CN110013873A - Catalytic decomposition nitrate, the catalyst of nitrite or dust technology and its preparation and application - Google Patents
Catalytic decomposition nitrate, the catalyst of nitrite or dust technology and its preparation and application Download PDFInfo
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- CN110013873A CN110013873A CN201910387818.6A CN201910387818A CN110013873A CN 110013873 A CN110013873 A CN 110013873A CN 201910387818 A CN201910387818 A CN 201910387818A CN 110013873 A CN110013873 A CN 110013873A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention provides the catalyst of a kind of catalytic decomposition nitrate, nitrite or dust technology and preparations and application, preparation method: (1) ZSM-5 molecular sieve roasting, grinding are obtained HZSM-5 molecular sieve powder；(2) obtained HZSM-5 molecular sieve powder is stirred and evenly mixed and is formed with additive, roasting obtains catalyst after drying；Additive includes active carbon powder, and the mass ratio of HZSM-5 molecular sieve powder and active carbon powder is 2.0:0.5-2.0:4.0.Utilize the method for above-mentioned molecular sieve catalyst catalytic decomposition nitrate: under nitrogen atmosphere, in fixed bed reactors by one of nitrate aqueous solution, nitrite aqueous solution or diluted nitric acid aqueous solution or it is a variety of catalytic reduction reaction is carried out by catalyst bed, the molecular sieve catalyst filled with catalytic decomposition nitrate in catalyst bed.The method that the present invention is catalytically decomposed is simple, at low cost, reduces environmental pollution, increases economic efficiency, and can be used for the nitrate catalytic decomposing method of environmental functional reparation.
Description
Technical field
The present invention relates to a kind of preparation methods of the molecular sieve catalyst of catalytic decomposition nitrate, nitrite or dust technology
And application, belong to petrochemical industry.
Background technique
Since the discharge of industrial production nitrogenous effluent, the application of agriculture nitrogen fertilizer, the discharge of sanitary sewage are caused by environment
Pollute increasingly severe, azotate pollution problem is increasingly subject to extensive concern, and drinking the underground water after by azotate pollution can be tight
Human health is damaged again, and nitrate is reduced into nitrous acid under nitrate reduction bacterium and metabolism in human body intestinal canal
Salt, the ability that the hemoglobin of blood of human body can be made to carry oxygen atom reduce so as to cause histanoxia, lead to " blue baby's disease "；Nitre
Hydrochlorate is also the predecessor that nitrosamino- (NOC) is formed, and is a kind of determining presence of genotoxic compound of easy induced tumor disease.
Currently, the processing method of nitrate is important in water uses physico-chemical process, bioanalysis, chemical method.Common physico-chemical process (from
Son exchange, reverse osmosis, electrodialysis) mainly nitrate is concentrated and separated, it is not harmless object by nitrate transformation, needs to add
Subsequent processing method or device.Patent CN201610283886.4 just describes a kind of electrodialysis-ion exchange film reduction decomposition
The method of nitrate, nitrate reduction decomposition method is complicated, needs that bioreactor is cooperated to use, and nitrate transformation rate
It is not high.Furthermore patent CN201520393462.4 equally describes the device using Cadmium column reduction nitrate, and the key of this method exists
There is the cadmium column of reduction activation in preparation, there are the pollution problems of heavy metal cadmium.Biological anti-digestion is a kind of to select nitrate
Property conversion reduction economic means, principle is similar to the decomposition of nitrate in human body, but practical operation control difficulty, it is understood that there may be
The problems such as germ contamination.Point out that aspergillus parasiticus imitates nitrite with good degradation in patent CN201410370569.7
Fruit；(nitrate reductase of lactic acid bacteria containing selenium and Study of Antioxidation, Hubei University Of Technology's Master's thesis, 2016) what plug et al.
Think that lactic acid bacteria containing selenium equally has actively beneficial degradation effect to nitrite.
Use chemical catalysis reduction method can be at normal temperature by nitrate, Nitrite transformation NOx, NH3, even N2,
The activity of catalyst activity digestive ferment more anti-than biology is high, and with H2It will not cause secondary pollution for reducing agent.Moreover, high
Active catalyst type is more and modification method for preparing is more, most common method giving using nano zero valence iron as reduction nitrate
Electron, lot of documents reaction, under the conditions of existing for the inanimate object cell, the main reduzate of nitrate is ammonium, furthermore zero
Valence iron surface adulterates bimetallic (Pt, Pd, Cu) and provides new path for the reduction of nitrate.Patent CN201610010239.6 and
CN201610010039.0 just describes iron copper, iron silver bimetal fragment and disodium ethylene diamine tetraacetate in isolation air respectively
Under the conditions of, the anti-digestion reaction of nitrite generation can be caused by adjusting wastewater pH to highly acid, although final conversion ratio highest can
Up to 100%, on condition that under the case where completely cutting off air and introducing reducing agent urea.Wang Kun equality people research uses supported palladium-
Copper activity Pd/carbon catalyst catalysis reduction removal nitrate, moreover lot of documents is reported, using TiO2Photocatalysis is in certain item
Reduction nitrate can be equally catalyzed under part, although these catalyst have high catalytic activity, nitrate transformation rate is close
100%, it also needs to introduce H2、NH3Equal reducing agents can be by the thorough reduction decomposition of nitrate at N2。
It is worth noting that the rise of coal-ethylene glycol industry, dilute in relation to synthesis system by-product in coal-ethylene glycol technique
The processing of nitric acid evokes the research interest of people, and from the point of view of nearest Research Literature, is gone back by chemical method catalysis
The method of orthonitric acid salt.Following patent CN201410062618.0, CN201410123581.8, CN201410120309.4 are just adopted
The dust technology of by-product can be restored under certain condition with activated carbon supported Fe, Mo, Cu, V, Mn, Zr isoreactivity metallic element
At nitrous acid, moreover it is immersed in molecular sieve gel mother liquor in patent CN201410456172.X using active carbon and work is made
Property charcoal wrap up molecular screen membrane carrier, then again the metals such as dip loading Fe, Cu be made the dust technology with catalytic activity reduction urge
Agent has good nitrate reductase, and without additionally introducing reducing agent.
So far, not yet occur utilizing the report of molecular sieve catalytic reduction decomposition nitrate.
Summary of the invention
The molecular sieve catalyst discarded in preparing propylene from methanol commercial plant is used to prepare catalysis the present invention provides a kind of
The catalyst to reduce nitrate and application.
In order to achieve the object of the present invention, present invention employs the following technical solutions:
First aspect present invention provides a kind of method for preparing catalyst that catalysis reduction nitrate decomposes:
(1) by after ZSM-5 molecular sieve roasting, grinding, HZSM-5 molecular sieve powder is obtained；
(2) obtained HZSM-5 molecular sieve powder is stirred and evenly mixed and is formed with additive, roasting is urged after drying
Agent；
The additive includes active carbon powder, and the mass ratio of the HZSM-5 molecular sieve powder and active carbon powder is
2.0:0.5-2.0:4.0.
After HZSM-5 molecular sieve powder and additive are mixed into plastic body in preparation method of the invention, squeezed
It forms out.Extrusion molding it is specific as follows: after HZSM-5 molecular sieve powder and additive enter barrel from banded extruder hopper, in spiral shell
Under bar turning effort, by being fed forward to feeding section under the action of material tube inner wall and screw surface fricting shearing, so that loosely
Solid is compacted while being fed forward；Into after compression section, the depth shallower of screw channel is further compacted；Meanwhile in barrel
Under external heat and the effect of screw rod and material tube inner wall fricting shearing, material temperature raising, which starts melting, keeps material uniform, fixed warm, quantitative, fixed
Press melt extrusion, to head after form, through sizing obtain product.
Preferably, additive described in step (2) further includes molding adhesive, auxiliary agent, peptizing agent and water, addition it is described
The mass ratio of HZSM-5 molecular sieve powder and the active carbon powder, molding adhesive, auxiliary agent, water and peptizing agent is 2.0:0.5-
4.0:0.12-0.15:0.15-0.25:1:0.2-0.25；It is further preferred that the HZSM-5 molecular sieve powder and the work
Property carbon powder, molding adhesive, auxiliary agent, water and peptizing agent mass ratio be 2.0:0.5:0.14:0.2:1:0.22.
Present invention utilizes to draw off discarded ZSM-5 molecular sieve on preparing propylene from methanol commercial plant (MTP commercial plant)
Catalyst is that raw material combines ZSM-5 molecular sieve and active carbon powder, has given full play to the unique duct of ZSM-5 molecular sieve
Structure and hydrothermal stability；Meanwhile being easy to the advantages of vulcanizing using active powdered carbon large specific surface area, active component, the two is had
Effect ground combines, and prepares the new catalyst of suitable nitrate or dust technology catalysis reduction.Under certain condition, of the invention
The catalyst of preparation can effectively be catalyzed reduction nitrate, even dust technology, and catalytic activity with higher, for waste water
There are Important Economic, technical application valence in processing, environmental statement, even coal chemical technology, especially coal-ethylene glycol industry
Value, has widened the application field of ZSM-5 molecular sieve catalyst, has certain reference value.
Preferably, the active carbon powder is in wood activated charcoal powder, coconut husk, shell or coaly activated carbon powder
It is one or more；It is further preferred that the active carbon powder is partial size 200-400 mesh, ash content mass content is 15%-20%
Coaly activated carbon powder；
Preferably, the active carbon powder is selected from coconut husk or active fruit shell carbon, and metal is added in active carbon powder
Active component, the quality of the metal active constituent are the 0.1-1% of the HZSM-5 molecular sieve powder quality；
It is further preferred that the metal active constituent is metal salt；Metallic element in the metal salt is selected from the
One of VIII race's metallic element, I B-group metal element are a variety of, further preferably one or both of iron or copper.
Preferably, the molding adhesive is selected from one of boehmite, SB powder, kaolin or bentonite or more
Kind, preferably boehmite；
The auxiliary agent is selected from one of methylcellulose, sesbania powder, glycerol or polyethylene glycol or a variety of, preferably methyl
Cellulose；
The peptizing agent is one of concentrated nitric acid solution, acetic acid solution or citric acid solution, and preferably concentrated nitric acid is molten
Liquid；It is further preferred that the mass concentration of the peptizing agent is 60-70%.
Preferably, ZSM-5 molecular sieve described in step (1) is discarded with what is drawn off on preparing propylene from methanol commercial plant for industry
ZSM-5 molecular sieve catalyst.ZSM-5 molecular sieve catalyst in MTP commercial plant the regeneration period less than two weeks when need unload
Out, the catalyst more renewed, then the above-mentioned ZSM-5 molecular sieve drawn off passes through purge, after removing molecular sieve surface dust
ZSM-5 molecular sieve as in the present invention as reactant.
Preferably, the maturing temperature of ZSM-5 molecular sieve described in step (1) be 500-600 DEG C, further preferably 550
DEG C, it is described to be ground to the partial size of the ZSM-5 molecular sieve be 100-200 mesh；In step (2) at 120 DEG C after dry 8-10h
In 300-500 DEG C of roasting temperature 2-12h.In a preferred embodiment, to prevent catalyst during roasting
The phenomenon that being broken, the roasting can be using roasting, i.e., first on the basis of room temperature with the heating speed of 2 DEG C/min stage by stage
Rate is warming up to 300 DEG C, after keeping 4h, is continuously heating to 500 DEG C of holding 6h.
Second aspect of the present invention provides a kind of catalytic decomposition nitrate, nitrite being prepared using the above method
Or the molecular sieve catalyst of dust technology.
Third aspect present invention provide it is a kind of using above-mentioned molecular sieve catalyst catalytic decomposition nitrate, nitrite or
The method of dust technology, under nitrogen atmosphere, by nitrate aqueous solution, nitrite aqueous solution or dust technology in fixed bed reactors
One of aqueous solution or it is a variety of catalytic reduction reaction is carried out by catalyst bed, fill in the catalyst bed above-mentioned
Molecular sieve catalyst.
Preferably, the reaction temperature of the fixed bed reactors is 60-120 DEG C, reaction pressure 0.20-0.30Mpa, liquid
Phase air speed is 0.3-1.5h-1, gas phase air speed and the ratio of liquid phase air speed are 1-5, and above-mentioned gas phase and liquid phase air speed refers to per hour
The admission space of volume (liquid (LHSV) or gas (GHSV))/catalyst of charging)；Nitrate in the nitrate aqueous solution
Mass fraction be 0.1-2%, the mass fraction of nitrite is 0.1-2%, dilute nitre in the nitrite aqueous solution
The mass fraction of nitric acid is 0.1-2% in aqueous acid；
It is further preferred that the temperature of the fixed bed reactors is 80-100 DEG C, reaction pressure 0.25-0.30Mpa,
Liquid phase air speed is 0.5-1.0h-1, the ratio of gas phase air speed and liquid phase air speed is 1-3.
In the fixed bed reactors in nitrogen and nitrate aqueous solution, nitrite aqueous solution or diluted nitric acid aqueous solution
It is one or more to pass through catalyst bed in a manner of any in cocurrent, cross-flow or adverse current, preferably in manner of cocurrent flow by urging
Agent bed.
Using above-mentioned technical solution, have the following technical effect that:
The method that nitrate is catalytically decomposed in the present invention is simple, and strong operability is at low cost, using being mixed with active powdered carbon
ZSM-5 molecular sieve catalyst, without additionally introducing reducing agent；Meanwhile the method for catalytic decomposition nitrate of the invention is utilized
Discarded ZSM-5 molecular sieve extends the processing means of dangerous waste object, also saves the expense of processing dangerous waste.
The method reaction temperature that nitrate is catalytically decomposed in the present invention is low, and pressure is low, is catalyzed the condition temperature of reduction decomposition process
With, it is easy to accomplish.
Specific embodiment
In order to better understand the present invention, below with reference to the embodiment content that the present invention is furture elucidated.
It is detected in following each examples using following methods:
(1) method of nitric acid maximum conversion is detected are as follows: XNO3=(1-CNO3/C°NO3)
Wherein, C °NO3And CNO3The respectively measurement of nitrate flows in and out molar concentration；
When the conversion ratio of nitric acid is less than 75%, stopping experiment, highest conversion ratio is the highest of nitric acid during reaction
Conversion ratio；
(2) method of nitric acid average conversion is detected are as follows: when the conversion ratio of nitric acid is less than 75%, stopping experiment being reacted
The average value of period conversion ratio is the maximum conversion of nitric acid；
Following each example Instrumental equipment and raw material sources information:
(1) fixed bed reactors: Beijing Bo Luming Science and Technology Ltd.；
(2) banded extruder: South China Science & Engineering University's science and technology industry head factory, model: the multi-functional kneading banded extruder of CD4-1TS type；
(3) methylcellulose: Zhengzhou feudal dynasty chemical products Co., Ltd, onychostroma content are 26%-33%；
(4) polyethylene glycol: Hubei Ju Sheng Science and Technology Ltd., model: capacitor stage；
(5) cocoanut active charcoal: Shuan Hui active carbon company, model: top grade product；
(6) coaly activated carbon: Ningxia Heng Hui active carbon Co., Ltd, model: HCP-200.
(7) discard ZSM-5 molecular sieve powder: operation is drawn off after 7-14 days in preparing propylene from methanol commercial plant (MTP device)
ZSM-5 molecular sieve catalyst, and pass through simple purge.
Embodiment 1
(1) the 80g ZSM-5 molecular sieve discarded roast at 550 DEG C 5h, be ground to partial size to obtain after 200 mesh
HZSM-5 molecular sieve powder；
It (2) is the boehmite powder and 20g of 200 mesh by the partial size of above-mentioned 80gHZSM-5 molecular sieve powder, 5.2g
Partial size be 200 mesh, the coaly activated carbon powder that content of ashes is 15% is stirred continuously uniformly in banded extruder loading hopper；So
Afterwards, concentrated nitric acid solution, 6g methylcellulose, 2g polyethylene glycol that 9.52g mass fraction is 63% are added in 40g water, constantly
It is slowly added under conditions of stirring into the mixture of above-mentioned HZSM-5 molecular sieve powder, is squeezed after promoting material to be kneaded into plastic body
Item molding, in 120 DEG C of at a temperature of drying 8h, by the catalyst after drying, 500 DEG C of roasting 6h are stand-by in Muffle furnace.
Embodiment 2
(1) by 80g discard ZSM-5 molecular sieve powder at 550 DEG C roast 3h, be ground to partial size be 100 mesh after, obtain
To HZSM-5 molecular sieve powder；
It (2) is the boehmite powder and 20g of 200 mesh by the partial size of above-mentioned 80gHZSM-5 molecular sieve powder, 5.2g
The coconut activated carbon powder that partial size is 200 mesh, content of ashes is 15% is stirred continuously uniformly in banded extruder loading hopper；Then,
By 9.52g mass fraction be 63% concentrated nitric acid solution, 6g methylcellulose, 7.21g Fe(NO3)39H2O, 1.89g copper nitrate,
2g polyethylene glycol is added in 40g water, is slowly added in the mixture of above-mentioned HZSM-5 molecular sieve powder under conditions of being stirred continuously,
Extruded moulding after promoting material to be kneaded into plastic body, the dry 8h at 120 DEG C, by the catalyst after drying 500 in Muffle furnace
DEG C roasting 6h it is stand-by.
Embodiment 3
(1) by 80gZSM-5 molecular sieve powder at 550 DEG C roast 5h, be ground to partial size be 200 mesh after, obtain
HZSM-5 molecular sieve powder；
It (2) is the boehmite powder and 20g of 200 mesh by the partial size of above-mentioned 40gHZSM-5 molecular sieve powder, 5.2g
The coconut activated carbon powder that partial size is 200 mesh, content of ashes is 15% is stirred continuously uniformly in banded extruder loading hopper；Then,
By 9.52g mass fraction be 63% concentrated nitric acid solution, 6g methylcellulose, 7.21g Fe(NO3)39H2O, 1.89g copper nitrate,
0.49g nickel nitrate, 2g polyethylene glycol are added in 40g water, and above-mentioned HZSM-5 molecular sieve powder is slowly added under conditions of being stirred continuously
In the mixture at end, extruded moulding after promoting material to be kneaded into plastic body, the dry 8h at 120 DEG C, by the catalyst after drying
500 DEG C of roasting 6h are stand-by in Muffle furnace.
Embodiment 4
By the catalyst filling prepared in 1g embodiment 1 in the catalyst bed of fixed bed reactors, by reaction temperature
90 DEG C are warming up to, N is led to2It purges and controls reaction pressure in 0.25Mpa, introduce quality point into reactor by Micro-metering Pumps
The diluted nitric acid aqueous solution that number is 1%, two strands of raw materials of gas, liquid pass through catalyst bed in manner of cocurrent flow, control
Liquid phase air speed 0.75h-1, the ratio of gas phase air speed and liquid phase air speed is 2, is catalyzed reduction decomposition diluted nitric acid aqueous solution.Through detecting, nitre
Sour maximum conversion 93.75%, average conversion 81.85%.
Embodiment 5
By the catalyst filling prepared in 1g embodiment 2 in the catalyst bed of fixed bed reactors, by reaction temperature
90 DEG C are risen to, N is passed through2Purging and controlling reaction pressure is 0.25Mpa, introduces quality point into reactor by Micro-metering Pumps
The diluted nitric acid aqueous solution that number is 1%, two strands of raw materials of gas, liquid pass through catalyst bed in manner of cocurrent flow, control
Liquid phase air speed is 0.75h-1, the ratio of gas phase air speed and liquid phase air speed is 3, is catalyzed reduction decomposition diluted nitric acid aqueous solution.Through detecting,
Nitric acid maximum conversion is 91.92%, average conversion 82.77%.
Embodiment 6
By the catalyst filling being prepared in 1g embodiment 3 in fixed bed reactors, and using same as Example 5
Reaction condition under, the performance for preparing catalyst is evaluated, through detecting, the maximum conversion 92.48% of nitric acid is average to turn
Rate 84.82%.
Embodiment 7
By the catalyst filling prepared in 1g embodiment 1 in fixed bed reactors, reaction temperature is warming up to 90 DEG C, is led to
N2It purges and controls reaction pressure in 0.25Mpa, introduce the nitre that mass fraction is 1.1% into reactor by Micro-metering Pumps
Acid salt aqueous solution, two strands of raw materials of gas, liquid pass through catalyst bed in manner of cocurrent flow, control liquid phase air speed
0.75h-1, the ratio of gas phase air speed and liquid phase air speed is 2, is catalyzed reduction decomposition dust technology.Through detecting, nitrate maximum conversion
91.0%, average conversion 82%.
Embodiment 8
By the catalyst filling prepared in 1g embodiment 2 in fixed bed reactors, and using same as Example 7 anti-
Under the conditions of answering, the performance for preparing catalyst is evaluated.Through detecting, nitrate maximum conversion is 90.1%, average transformation
Rate is 81.1%.
Embodiment 9
By the catalyst filling being prepared in 1g embodiment 3 in fixed bed reactors, and using same as Example 7
Reaction condition under, the performance for preparing catalyst is evaluated, through detecting, the maximum conversion 92.1% of nitrate is average
Conversion ratio 83.0%.
Embodiment 10
By the catalyst filling prepared in 1g embodiment 1 in fixed bed reactors, reaction temperature is warming up to 90 DEG C, is led to
N2It purges and controls reaction pressure in 0.25Mpa, introduce the Asia that mass fraction is 1.5% into reactor by Micro-metering Pumps
Nitrate aqueous solution, two strands of raw materials of gas, liquid pass through catalyst bed in manner of cocurrent flow, control liquid phase air speed
0.75h-1, the ratio of gas phase air speed and liquid phase air speed is 2, is catalyzed reduction decomposition dust technology.Through detecting, nitrate maximum conversion
91.8%, average conversion 82.8%.
Claims (10)
1. a kind of for being catalyzed reduction nitrate, nitrite or the method for preparing catalyst of dust technology, which is characterized in that including
Following steps:
(1) by after ZSM-5 molecular sieve roasting, grinding, HZSM-5 molecular sieve powder is obtained；
(2) obtained HZSM-5 molecular sieve powder is stirred and evenly mixed and is formed with additive, roasting obtains catalyst after drying；
The additive includes active carbon powder, and the mass ratio of the HZSM-5 molecular sieve powder and active carbon powder is 2.0:
0.5-2.0:4.0.
2. preparation method according to claim 1, it is characterised in that: additive described in step (2) further includes that molding is viscous
Tie agent, auxiliary agent, peptizing agent and water, the HZSM-5 molecular sieve powder of addition and the active carbon powder, help molding adhesive
The mass ratio of agent, water and peptizing agent is 2.0:0.5-0.4:0.12-0.15:0.15-0.25:1:0.2-0.25.
3. preparation method according to claim 1 or 2, it is characterised in that: the active carbon powder is selected from wood activated charcoal
One of powder, coconut husk, shell or coaly activated carbon powder are a variety of；
Preferably, the coaly activated carbon that the active carbon powder is partial size 200-400 mesh, ash content mass content is 15%-20%
Powder；
Preferably, the active carbon powder is selected from coconut husk or active fruit shell carbon, and metal active is added in active carbon powder
Component, the quality of the metal active constituent are the 0.1-1% of the HZSM-5 molecular sieve powder quality；
It is further preferred that the metal active constituent is metal salt；Metallic element in the metal salt is selected from the VIIIth race
One of metallic element, I B-group metal element are a variety of, further preferably one or both of iron or copper.
4. preparation method according to claim 2, it is characterised in that: the molding adhesive be selected from boehmite,
One of SB powder, kaolin or bentonite are a variety of, preferably boehmite；
The auxiliary agent is selected from one of methylcellulose, sesbania powder, glycerol or polyethylene glycol or a variety of, and preferably methyl is fine
Dimension element；
The peptizing agent is one of concentrated nitric acid solution, acetic acid solution or citric acid solution, preferably concentrated nitric acid solution；Into
One step is preferred, and the mass concentration of the peptizing agent is 60-70%.
5. preparation method according to claim 1-4, it is characterised in that: ZSM-5 molecular sieve described in step (1)
For the discarded ZSM-5 molecular sieve catalyst drawn off on MTP commercial plant.
6. preparation method according to claim 1-5, it is characterised in that: carry out the roasting in step (1)
Temperature is 500-600 DEG C, described to be ground to for the ZSM-5 molecular sieve to be ground to partial size to be 100-200 mesh；In step (2)
In 300-500 DEG C of roasting temperature 2-12h after dry 8-10h at 120 DEG C.
7. the molecular sieve catalyst of a kind of catalytic decomposition nitrate, nitrite or dust technology, it is characterised in that: wanted using right
The described in any item methods of 1-6 are asked to be prepared.
8. a kind of method of catalytic decomposition nitrate, nitrite or dust technology, it is characterised in that: under nitrogen atmosphere, in fixation
By one of nitrate aqueous solution, nitrite aqueous solution or diluted nitric acid aqueous solution or a variety of pass through catalyst in bed reactor
Bed carries out catalytic reduction reaction, is filled with molecular sieve catalyst as claimed in claim 7 in the catalyst bed.
9. according to the method described in claim 8, it is characterized by: the reaction temperature of the fixed bed reactors is 60-120
DEG C, reaction pressure 0.20-0.30Mpa, liquid phase air speed is 0.3-1.5h-1, the ratio of gas phase air speed and liquid phase air speed is 1-5,
The mass fraction of nitrate is 0.1-2% in the nitrate aqueous solution, the matter of nitrite in the nitrite aqueous solution
Amount score is 0.1-2%, and the mass fraction of nitric acid is 0.1-2% in the diluted nitric acid aqueous solution；
Preferably, the temperature of the fixed bed reactors is 80-100 DEG C, reaction pressure 0.25-0.30Mpa, and liquid phase air speed is
0.5-1.0h-1, the ratio of gas phase air speed and liquid phase air speed is 1-3.
10. method according to claim 8 or claim 9, it is characterised in that: nitrogen and nitric acid salt water in the fixed bed reactors
One of solution, nitrite aqueous solution or diluted nitric acid aqueous solution are a variety of in a manner of any in cocurrent, cross-flow or adverse current
By catalyst bed, preferably pass through catalyst bed in manner of cocurrent flow.
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