fig. 1, the adsorbent prepared in example 1 has the structural characteristics of hydrotalcite-like material. The adsorbents prepared in examples 2-8 have similar XRD patterns and have hydrotalcite-like material structure characteristics.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples. In the present invention, wt% is a mass fraction and ppm is a volume fraction.
In the invention, the XRD test method comprises the following steps: the sample phase analysis measurements were carried out on an X-ray diffractometer model Bruker D8, with the instrument operating conditions: cu target, Kalpha radiation source, graphite monochromator, tube voltage of 40kv, tube current of 40mA, scanning range of 5-70 degrees, and scanning speed of 2 degrees/min.
[ example 1 ]
Preparation of solution A: in deionized water at room temperature as follows: 1: 2, fully stirring the nickel nitrate, the magnesium nitrate and the ferric nitrate until the mixture is clear, adding 300mL of polyethylene glycol solution with the concentration of 5 wt%, and stirring for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain the adsorbent product A.
20g of the adsorbent A prepared as described above was added to 1L of an aqueous solution containing 500ppm of nitric oxide and dinitrogen monoxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 2 ]
Preparation of solution A: in deionized water at room temperature according to 3: 3: 2, fully stirring the nickel nitrate, the magnesium nitrate and the ferric nitrate until the mixture is clear, adding 300mL of 5 wt% polyethylene glycol solution, and dispersing for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 550 ℃ muffle furnace for 2h to obtain the adsorbent product B.
20g of the adsorbent B prepared above was added to 1L of an aqueous solution containing 300ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 3 ]
Preparation of solution A: 1: 5: 2, nickel nitrate, magnesium nitrate and ferric nitrate are dissolved, fully stirred until the mixture is clear, 100mL of 2 wt% urea solution is added, and the mixture is dispersed for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 500 ℃ muffle furnace for 4h to obtain the adsorbent product C.
20g of the adsorbent C prepared above was added to 1L of an aqueous solution containing 200ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 4 ]
Preparation of solution A: in deionized water at room temperature as follows: 1: 2 molar ratio nickel nitrate, magnesium nitrate and aluminium nitrate were dissolved, stirred well to clarify, 300mL of 5 wt% polyethylene glycol solution was added and dispersed for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 550 ℃ muffle furnace for 2h to obtain the adsorbent product D.
20g of the adsorbent D obtained as described above was added to 1L of an aqueous solution containing 60ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 5 ]
Preparation of solution A: in deionized water at room temperature according to 3: 3: 2 molar ratio nickel nitrate, magnesium nitrate and aluminium nitrate are dissolved, stirred well to be clear, added with 300ml of 5% polyethylene glycol solution and dispersed for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain the adsorbent product E.
20g of the adsorbent E prepared above was added to 1L of an aqueous solution containing 80ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 6 ]
Preparation of solution A: in deionized water at room temperature as follows: 1: 2 molar ratio nickel nitrate, magnesium nitrate and ferric nitrate were dissolved and stirred well to clarify. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain the adsorbent product F.
20g of the adsorbent F prepared above was added to 1L of an aqueous solution containing 500ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 7 ]
Preparation of solution A: in deionized water at room temperature as follows: 1: 2, dissolving nickel nitrate, magnesium nitrate and ferric nitrate, fully stirring until the mixture is clear, adding 3% polyvinylpyrrolidone (PVP) solution, and dispersing for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 75 ℃ for 10 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain the adsorbent product G.
20G of the adsorbent G prepared above was added to 1L of an aqueous solution containing 500ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ example 8 ]
Preparation of solution A: in deionized water at room temperature as follows: 1: 2, fully stirring the nickel nitrate, the magnesium nitrate and the ferric nitrate until the mixture is clear, adding 300mL of polyethylene glycol solution with the concentration of 5 wt%, and stirring for 10 mins. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 10, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10H, and roasting in a 450 ℃ muffle furnace for 4H to obtain the adsorbent product H.
20g of the adsorbent H prepared above was added to 1L of an aqueous solution containing 500ppm of dinitrogen monoxide and nitric oxide, and sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
Preparation of solution A: in deionized water at room temperature according to 6: 2, dissolving nickel nitrate and ferric nitrate, and fully stirring until the mixture is clear. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain the adsorbent product I.
20g of the adsorbent I prepared above was added to 1L of an aqueous solution containing 500ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of solution A: in deionized water at room temperature according to 6: 2, dissolving magnesium nitrate and ferric nitrate, and fully stirring until the mixture is clear. Preparation of solution B: sodium hydroxide was dissolved in deionized water at room temperature and stirred well until clear. And (3) quickly dropwise adding the solution B into the solution A until the pH value of the mixed solution reaches 8.5, and continuously stirring for 2 hours at room temperature to obtain a mixed material C. And placing the mixture C in a crystallization kettle, and carrying out hydrothermal treatment at 95 ℃ for 5 hours. And filtering the product, washing with deionized water, drying in a 120 ℃ oven for 10h, and roasting in a 450 ℃ muffle furnace for 4h to obtain an adsorbent product J.
20g of the adsorbent J prepared above was added to 1L of an aqueous solution containing 500ppm of dinitrogen monoxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the contents of dinitrogen monoxide and nitric oxide in water were measured, and the measurement results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
Same as example 4, except that: solution a differs, i.e. in the ratio 6: 2 molar ratio nickel nitrate and aluminium nitrate were dissolved, stirred well to clarify, 300mL of 5 wt% polyethylene glycol solution was added and dispersed for 10 mins. The obtained product is an adsorbent product K.
20g of the adsorbent K prepared above was added to 1L of an aqueous solution containing 500ppm of nitrous oxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the content of nitrous oxide and nitric oxide in water was measured, and the measurement results are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
Same as example 4, except that: solution a differs, i.e. in the ratio 6: 2 molar ratio magnesium nitrate and aluminium nitrate were dissolved, stirred well to clarify, 300mL of 5 wt% polyethylene glycol solution was added and dispersed for 10 mins. The resulting product is adsorbent product L.
20g of the adsorbent L prepared above was added to 1L of an aqueous solution containing 500ppm of nitrous oxide and nitric oxide, sufficiently stirred at room temperature for 20mins, and the content of nitrous oxide and nitric oxide in water was measured, and the measurement results are shown in Table 1.
TABLE 1
Figure BDA0002241358880000081
[ examples 9 to 11 ] of the present invention
The adsorbent A was subjected to the nitrous oxide and nitric oxide removal experiments in water under the conditions of different amounts, temperatures, process modes and contact times, and the results are shown in Table 2.
TABLE 2
Figure BDA0002241358880000091

Claims (10)

1. An adsorbent for removing nitrogen oxides from a fluid, comprising: nixMg6-xFe2O9Or NixMg6-xAl2O9Wherein x is 1 to 6, preferably 1 to 5.
2. The sorbent of claim 1, wherein: the adsorbent has a hydrotalcite-like structure.
3. The sorbent of claim 1, wherein: the adsorbent contains a binder, and the content of the binder is less than 25% by weight of the adsorbent.
4. A process for the preparation of a getter according to any of claims 1 to 3, comprising:
preparing a solution containing nickel, magnesium, iron or aluminum, and marking as a solution A; preparing an alkaline solution, and marking as a solution B;
dripping the solution B into the solution A, and continuing stirring for 2-4 hours when the pH value of the solution reaches 7-11 to obtain a mixture C;
carrying out hydrothermal crystallization on the mixture C obtained in the step II, and drying to obtain a dried material;
fourthly, roasting the dried material obtained in the third step to obtain the adsorbent; or adding a binder into the dried material obtained in the step three, mixing and molding, and drying and roasting to obtain the adsorbent.
5. The method of claim 4, wherein: and adding a dispersing agent into the solution A and/or the mixture C, wherein the dispersing agent is selected from at least one of urea, polyvinylpyrrolidone and polyethylene glycol.
6. The method of claim 5, wherein: the dispersing agent is added in a solution mode, and the mass concentration of the dispersing agent is 5-35%; the addition amount of the dispersant solution is calculated by the solid volume of nickel, magnesium and iron or aluminum precursor used for preparing the solution A, and the solid-liquid volume ratio is 1: 20 to 100.
7. The method of claim 5, wherein: in the alkaline solution of the step I, the alkali source is at least one of sodium hydroxide, potassium hydroxide or ammonia water.
8. The method of claim 5, wherein: the hydrothermal crystallization conditions are as follows: the crystallization temperature is 70-150 ℃, and the treatment time is 4-36 h.
9. The method of claim 5, wherein: the hydrothermal crystallization conditions are as follows: the crystallization temperature is 75-120 ℃, and the treatment time is 4-15 h.
10. Use of the adsorbent of any one of claims 1 to 3 for removing nitrogen oxides from a fluid.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452980A (en) * 2021-12-30 2022-05-10 浙江微通催化新材料有限公司 Preparation method of platinum-supported Ni/Mg/Fe hydrotalcite catalyst and application of catalyst in preparation of aniline

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109692653A (en) * 2017-10-20 2019-04-30 中国石油化工股份有限公司 The adsorbent and preparation method thereof of phosphate anion in efficient absorption water
CN109692648A (en) * 2017-10-20 2019-04-30 中国石油化工股份有限公司 The adsorbent and preparation method thereof of sulfate ion in efficient absorption water

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109692653A (en) * 2017-10-20 2019-04-30 中国石油化工股份有限公司 The adsorbent and preparation method thereof of phosphate anion in efficient absorption water
CN109692648A (en) * 2017-10-20 2019-04-30 中国石油化工股份有限公司 The adsorbent and preparation method thereof of sulfate ion in efficient absorption water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陶炎鑫等: ""Co-Mg/Al类水滑石衍生复合氧化物上N2O催化分解"", 《物理化学学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452980A (en) * 2021-12-30 2022-05-10 浙江微通催化新材料有限公司 Preparation method of platinum-supported Ni/Mg/Fe hydrotalcite catalyst and application of catalyst in preparation of aniline
CN114452980B (en) * 2021-12-30 2023-04-11 浙江微通催化新材料有限公司 Preparation method of platinum-supported Ni/Mg/Fe hydrotalcite catalyst and application of catalyst in preparation of aniline

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