CN107398248A - A kind of cleanser for removing nitrogen oxides and preparation method thereof - Google Patents

A kind of cleanser for removing nitrogen oxides and preparation method thereof Download PDF

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Publication number
CN107398248A
CN107398248A CN201610328956.3A CN201610328956A CN107398248A CN 107398248 A CN107398248 A CN 107398248A CN 201610328956 A CN201610328956 A CN 201610328956A CN 107398248 A CN107398248 A CN 107398248A
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China
Prior art keywords
cleanser
carrier
transition metal
active component
soluble
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CN201610328956.3A
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Inventor
陈松
黄文氢
张颖
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN201610328956.3A priority Critical patent/CN107398248A/en
Publication of CN107398248A publication Critical patent/CN107398248A/en
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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
    • 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
    • B01J20/06—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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

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  • Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Nanotechnology (AREA)
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Abstract

The present invention relates to the cleanser technical field of removing nitrogen oxides.It includes active component and can load the carrier of the active component, wherein, the one or more in transition metal are contained in the active component.Wherein described transition metal is selected from least one of iron, cobalt, nickel, copper and zinc.Its composition is simple, easily obtains, cost is cheap, and cleanser preparation process is simple, and raw material is easy to get, and production cost is low, non-environmental-pollution.Cleanser, which is fitted into purification pipe, is widely portable to the purification containing ppm levels NOx in factory and use for laboratory lighter hydrocarbons tail gas, NOx content is less than 1.0ppm (volume fraction) after purification, it is high with the adsorptive selectivity to NOx and adsorption capacity, the advantages of using facilitating.

Description

A kind of cleanser for removing nitrogen oxides and preparation method thereof
Technical field
The present invention relates to the cleanser technical field of removing nitrogen oxides.
Background technology
Gaseous state light hydrocarbon feedstocks mainly include C1Natural gas, C2Ethene, C3Propylene, C4Oil gas, be main at present Energy fuel and industrial chemicals.The main feature of China's petroleum resources is exactly high nitrogen, the organic-inorganic nitride pole in crude oil The nitrogen oxides (NOx) of small molecule is easily changed into, it not only easily inactivates catalyst poisoning, influences the process of petrochemical industry With the performance of product.And NOx also easily forms the peace of nitro compound strong influence accumulating during transport is stored It is qualitative.NOx or air major pollutants, the ozone in stratosphere is not only broken up, but also be acid rain, acid mist and photochemistry Cigarette fog origin, greatly threat is formed to the health of the mankind and other life.
By taking NOx as an example, suction gas non-evident sympton or can have eye and upper respiratory tract irritation at that time, such as it is pharyngeal not Suitable, dry cough etc..Often there is Delayed onset pulmonary edema, adult respiratory distress syndrome (ARDS) after 6-7 incubation periods hour.Can complicated with pneumothorax and Mediastinal emphesema.Pulmonary edema occur within 2 weeks or sos after disappearing Delayed onset it is cloudy fill in property capillary bronchitis and occur to cough, progressive is uncomfortable in chest, Respiratory distress and cyanosis.After gas is sucked without obvious poisoning symptom above lesion occurs after 2 weeks for small number of patients.Vim and vigour point Arterial partial pressure of oxygen reduction is shown in analysis.C-XF is abound with the granular shade of grain in the performance or two lungs of pulmonary edema.Such as an oxygen in niter air Methemoglobinemia can be caused by changing nitrogen concentration height.
Chinese patent CN102266788A discloses the catalyst for removing oxygen and nitrogen oxides, preparation method and its answered With；Chinese patent CN101391224 discloses scavenger and its application of nitrogen oxides.But the catalyst in this two patents All it is for purifying and removing the nitrogen oxides in air or flue gas or nitrogen, it can not be used for gaseous state light hydrocarbon feedstocks, because Alkane, alkene, alkynes, double bond alkene and alkynes to be included in gaseous state light hydrocarbon feedstocks known in those skilled in the art are bound to Being reacted with catalyst activity component reduces the removing ability of nitrogen oxides, or directly makes catalyst inactivation, therefore cannot be used for gas State olefin feedstock.
It can be seen that removing NOx patent and article are mainly used in combustion product gases and vehicle exhaust at present, and gaseous state lighter hydrocarbons Raw material removes NOx patent and document is not reported substantially,.Removing for NOx in gaseous state light hydrocarbon feedstocks requires removing precision The features such as high, cleanser can not react with gaseous hydrocarbons, both at home and abroad without the patent application of this cleanser.
The content of the invention
One of present invention provides a kind of cleanser for removing nitrogen oxides, and it includes active component and can loaded described The carrier of active component, wherein, the one or more in transition metal are contained in the active component.
In a specific embodiment, the transition metal is selected from iron, cobalt, nickel, copper and zinc.
In a specific embodiment, in terms of the transition metal ions in the active component, the matter of the active component Amount accounts for the 2.5-10% of the cleanser quality, and the quality of preferably described active component accounts for the 4-7.5% of the cleanser quality.
In a specific embodiment, by percentage to the quality, the carrier accounts for the 80-95% of the cleanser, preferably The carrier accounts for the 85-92% of the cleanser.
In a specific embodiment, the carrier is selected from TiO2And/or Al2O3。
In a specific embodiment, the TiO2For Detitanium-ore-type, its particle diameter is more than or equal to 20nm and is less than or waits In 100nm, pore volume>0.4cm3/ g, specific surface area>200m2/g；It is preferred that the Al2O3For γ-Al2O3.Particle diameter is more than or equal to 20nm and it is less than or equal to 100nm, pore volume>0.4cm3/ g, specific surface area>200m2/g。
The two of the present invention provide a kind of method for preparing the as above cleanser of any one technical scheme, and it includes as follows Step：
(1) aqueous solution is prepared into by the soluble-salt of transition metal is soluble in water；
(2) aqueous solution that the carrier impregnation of the soluble-salt of the transition metal is prepared in step (1) can will be loaded In obtain first load mixed liquor so that the soluble-salt of the transition metal is carried on the carrier, and then born Carry the suspension of the carrier of the soluble-salt of the transition metal, preferably at 80-120 DEG C stir 6-12 hours make the transition The soluble-salt of metal is carried on the carrier；
(3) suspension in step (2) is dried, obtains the particle of the carrier of load active component, preferably described drying Condition be 100-150 DEG C；
(4) after the particle being carried out into oxidation processes with the mixed solution of nitric acid and hydrogen peroxide, it is washed with water, is calcined afterwards The cleanser is obtained, the condition of preferably described roasting is that 6-10 hours are kept at 200-700 DEG C.
In a specific embodiment, the soluble-salt of the transition metal be selected from the halide salt of transition metal, sulfate, Nitrate, acetate and carbonate.It is preferred that the halide salt is chlorate and/or Bromide.
In a specific embodiment, in step (1), by percentage to the quality, the soluble-salt of the transition metal Weight/mass percentage composition in aqueous is 16-30%.
In a specific embodiment, in step (2), the matter of the carrier and the aqueous solution of transition metal soluble-salt It is (1 to measure ratio:1)-(1:3).Wherein when the mass ratio of the carrier and the aqueous solution of transition metal soluble-salt is 1:When 3 just Through for hypersaturated state, therefore waste is easily caused using the aqueous solution of more transition metal soluble-salts.
In a specific embodiment, in step (4), the volume ratio of nitric acid and hydrogen peroxide is (1:2)-(2:1)；It is preferred that The volume content of the nitric acid is 68-70%, and the volume content of the hydrogen peroxide is 50%.That is nitric acid can be volume Percentage composition is 68-70% aqueous solution of nitric acid, and hydrogen peroxide can be the aqueous hydrogen peroxide solution that volume content is 50%.
In a specific embodiment, in step (4), in step (4), by the particles with water after oxidation processes Washing to the pH value of the water is 4-5, and more preferably described is distilled water and/or ultra-pure water.
The soluble-salt of wherein transition metal is supported on TiO2、Al2O3Crystalline phase is not formed when on surface but with list The scattered form of layer improves adsorption efficiency in the presence of the specific surface area for improving compound system so as to increase avtive spot.Secondly formed Compound system be similar to metal oxide semiconductor material, the energy gap increase electronics and hole for effectively reducing system have Effect separation improves purification efficiency.Inventor has found during invention, using nitric acid and hydrogen peroxide mixed solution to supported active The molecular sieve of component, which carries out oxidation processes, can effectively reduce after baking temperature.Although improving sintering temperature can equally reach To the purpose that oxidation processes are carried out to the molecular sieve of load active component, but too high (such as more than the 701 DEG C) meeting of sintering temperature Saboteur sieves configuration of surface and channel design causes surface sintering and passage to cave in so as to reduce than surface and pore volume aperture The final purification efficiency for influenceing cleanser, therefore sintering temperature should be controlled below 700 DEG C.
The cleanser of the present invention is including the gaseous light of at least one of alkane, alkene, alkynes, double bond alkene and alkynes Application in hydrocarbon feed.
The beneficial effects of the invention are as follows：Provided by the present invention for absorption lighter hydrocarbons tail gas in NOx normal temperature cleanser, its into Divide simply, easily obtain, cost is cheap, and cleanser preparation process is simple, and raw material is easy to get, and production cost is low, non-environmental-pollution.Only Agent, which is fitted into purification pipe, is widely portable to the purification containing ppm levels NOx in factory and use for laboratory lighter hydrocarbons tail gas, after purification NOx content is less than 1.0ppm (volume fraction), have it is high to NOx adsorptive selectivity and adsorption capacity, the advantages of using facilitating.
Brief description of the drawings
Fig. 1 is that finished product cleanser loads purification pipe schematic diagram；
Fig. 2 is the gas phase color before and after purified dose of mixed light-hydrocarbon tail gas absorbs containing 19.0ppm (volume fraction) NOx gases Monitoring system comparison diagram is composed, wherein peak value 3.63 is retention time, and peak area represents NOx concentration, is 1472.
Embodiment
The present invention is described below with reference to embodiment and accompanying drawing.
The percentage of each component in following cleanser prepared by the present invention using Xray fluorescence spectrometer measurement metal from The content of son.Xray fluorescence spectrometer manufactures for Dutch PANalytical companies, and technical parameter is：Rh targets, 4.0KW high powers X-ray tube, up to 60KV, maximum current is equipped with C, N and fixes road up to 160mA ceiling voltage, IQ+ Unmarked word sxemiquantitative softwares and FPMULTI multilayer elemental analysis softwares, can determine elemental range from6C-92U, content range can be surveyed from mg/kg-100%.
Embodiment 1
Weigh 16.5g copper sulphate and be configured to mixed solution with 100mL water containing 4 crystallizations water, then by 40g TiO2Particle Immerse in the mixed solution prepared, stirred 12 hours at 80 DEG C.Of supported active metals carrier is obtained in 100 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 5.Under the conditions of 200 DEG C of sintering temperature, it is calcined 10 hours, obtains finished product cleanser.Active component in cleanser is with copper ion Mass percent be calculated as 4.0%；Carrier TiO in cleanser2Mass percent for carrier quality/cleanser quality =92.0%.
Embodiment 2
Weigh 32.0g zinc nitrates and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g TiO2Particle Immerse in the mixed solution prepared, stirred 6 hours at 120 DEG C.Of supported active metals carrier is obtained in 150 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:2) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 4.Under the conditions of 700 DEG C of sintering temperature, it is calcined 6 hours, obtains finished product cleanser.Active component in cleanser is with zinc ion Mass percent is calculated as 7.5%；Carrier TiO in cleanser2Mass percent for carrier quality/cleanser quality= 85.0%.
Embodiment 3
Weigh 12.0g nickel sulfates and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g Al2O3Particle Immerse in the mixed solution prepared, stirred 10 hours at 100 DEG C.Supported active metals carrier is obtained in 120 DEG C of drying Particle.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume hundred that volumn concentration is 68%-70% Divide mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide for the aqueous hydrogen peroxide solution that content is 50% The volume ratio of the aqueous solution is 2:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle For 5.Under the conditions of 600 DEG C of sintering temperature, it is calcined 7 hours, obtains finished product cleanser.Active component in cleanser is with nickel ion Mass percent be calculated as 2.5%；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality =95.0%.
Embodiment 4
Weigh 43.5g iron chloride and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g Al2O3Particle Immerse in the mixed solution prepared, stirred 9 hours at 100 DEG C.Of supported active metals carrier is obtained in 110 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 4.Under the conditions of 300 DEG C of sintering temperature, it is calcined 9 hours, obtains finished product cleanser.Active component in cleanser is with copper ion Mass percent is calculated as 10.0%；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality =80.0%.
Embodiment 5
Weigh 22.5g cobalt acetates and be configured to mixed solution with 100mL water containing 4 crystallizations water, then by 40g Al2O3Particle Immerse in the mixed solution prepared, stirred 12 hours at 80 DEG C.Of supported active metals carrier is obtained in 100 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 5.Under the conditions of 400 DEG C of sintering temperature, it is calcined 8 hours, obtains finished product cleanser.Active component in cleanser is with cobalt ions Mass percent is calculated as 5.0%；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality= 90.0%.
Embodiment 6
Weigh 3.9g copper nitrates and contain 2.5 crystallizations water, weigh 4.2g zinc acetates and contain 2 crystallizations water, weigh 3.8g nickel nitrates Containing 6 crystallizations water, weigh 4.4g cobalt chlorides and contain 6 crystallizations water, weigh 5.0g ferric nitrates and prepared containing 9 crystallizations water and 100mL water Into mixed solution, then by 40g TiO2Particle is immersed in the mixed solution prepared, is stirred 6 hours at 120 DEG C.150 DEG C drying obtains the particle of supported active metals carrier.The particle of supported active metals carrier is immersed into volumn concentration is 68%-70% aqueous solution of nitric acid and volumn concentration is mixed solution (the wherein 68%- of 50% aqueous hydrogen peroxide solution The volume ratio of 70% aqueous solution of nitric acid and 50% aqueous hydrogen peroxide solution is 1:1) in, to be produced until there is no gas.Filtering Go out after particle and detect its pH value with distillation water washing as 4.Under the conditions of 700 DEG C of sintering temperature, it is calcined 6 hours, it is net obtains finished product Agent.Active component in cleanser is in terms of the mass percent of metal ion, including copper nitrate mass percent is 0.8%, Zinc acetate mass percent is 0.9%, and nickel nitrate mass percent is 0.8%, and cobalt chloride mass percent is 0.9%, nitric acid Weight of iron percentage is 1.1%；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality= 90.7%.
Comparative example 1
Weigh 5.5g copper sulphate and be configured to mixed solution with 100mL water containing 4 crystallizations water, then by 40g TiO2Particle soaks Enter in the mixed solution prepared, stirred 12 hours at 80 DEG C.Of supported active metals carrier is obtained in 100 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 5.Under the conditions of 200 DEG C of sintering temperature, it is calcined 10 hours, obtains finished product cleanser.Active component in cleanser is with copper ion Mass percent be calculated as 1.2%；Carrier TiO in cleanser2Mass percent for carrier quality/cleanser quality= 97.5%.
Comparative example 2
Weigh 6.6g zinc nitrates and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g TiO2Particle soaks Enter in the mixed solution prepared, stirred 6 hours at 120 DEG C.Of supported active metals carrier is obtained in 150 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:1) in, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing after particle and be 4.Under the conditions of 700 DEG C of sintering temperature, it is calcined 6 hours, obtains finished product cleanser.Active component in cleanser is with zinc ion Mass percent is calculated as 1.5%；Carrier TiO in cleanser2Mass percent for carrier quality/cleanser quality= 97.0%.
Comparative example 3
Weigh 5.2g nickel sulfates and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g Al2O3Particle soaks Enter in the mixed solution prepared, stirred 10 hours at 100 DEG C.Of supported active metals carrier is obtained in 120 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:In 1, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing as 5 after particle. Under the conditions of 600 DEG C of sintering temperature, it is calcined 7 hours, obtains finished product cleanser.Active component in cleanser is with the matter of nickel ion It is 1.2% to measure percentages；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality= 97.6%.
Comparative example 4
Weigh 4.3g iron chloride and be configured to mixed solution with 100mL water containing 6 crystallizations water, then by 40g Al2O3Particle soaks Enter in the mixed solution prepared, stirred 9 hours at 100 DEG C.Of supported active metals carrier is obtained in 110 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:In 1, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing as 4 after particle. Under the conditions of 300 DEG C of sintering temperature, it is calcined 9 hours, obtains finished product cleanser.Active component in cleanser is with the matter of copper ion It is 0.8% to measure percentages；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality= 98.1%.
Comparative example 5
Weigh 5.2g cobalt acetates and be configured to mixed solution with 100mL water containing 4 crystallizations water, then by 40g Al2O3Particle soaks Enter in the mixed solution prepared, stirred 12 hours at 80 DEG C.Of supported active metals carrier is obtained in 100 DEG C of drying Grain.The particle of supported active metals carrier is immersed into the aqueous solution of nitric acid and volume basis that volumn concentration is 68%-70% Content is mixed solution (wherein the 68%-70% aqueous solution of nitric acid and 50% hydrogen peroxide water of 50% aqueous hydrogen peroxide solution The volume ratio of solution is 1:In 1, to be produced until there is no gas.Filter out and detect its pH value with distillation water washing as 5 after particle. Under the conditions of 400 DEG C of sintering temperature, it is calcined 8 hours, obtains finished product cleanser.Active component in cleanser is with the matter of cobalt ions It is 1.1% to measure percentages；Carrier Al in cleanser2O3Mass percent for carrier quality/cleanser quality= 97.7%.
Effect after purification
Be 15mm by cleanser (embodiment 1-6) loading internal diameter such as accompanying drawing 1, in long 100mm pipe, pipe both ends 1,3 are close Close threaded connection.Containing 19.0ppm (volume fraction) NOx gases, mixed light-hydrocarbon tail gas is passed through equipped with cleanser with 100mL/min Purification pipe.Continuing purge gas-chromatography monitoring spectrogram 2 after 10 hours, illustrate that being cleaned absorption is less than 1.0ppm (volume integrals Number).Embodiment after 10 hours, gas-chromatography NCD monitoring NOx contents, the results are shown in Table 1 with comparative example continuing purge.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
NOx content (ppm) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
NOx content (ppm) 5.1 4.7 4.6 4.8 5.2
The preferable possible embodiments of the present invention are the foregoing is only, not thereby limit to the scope of the claims of the present invention, thus it is all It is the equivalent structure change made with description of the invention and accompanying drawing content, is both contained in protection scope of the present invention.

Claims (10)

1. a kind of cleanser for removing nitrogen oxides, it includes active component and can load the carrier of the active component, its In, the one or more in transition metal are contained in the active component.
2. cleanser according to claim 1, it is characterised in that the transition metal is in iron, cobalt, nickel, copper and zinc At least one.
3. cleanser according to claim 1 or 2, it is characterised in that with the transition metal ions in the active component Meter, the quality of the active component account for the 2.5-10% of the cleanser quality, and the quality of preferably described active component accounts for described The 4-7.5% of cleanser quality；By percentage to the quality, the carrier accounts for the 80-95% of the cleanser；It is preferred that the carrier Account for the 85-92% of the cleanser.
4. according to the cleanser described in any one in claim 1-3, it is characterised in that the carrier is selected from TiO2And/or Al2O3；
It is preferred that the TiO2For Detitanium-ore-type, its particle diameter is more than or equal to 20nm and is less than or equal to 100nm, pore volume>0.4cm3/ G, specific surface area>200m2/g；
It is preferred that the Al2O3For γ-Al2O3, particle diameter is more than or equal to 20nm and to be less than or equal to 100nm, pore volume>0.4cm3/ G, specific surface area>200m2/g。
5. a kind of method for preparing the cleanser as described in any one in claim 1-4, it comprises the following steps：
(1) aqueous solution is prepared into by the soluble-salt of transition metal is soluble in water；
(2) carrier impregnation that will can load the soluble-salt of the transition metal is first in the aqueous solution of preparation in step (1) First obtain loading mixed liquor, so that the soluble-salt of the transition metal is carried on the carrier, and then obtain loading institute State the suspension of the carrier of the soluble-salt of transition metal, preferably at 80-120 DEG C stir 6-12 hours make the transition metal Soluble-salt be carried on the carrier；
(3) suspension in step (2) is dried, obtains the particle of the carrier of load active component, the bar of preferably described drying Part is 100-150 DEG C；
(4) after the particle being carried out into oxidation processes with the mixed solution of nitric acid and hydrogen peroxide, it is washed with water, roasting afterwards obtains The cleanser, the condition of preferably described roasting are that 6-10 hours are kept at 200-700 DEG C.
6. according to the method for claim 5, it is characterised in that the soluble-salt of the transition metal is selected from transition metal Halide salt, sulfate, nitrate, acetate and carbonate.
7. the method according to claim 5 or 6, it is characterised in that in step (1), by percentage to the quality, the mistake It is 16-30% to cross the weight/mass percentage composition of the soluble-salt of metal in aqueous.
8. according to the method described in any one in claim 5-7, it is characterised in that in step (2), the carrier and mistake The mass ratio for spending the aqueous solution of metal soluble-salt is (1:1)-(1:3).
9. according to the method described in any one in claim 5-8, it is characterised in that in step (4), nitric acid and hydrogen peroxide Volume ratio be (1:2)-(2:1)；
It is preferred that the volume content of the nitric acid is 68-70%, the volume content of the hydrogen peroxide is 50%.
10. according to the method for claim 9, it is characterised in that in step (4), by the particle after oxidation processes The pH value for being washed with water to the water is 4-5, and more preferably described is distilled water and/or ultra-pure water.
CN201610328956.3A 2016-05-18 2016-05-18 A kind of cleanser for removing nitrogen oxides and preparation method thereof Pending CN107398248A (en)

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Application publication date: 20171128