CN108927184A - A kind of porous composite oxide and preparation method thereof - Google Patents

A kind of porous composite oxide and preparation method thereof Download PDF

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Publication number
CN108927184A
CN108927184A CN201810777641.6A CN201810777641A CN108927184A CN 108927184 A CN108927184 A CN 108927184A CN 201810777641 A CN201810777641 A CN 201810777641A CN 108927184 A CN108927184 A CN 108927184A
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porous composite
composite oxide
catalyst
atom
aluminium
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高培海
高金鹏
孙钦磊
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Shandong Aytek Environmental Polytron Technologies Inc
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Shandong Aytek Environmental Polytron Technologies Inc
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/615—
    • B01J35/617—
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a kind of porous composite oxides, which is characterized in that x-ray inflection analysis at least has 2 or more diffraction maximums between 5-10o, at least there is 4 or more diffraction maximums, BET specific surface area 200m between 20-25o2/ g or more at least containing three kinds of elements such as silicon, aluminium, phosphorus, while at least containing one of copper and ferro element element.The mass content of the element silicon is 6%-20%；The mass content of aluminium element is 10%-30%；The mass content of P elements is 10%-30%；The mass content of iron or copper is 5% or less.Porous composite oxide of the invention can be used as the catalyst of denitrification, not only have very high catalytic denitration activity in 150-200 DEG C of low-temperature range, but also also have higher catalytic denitration activity in 500 DEG C or more of high temperature section.The present invention is higher in the oxynitrides purifying property of low temperature and high temperature, and high-temperature hydrothermal stability can be good, is suitable for use as SCR catalyst.

Description

A kind of porous composite oxide and preparation method thereof
Technical field
The present invention relates to nitrogen oxides removal technology field, specifically a kind of porous composite oxide and its preparation side Method.
Background technique
It, can be with using urea water or ammonia using metal oxide catalysts such as vanadium titaniums by selective catalytic reduction (SCR) To power plant, Industrial Boiler, nitrogen oxides contained by the exhaust gas of the plant gas such as kiln and internal combustion engine discharge is purified.But Vanadium in this catalyst, due to being easy distillation at high temperature, so that the activity decline of catalyst.And catalyst is due to containing Harmful element vanadium, so that the recovery processing of catalyst is more difficult.For the denitrating catalyst of moving source, vanadium has It may be discharged from exhaust gas, so being especially unsuitable for the purification of vehicle exhaust.
CN104971736A discloses a kind of natural ferro manganese composite oxides SCR denitration and de- to flue gas using it The method of pin, catalyst are containing nano-iron oxide and nano manganese oxide and with nano-micrometre hierarchical porous structure Natural iron and manganese oxides ore is raw material.Although the low-temperature catalytic activity in 300 degree of this catalyst or less low-temperature range is preferable, But catalytic activity of this molecular sieve SCR catalyst in 400 degree or more of high temperature section is lower, tends not to meet conduct High activity required by the denitrating catalyst of moving source, especially vehicle exhaust denitrating catalyst, the requirement of wide temperature window.
CN104971780A discloses a kind of SCR denitration, use diatomite and molecular sieve substitute titanium dioxide as Carrier, and rare earth oxide is added, the heat resistance of catalyst can be improved, play stable lattice structure and prevent volume contraction Double action；The denitrification rate that poly-ferrocene improves denitrating catalyst is added, but this catalyst is still unable to satisfy the de- of moving source The requirement of 700 DEG C of denox catalyst or more high-temperature hydrothermal stabilities.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of porous composite oxides and preparation method thereof.
In order to solve the above technical problems, the technical scheme is that a kind of porous composite oxide, x-ray inflection analysis, At least there is 2 or more diffraction maximums between 5-10 o, at least there is 4 or more diffraction maximums, BET ratio between 20-25 o Surface area 200m2/ g or more, at least containing three kinds of elements such as silicon, aluminium, phosphorus, and meanwhile it is at least first containing one of copper and ferro element Element.
Preferably, the mass content of the element silicon is 6%-20%；The mass content of aluminium element is 10%-30%；P elements Mass content be 10%-30%；The mass content of iron or copper is 5% or less.
Preferably, the porous composite oxide can be used as catalyst for cleaning up nitrogen oxides.
Preferably, a kind of porous composite oxide, preparation method includes the following steps: at least former containing silicon atom, aluminium Primogel A composed by son, phosphorus atoms, copper atom or iron atom and quaternary ammonium salt and water, at a temperature of 100 DEG C -250 DEG C Hydrothermal synthesis, the solid precursor prepared is separated from the mother liquor after hydrothermal synthesis, is added at least containing silicon atom, aluminium In the Primogel B of atom, phosphorus atoms, copper atom or iron atom and organic amine and water, gained mixture is at 100 DEG C -250 DEG C At a temperature of carry out hydrothermal synthesis, isolate solid powder from the mother liquor after hydrothermal synthesis, by drying, washing and roasting after Obtain porous composite oxide.
Preferably, quaternary ammonium salt used is tetraethyl ammonium hydroxide, and organic amine used is morpholine.
Preferably, prepared porous composite oxide can be used as catalyst.
By adopting the above-described technical solution, the invention has the following advantages: porous composite oxide of the invention It can be used as the catalyst of denitrification, not only there is very high catalytic denitration activity in 150-200 DEG C of low-temperature range, And also there is higher catalytic denitration activity in 500 DEG C or more of high temperature section.The present invention is closed in the nitrogen oxidation of low temperature and high temperature Object purifying property is all higher, and high-temperature hydrothermal stability can be good, is suitable for use as SCR catalyst.
Detailed description of the invention
Fig. 1: the XRD of porous composite oxide 1 prepared by embodiment 1.
Fig. 2: the XRD of porous composite oxide 2 prepared by embodiment 2.
Fig. 3: the XRD of porous composite oxide 3 prepared by embodiment 3.
Hereinafter, being described in detail with regard to embodiments of the present invention, but following explanation is embodiments of the present invention An example (typical example) is not to specify these contents.
Nitrogen oxides and its purification
For example there are nitric oxide, nitrogen dioxide, nitrous oxides etc. for the catalyst cleaning nitrogen oxides of object through the invention. In this specification, purification nitrogen oxides is that nitrogen oxides is instigated to react on a catalyst, is converted to nitrogen and oxygen etc..
At this point, nitrogen oxides can directly react, can also be coexisted in for the purpose for improving purification efficiency with reducing agent In catalyst.Ammonia, urea, organic amine, carbon monoxide, hydrocarbon, hydrogen etc. can be used for reducing agent, it is preferable to use ammonia, urea.
Catalyst
Object catalyst of the invention is as described above, refer to the catalyst that can purify nitrogen oxides, in particular to containing porous The catalyst for cleaning up nitrogen oxides of composite oxides.
Each component content in porous composite oxide
The ratio of contained each element is not particularly limited in oxide.Wherein the mass content of element silicon is 6%-20%, preferably 7%- 18%；The mass content of aluminium element is 10%-30%, preferably 15%-25%；The mass content of P elements is 10%-30%, preferably 15%- 25%；The mass content of iron or copper is 5% hereinafter, it is preferred that 4% or less.
The synthetic method of porous composite oxide catalyst
The synthetic method of porous composite oxide is hydro-thermal method, the specific steps are as follows:
(a) sodium hydroxide and/or potassium hydroxide, quaternary ammonium salt and water mixing are sequentially added in a kettle, add silicon source and silicon Source is eventually adding copper source or source of iron, and being formed after being sufficiently stirred has the gel mixture A matched as follows:
SiO2: Al2O3Molar ratio=5-200；
Na2O and/or KOH:SiO2Molar ratio=0.05-0.5；
Water: SiO2Molar ratio=5-200；
Quaternary ammonium salt: SiO2Molar ratio=0.02-1.
CuO or Fe2O3: SiO2Molar ratio=0.005-0.03
(b) gel mixture A is transferred in reaction kettle, carries out hydrothermal synthesis reaction；After hydrothermal synthesis reaction, is filtered, washed It washs, dry, obtain the precursor A of porous composite oxide described in claim 1；
(c) copper source or source of iron are added in phosphate aqueous solution and is dissolved, silicon source is then added, titanium dioxide is added after reaction is sufficiently stirred Silica solution；Then organic amine is added, stirs, sufficiently obtains the gel mixture B with composition below after reaction:
P2O5: Al2O3Molar ratio=0.5-1.5；
SiO2: Al2O3Molar ratio=0.05-1.0；
Organic amine: Al2O3Molar ratio=0.5-5；
CuO or Fe2O3: Al2O3 molar ratio=0.005-0.03
Water: Al2O3Molar ratio=25-100.
(d) gel mixture B is put into autoclave, and the precursor A of porous composite oxide is added, carry out water Thermal synthesis reaction.
SiO in precursor A2: Al in gel mixture B2O3Molar ratio=0.05-1
(e) the resulting product of step (d) is filtered, washed, dried, porous composite oxide is obtained after roasting.
Synthesis material
Silicon source described in step (a, c), is not particularly limited, usually boehmite, aluminium isopropoxide, the alkanols such as three aluminium ethylates Aluminium, aluminium hydroxide, alumina sol, sodium aluminate etc., preferably boehmite, aluminium hydroxide and sodium aluminate.Step (a, c) institute The silicon source stated, is not particularly limited, usually fumed silica, silicon dioxide gel, colloidal silicon dioxide, waterglass, silicic acid Ethyl ester, methyl silicate etc., preferably gas phase fumed silica, silicon dioxide gel and colloidal silicon dioxide；Step (a, c) institute The copper source or source of iron stated, are not particularly limited, and usually using mantoquita or molysite, nitrate, sulfate, acetic acid can be used for example Salt, hydrochloride etc..Also the oxide for closing copper or iron can be used.
Quaternary ammonium salt described in step (a), is not particularly limited, usually tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, and four Propyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, methyl triethylammonium hydroxide, trimethylethyl ammonium hydroxide etc..It is excellent Select tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide.
Organic amine described in step (c), is not particularly limited, and the ester ring type heterocyclic compound of the nitrogen containing hetero atom both can be used Object, it is possible to use alkylamine can also use the mixture of the two kind aminated compounds.For the rouge containing hetero atom nitrogen Ring type heterocyclic compound, preferably morpholine, N-methyl morpholine, piperidines, piperazine, N, N'-lupetazin, Isosorbide-5-Nitrae-diaza two Ring (2,2,2) octane, N-methyl piperidine, 3- methyl piperidine, quinuclidine, pyrrolidines, N-Methyl pyrrolidone, hexa-methylene are sub- Amine etc., preferably morpholine, hexamethylene imine, piperidines, particularly preferred morpholine.For alkylamine, preferably diethylamine, diη-propyl Amine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, triethanolamine, N, N-diethyl ethylene diamine, N, N-dimethylethanolamine, N- Methyl diethanolamine, N-methylethanolamine, two-n-butylamines, neopentyl amine, two n-amylamines, isopropylamine, tert-butylamine, ethylenediamine, two Wopropyl ethyl amine, N-methyl n-butylamine etc., preferably di-n-propylamine, Tri-n-Propylamine, Tri-n-Propylamine, triethylamine, di-n-butylamine are different Propylamine, tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl n-butylamine, particularly preferred diethylamine, triethylamine.
The allotment of gel mixture A and B
The allocation process of gel mixture is influenced by dissolution sequence, dissolution conditions in step (a, c) of the present invention.Usually first handle Inorganic base is dissolved in water, and organic matter mixing is then added, and water/organic matter quality selects 0.1-10 than range in the above process, It is preferred that 1.0-5.0.I.e. there are a degree of dissolutions at room temperature for mixed liquor.Usual 0 DEG C of mixing temperature selection or more, preferably 10 DEG C or more；The ceiling temperature of dissolution at 100 DEG C hereinafter, it is preferred that 80 DEG C hereinafter, more preferable 60 DEG C or less.
Hydrothermal synthesis
During step (b, d) hydrothermal synthesis, above-mentioned gel mixture is transferred in autoclave.Hydrothermal synthesis it is anti- Temperature is answered to be normally controlled in 120 DEG C or more, preferably 140 DEG C or more, more preferable 150 DEG C or more；Ceiling temperature control is reacted 300 DEG C hereinafter, it is preferred that 250 DEG C hereinafter, more preferable 220 DEG C or less.Reaction time is normally controlled in 8h or more, preferably 12h or more, more It is preferred that 16h or more；The reaction time upper limit is normally controlled in 120h hereinafter, it is preferred that 60h is hereinafter, more preferably 48h or less.
Hydrothermal synthesis post-processing
Being filtered, washed, in drying process in step (b, e), drying process temperature select 60-200 DEG C, preferably 80-100 DEG C drying time selects 12-36h, preferably 12-24h.Product after drying, which needs heating and calcining to remove organic matter, just has suction Attached, catalytic performance, maturing temperature select 400-800 DEG C, preferably 500-600 DEG C.Calcination time selects 0.5-24h, preferably 1- For 24 hours, more preferable 3-10h.
The application method of porous composite oxide catalyst
Porous composite oxide catalyst of the invention can directly with powdered use, can also with silica, aluminium oxide, The mixing of the adhesive such as zirconium oxide, uses after being made the mixture containing catalyst.
Adhesive used in porous composite oxide catalyst of the invention is usually silica, aluminium oxide, zirconium oxide Equal inorganic adhesives or polysiloxane-based organic adhesion agent.The polysiloxane-based oligomer for referring to main chain and there is polysiloxanes key Or polymer, also a part of the substituent group of the main chain including polysiloxanes key is hydrolyzed and the substance of Xing Cheng Hydroxyalkyl base.Adhesive Concentration be not particularly limited, usually 1-20 mass %, from the aspect of intensity when following formings, preferably 2-15 mass %.
Porous composite oxide catalyst of the invention or the mixture containing the catalyst it is also pelletized or forming after make With.It is granulated or the method for forming is not particularly limited, can be carried out using various well known methods.In general, keeping the catalyst mixed Object forming is closed, is used as formed body.It is preferable to use honeycombs for the shape of formed body.In addition, the exhaust gas for being used as automobile etc. is urged When agent, the method for forming uses coating process or forming process, is made honeycombed catalyst.When using coating process, in general, this is sent out Bright catalyst and silica, aluminium oxide, the mixing of the inorganic adhesives such as zirconium oxide, production are slurried, then are coated on violet blueness The surface of the honeycombs of the inorganic matters such as stone production, is fired, is thus made.When using forming process, in general, this is sent out The inorganic adhesives or alumina fibre, glass fibre etc. such as bright catalyst for cleaning up nitrogen oxides and silica, aluminium oxide Inorfil is kneaded, and is carried out the forming of extrusion molding or compression method etc., is continued to fire, and preferably cellular urge thus is obtained Agent.
It, can be with when porous composite oxide catalyst of the invention is used as the exhaust gas purifying catalyst of the moving sources such as automobile It is used after being formed using coating process or extrusion molding method.The catalyst mouldings obtained according to the present invention are passing through coating process When manufacture, in general, the inorganic adhesives such as zeolite catalyst and silica, aluminium oxide are mixed, production is slurried, then by cordierite On the surface of equal formed body of the inorganic matters coated in production, it is fired, at this time preferably by being coated in honeycomb shape On formed body, cellular catalyst is obtained.The catalyst mouldings obtained according to the present invention are manufactured by extrusion molding method When, in general, by inorfils such as the inorganic adhesive of zeolite and silica, aluminium oxide etc. or alumina fibre, glass fibres It is kneaded, via the forming of extrusion molding or compression method etc., continues to fire, preferably obtain bee and being configured to honeycomb at this time Nest champion part.
Catalyst in the present invention is by purifying nitrogen oxides with the exhaust gas contact containing nitrogen oxides.The exhaust gas can be with Comprising the ingredient other than nitrogen oxides, such as it can wrap hydrocarbonaceous, carbon monoxide, carbon dioxide, hydrogen, nitrogen, oxygen, sulfur oxide, water.Tool Body, with method of the invention, can purify from diesel car, gasoline automobile, the construction of stationary power generation ship agricultural machinery Nitrogen contained by the various exhaust gas being discharged in the various diesel engines of mechanical cart aviation machine, boiler, gas turbine etc. Oxide.
When using catalyst in the present invention, the contact conditions of catalyst and exhaust gas are not particularly limited, usually space speed 100/h or more is spent, preferably 1000/h or more, usual 500000/h are hereinafter, it is preferred that 100000/h is hereinafter, temperature is usually 100 DEG C More than, preferably 150 DEG C or more, usual 700 DEG C hereinafter, it is preferred that 500 DEG C or less.
Specific embodiment
Embodiment
Hereinafter, carrying out further description to the present invention by embodiment, but the present invention is not by embodiment below It is limited.
X-ray diffraction (XRD) measurement
X-ray diffraction measure instrument is Panalytical X ' Pert PRO, detects light source Cu K α, tube voltage 40kV, pipe electricity Stream is 40mA, and detection angle range is 5-50 °, detection time 10min.Point that the present invention is synthesized by X-ray diffraction measure Sample powder after grinding is added in the square hole on glass plate, is then inserted into glass plate and surveys by the phase structure of son sieve The axial location of angle instrument, under the irradiation of Cu K α light source, probe is with 2 θ/min speed rotation.In addition, light source is not limited to Cu K α, Co K α, Mo K α, Ag K α also are used as the light source of material phase analysis.The raw material form of test can be powder, lotion or solid Particle.
The method of constituent analysis
The content that the present invention passes through each component in inductively coupled plasma spectroscopic assay porous composite oxide catalyst.Inductance coupling It closes plasma spectrum (ICP) measurement and uses PerkinElmer Optima8x00.Concentration gradient is made after standard sample is diluted Absorption curve.To be diluted with water after sample hydrofluoric acid dissolution, then by absorb peak intensity measure sample in each element it is dense Degree.
The measurement of specific surface area
Specific area measuring uses Quantachrome Autosorb-iQ2.The present invention measures the ratio of sample by gas absorption Surface area.It takes the sample of 100mg or so to be put into sample cell, is subsequently placed in liquid nitrogen, adsorptive pressure 0-1bar.All samples Product calcine 6h or more before absorption at 400-600 DEG C.
<evaluation method of catalyst activity>
After the catalyst punch forming of modulation, break into pieces, whole grain.The catalyst 1ml that whole grain is crossed is filled into atmospheric fixed bed stream In general formula reaction tube.With 1500ml/min(space velocity SV=100000/h), make the gas of the composition of table 1 on catalyst layer Circulation, while catalyst layer is heated.Respectively at different temperature, when fixed according to NO concentration at the outlet, the value of following formula To evaluate the nitrogen oxides of catalyst except deactivation.
(NO purifying rate)={ (entrance NO concentration)-(NO concentration at the outlet) }/(entrance NO concentration)
Table 1
Gas component Concentration
NO 500ppm
NH3 500ppm
O2 14 volume %
H2O 5 volume %
N2 Remaining ingredient
Embodiment 1
7.8g sodium aluminate (content 70%), 5g sodium hydroxide are dissolved in 50g water, be added 25% tetraethyl ammonium hydroxide it is water-soluble Then 200g silicon dioxide gel (dioxide-containing silica: 30%) is added dropwise to by liquid 70g, 1 hour formation mixed liquor of mixed at room temperature In above-mentioned mixed liquor, stir 2 hours at room temperature.Then it is added and contains 15% ferrous sulfate aqueous solution 60g, continue stirring 2 hours, obtain To the initially gel that sets out be put into the stainless steel synthesis reactor with polytetrafluoroethyllining lining, add 50g water, then heat to 160 DEG C, constant temperature 72 hours, after obtained solid product is washed with deionized, 100 DEG C drying 24 hours, obtain 78g and contain four The porous oxide precursor A of ethyl ammonium hydroxide.
69.2g phosphoric acid (content 85%) and 40.8g boehmite are slowly added into 152g water, after stirring 4 hours, Sequentially adding 30g silicon dioxide gel, (dioxide-containing silica: 30%), morpholine 52.2g and water 70g, mixture keep 40 DEG C of stirrings It 3 hours, is then added and contains 20% copper sulfate solution 25g, continue stirring 2 hours, obtain that there is the aqueous solidifying of composition below Glue.The aqueous gel is transferred in autoclave, 10g porous oxide precursor A, side stirring, side heating, most is added Height reaches to react 24 hours at 200 DEG C of temperature.After reaction, through cooling, supernatant liquor is removed by decantation, recycles sediment.With After water cleans sediment 3 times, filtering is dry at 100 DEG C.Then, it at 550 DEG C, under air draught, is fired, removes Organic matter obtains 85g porous composite oxide 1.
Test results are shown in figure 1 by the XRD of porous composite oxide 1.The mass concentration analysis of each component is as shown in table 2. Catalytic reaction activity test result is as shown in table 3.
Embodiment 2
69.2g phosphoric acid (content 85%) and 40.8g boehmite are slowly added into 152g water, after stirring 4 hours, successively 30g silicon dioxide gel is added, and (dioxide-containing silica: 30%), morpholine 52.2g and water 70g, mixture keep 40 DEG C of stirrings 3 small When, it is then added and contains 20% copper sulfate solution 25g, continue stirring 2 hours, obtain the aqueous gel with composition below.It will The aqueous gel is transferred in autoclave, and 20g porous oxide precursor A, side stirring, side heating, up to is added It is reacted 24 hours at up to 200 DEG C of temperature.After reaction, through cooling, supernatant liquor is removed by decantation, recycles sediment.It is clear with water After washing sediment 3 times, filtering is dry at 100 DEG C.Then, it at 550 DEG C, under air draught, is fired, removes organic Object obtains 98g porous composite oxide 1.
Test results are shown in figure 2 by the XRD of porous composite oxide 2.The mass concentration analysis of each component is as shown in table 2. Catalytic reaction activity test result is as shown in table 3.
Embodiment 3
69.2g phosphoric acid (content 85%) and 40.8g boehmite are slowly added into 152g water, after stirring 4 hours, successively 30g silicon dioxide gel is added, and (dioxide-containing silica: 30%), morpholine 52.2g and water 70g, mixture keep 40 DEG C of stirrings 3 small When, it is then added and contains 20% copper sulfate solution 25g, continue stirring 2 hours, obtain the aqueous gel with composition below.It will The aqueous gel is transferred in autoclave, and 30g porous oxide precursor A, side stirring, side heating, up to is added It is reacted 24 hours at up to 200 DEG C of temperature.After reaction, through cooling, supernatant liquor is removed by decantation, recycles sediment.It is clear with water After washing sediment 3 times, filtering is dry at 100 DEG C.Then, it at 550 DEG C, under air draught, is fired, removes organic Object obtains 104g porous composite oxide 1.
Test results are shown in figure 3 by the XRD of porous composite oxide 3.The mass concentration analysis of each component is as shown in table 2. Catalytic reaction activity test result is as shown in table 3.
Comparative example 1
Porous oxide precursor A is fired at 550 DEG C, under air draught, is removed organic matter, is obtained oxide 4.Respectively The mass concentration analysis of component is as shown in table 2.Catalytic reaction activity test result is as shown in table 3.
Comparative example 2
69.2g phosphoric acid (content 85%) and 40.8g boehmite are slowly added into 152g water, after stirring 4 hours, successively 30g silicon dioxide gel is added, and (dioxide-containing silica: 30%), morpholine 52.2g and water 70g, mixture keep 40 DEG C of stirrings 3 small When, it is then added and contains 20% copper sulfate solution 25g, continue stirring 2 hours, obtain the aqueous gel with composition below.It will The aqueous gel is transferred in autoclave, side stirring, and side heating is reacted 24 hours at 200 DEG C of maximum temperature reached.Instead Ying Hou removes supernatant liquor by decantation, recycles sediment through cooling.After washing with water sediment 3 times, filtering, at 100 DEG C Lower drying.Then, it at 550 DEG C, under air draught, is fired, removes organic matter, obtain 82g oxide 5.Each component Mass concentration analysis is as shown in table 2.Catalytic reaction activity test result is as shown in table 3.
Table 2
Al P Si Cu Fe BET
Embodiment 1 Oxide 1 18.3% 20.9% 8.1% 2.8% 0.2% 378 m2/g
Embodiment 2 Oxide 2 19.1% 20.5% 10.5% 2.8% 0.4% 294 m2/g
Embodiment 3 Oxide 3 19.4% 20.7% 14.5% 2.8% 0.7% 421 m2/g
Comparative example 1 Oxide 4 1.3% — 45% — 2.8% 320 m2/g
Comparative example 2 Oxide 5 19.7% 23.0% 5.1% 3.5% — 560 m2/g
Table 3
As can be seen from Table 3, the porous composite oxide in the embodiment of the present invention not only has in 200 DEG C of following temperature sections Excellent catalytic denitration performance, while higher catalytic denitration activity is also shown in 500 DEG C of temperatures above sections.
In addition, can be used as catalyst for cleaning up nitrogen oxides, especially by using porous composite oxide of the invention It is that the catalyst all shows excellent catalytic activity in wider temperature window, is suitable in exhaust gas, special as removing It is the denitrating catalyst of the nitrogen oxides in the exhaust gas of diesel engine.
SHAPE the equipment used in the * MERGEFORMAT present invention be this field commonly used equipment, herein no longer It repeats.
The foregoing is merely the schematical specific embodiment of the present invention, the range being not intended to limit the invention.It is any Those skilled in the art, made equivalent changes and modifications under the premise of not departing from design and the principle of the present invention, It should belong to the scope of protection of the invention.

Claims (6)

1. a kind of porous composite oxide, which is characterized in that x-ray inflection analysis, at least in the presence of 2 or more between 5-10 o At least there is 4 or more diffraction maximums, BET specific surface area 200m between 20-25 o in diffraction maximum2/ g or more, at least containing silicon, Three kinds of elements such as aluminium, phosphorus, while at least containing one of copper and ferro element element.
2. a kind of porous composite oxide according to claim 1, which is characterized in that the mass content of the element silicon is 6%-20%；The mass content of aluminium element is 10%-30%；The mass content of P elements is 10%-30%；The quality of iron or copper contains Amount is 5% or less.
3. according to claim 1 with 2 in a kind of porous composite oxide described in any claim, which is characterized in that it is described Porous composite oxide can be used as catalyst for cleaning up nitrogen oxides.
4. a kind of porous composite oxide described in any claim in -3 according to claim 1, which is characterized in that it is prepared Method is the following steps are included: at least containing silicon atom, aluminium atom, phosphorus atoms, copper atom or iron atom and quaternary ammonium salt and water institute The Primogel A of composition separates preparation by the hydrothermal synthesis at a temperature of 100 DEG C -250 DEG C from the mother liquor after hydrothermal synthesis Solid precursor out, be added at least containing silicon atom, aluminium atom, phosphorus atoms, copper atom or iron atom and organic amine and In the Primogel B of water, gained mixture carries out hydrothermal synthesis at a temperature of 100 DEG C -250 DEG C, from the mother liquor after hydrothermal synthesis In isolate solid powder, by drying, washing and roasting after obtain porous composite oxide.
5. a kind of preparation method of porous composite oxide according to claim 4, it is characterised in that: quaternary ammonium salt used is Tetraethyl ammonium hydroxide, organic amine used are morpholine.
6. a kind of preparation method of porous composite oxide according to claim 4, it is characterised in that: prepared is porous Composite oxides can be used as catalyst.
CN201810777641.6A 2018-07-16 2018-07-16 A kind of porous composite oxide and preparation method thereof Pending CN108927184A (en)

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Application publication date: 20181204