CN109433255A - Remove the preparation method of the catalyst of NOx - Google Patents
Remove the preparation method of the catalyst of NOx Download PDFInfo
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- CN109433255A CN109433255A CN201811623580.4A CN201811623580A CN109433255A CN 109433255 A CN109433255 A CN 109433255A CN 201811623580 A CN201811623580 A CN 201811623580A CN 109433255 A CN109433255 A CN 109433255A
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- catalyst
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- nox
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
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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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/082—Decomposition and pyrolysis
Abstract
The present invention relates to a kind of preparation methods of catalyst for removing NOx, belong to catalyst preparation technical field.Carrier, is then statically placed in salting liquid and impregnates by preparing metal salting liquid first, is drawn off processing drying, the molecular screen material slurry that synergistic effect is played with metal salt is coated on carrier again, carrier after coating is dried into ageing, is finally baked to roast to get the catalyst of NOx is arrived.The catalyst of removal NOx is prepared using the method for the present invention, preparation process is simple to operation, economizes on resources, and active component content is easier to control.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst for removing NOx, belong to catalyst preparation technical field.
Background technique
Molecular sieve removal NOx catalyst is hot spot studied both at home and abroad at present, molecular sieve due to its have catalysis window it is wide,
Low temperature active is high, thermal stability is high, acidity is strong, will not generate the features such as secondary pollution, is widely regarded as having excellent removal
NOx catalysis characteristics, environmental-friendly new waste gas handle catalyst material.There are countries and regions strong in Europe and America
System is using molecular sieve as vehicle exhaust post-processing catalyst.
The technical process of current molecular sieve SCR catalyst is first will in such a way that wet process exchanges by active metal component
It is introduced into molecular sieve pore passage, is then again being coated on the system with molecular sieve for preparing containing metal on carrier at slurry, prepared composition
Son sieve SCR catalyst.Wet process exchange therein, not only process is tedious, and the time is long, generates a large amount of waste water, and waste water resource
And generate environmental protection pressure.
Summary of the invention
It the purpose of the present invention is overcoming above-mentioned shortcoming, provides a kind of simple to operation, economizes on resources, active component contains
Measure the preparation method of the catalyst of removal NOx easier to control.
Technical solution of the present invention removes the preparation method of the catalyst of NOx, and steps are as follows: preparing metal salting liquid, so
Carrier is statically placed in salting liquid afterwards and is impregnated, processing drying is drawn off, then coating and metal salt synergistic effect on carrier
Molecular screen material slurry, the carrier after coating is dried into ageing, is finally baked to roast to get the catalyst of NOx is arrived.
Further, the metal in the metal salt is specially one or more of Cu, Fe, Co, Ni, Ce, Ag, Mn.
Mantoquita in the metal salt is specially copper nitrate or copper acetate；
Molysite in the metal salt is specially ferric nitrate, iron chloride or ferric sulfate；
Cobalt salt in the metal salt is specially cobalt chloride or cobaltous sulfate；
Nickel salt in the metal salt is specially nickel nitrate or nickel acetate；
Cerium salt in the metal salt is specially cerous nitrate or cerous acetate；
Silver salt in the metal salt is specially silver nitrate；
Manganese salt in the metal salt is specially manganese nitrate or manganese acetate.
Further, the concentration of the metal salt solution is 0.01-1mol/L.
Further, the carrier is specially the carrier of wall-flow type and through type unlike material；
Preferably, material specifically includes cordierite, silicon carbide, aluminium titanates and fiber.
Further, the drying temperature after the impregnating metal salting liquid is 50-80 DEG C, drying time 0.5-2h.
Further, the molecular screen material is specially one of BEA, CHA, MFI, LTA, AEI, AFX, FAU or several
Kind；
Preferably, the molecular screen material is specially octatomic ring small pore molecular sieve.
Further, the amount of metal of the carrier impregnation is the 1.5% ~ 4% of the molecular sieve dry weight of subsequent coated.
Further, the carrier after the coating keeps being aged 1 ~ 8h under 0% ~ 50% drying rate.
Further, the temperature of the drying roasting is 450-600 DEG C, time 1-3h.
Beneficial effects of the present invention: preparing the catalyst of removal NOx using the method for the present invention, and preparation process simply easily grasps
Make, economizes on resources, active component content is easier to control.
Detailed description of the invention
Fig. 1 embodiment 1-3 and comparative example 1 remove NOx ratio compared with result figure.
Fig. 2 embodiment 4-6 and comparative example 2 remove NOx ratio compared with result figure.
Specific embodiment
Embodiment 1
It will be stood in 0.01mol/L copper nitrate solution that violet cyanines stone carrier is placed in, the amount of metal of carrier impregnation is subsequent coated
Molecular sieve dry weight 1.5%.Being then taken out in drying temperature is 50 DEG C, drying time 2h.It is again that configuration adjustment is good
CHA type molecular sieve slurry coating carrier after the drying on, by the carrier after coating keep drying rate be 0% it is lower be aged 1h, most
After be baked to maturing temperature be 450 DEG C, the time be 3h obtain sample 1.
Embodiment 2
It will be stood in 0.5mol/L copper acetate solution that metatitanic acid alumina supporter is placed in, the amount of metal of carrier impregnation is subsequent coated
The 2% of molecular sieve dry weight.Being then taken out in drying temperature is 65 DEG C, drying time 1h.It is again that configuration adjustment is good
On the carrier of CHA type molecular sieve slurry coating after the drying, it is 25% lower ageing 4h that the carrier after coating, which is kept drying rate, most
After be baked to maturing temperature be 500 DEG C, the time be 2h obtain sample 2.
Embodiment 3
It will be stood in 1mol/L copper-bath that Carboround is placed in, the amount of metal of carrier impregnation is point of subsequent coated
The 4% of son sieve dry weight.Being then taken out in drying temperature is 80 DEG C, drying time 0.5h.It is again that configuration adjustment is good
On the carrier of CHA type molecular sieve slurry coating after the drying, it is 50% lower ageing 8h that the carrier after coating, which is kept drying rate, most
After be baked to maturing temperature be 600 DEG C, the time be 1h obtain sample 3.
Embodiment 4
It will be stood in 0.01mol/L iron nitrate solution that violet cyanines stone carrier is placed in, the amount of metal of carrier impregnation is subsequent coated
Molecular sieve dry weight 1.5%.Being then taken out in drying temperature is 50 DEG C, drying time 2h.It is again that configuration adjustment is good
MFI-type molecular sieve slurry coating carrier after the drying on, by the carrier after coating keep drying rate be 0% it is lower be aged 1h, most
After be baked to maturing temperature be 450 DEG C, the time be 3h obtain sample 4.
Embodiment 5
It will be stood in 0.5mol/L ferric chloride solution that metatitanic acid alumina supporter is placed in, the amount of metal of carrier impregnation is subsequent coated
The 2% of molecular sieve dry weight.Being then taken out in drying temperature is 65 DEG C, drying time 1h.It is again that configuration adjustment is good
On the carrier of MFI-type molecular sieve slurry coating after the drying, it is 25% lower ageing 4h that the carrier after coating, which is kept drying rate, most
After be baked to maturing temperature be 500 DEG C, the time be 1h obtain sample 5.
Embodiment 6
It will be stood in 1mol/L ferrum sulfuricum oxydatum solutum that Carboround is placed in, the amount of metal of carrier impregnation is point of subsequent coated
The 4% of son sieve dry weight.Being then taken out in drying temperature is 80 DEG C, drying time 0.5h.It is again that configuration adjustment is good
On the carrier of MFI-type molecular sieve slurry coating after the drying, it is 50% lower ageing 8h that the carrier after coating, which is kept drying rate, most
After be baked to maturing temperature be 600 DEG C, the time be 1h obtain sample 6.
Comparative example 1
Resulting copper content about 2%CHA type molecular sieve will be exchanged by wet process, according to identical Process configuration and regulate slurry,
It is coated on carrier, roasting is then baked to and obtains contrast sample 1.
Embodiment 1-3 and the removal NOx ratio of comparative example 1 are as shown in Figure 1 compared with result figure.
Comparative example 2
Resulting iron content about 2%MFI type molecular sieve will be exchanged by wet process, according to identical Process configuration and regulate slurry,
It is coated on carrier, roasting is then baked to and obtains contrast sample 2.
Embodiment 4-6 and the removal NOx ratio of comparative example 2 are as shown in Figure 2 compared with result figure.
Claims (10)
1. the preparation method of the catalyst of NOx is removed, it is characterized in that steps are as follows: preparing metal salting liquid, it is then that carrier is quiet
It is placed in salting liquid and impregnates, be drawn off processing drying, then coat the molecular sieve material for playing synergistic effect with metal salt on carrier
Carrier after coating is dried ageing by slurry body, is finally baked to roast to get the catalyst of NOx is arrived.
2. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the metal in the metal salt has
Body is one or more of Cu, Fe, Co, Ni, Ce, Ag, Mn.
3. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that:
Mantoquita in the metal salt is specially copper nitrate or copper acetate；
Molysite in the metal salt is specially ferric nitrate, iron chloride or ferric sulfate；
Cobalt salt in the metal salt is specially cobalt chloride or cobaltous sulfate；
Nickel salt in the metal salt is specially nickel nitrate or nickel acetate；
Cerium salt in the metal salt is specially cerous nitrate or cerous acetate；
Silver salt in the metal salt is specially silver nitrate；
Manganese salt in the metal salt is specially manganese nitrate or manganese acetate.
4. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the concentration of the metal salt solution
For 0.01-1mol/L.
5. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the carrier is specially wall-flow type
With the carrier of through type unlike material；
Preferably, material specifically includes cordierite, silicon carbide, aluminium titanates and fiber.
6. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: after the impregnating metal salting liquid
Drying temperature be 50-80 DEG C, drying time 0.5-2h.
7. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the molecular screen material is specially
One or more of BEA, CHA, MFI, LTA, AEI, AFX, FAU；
Preferably, the molecular screen material is specially octatomic ring small pore molecular sieve.
8. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the amount of metal of the carrier impregnation
It is the 1.5% ~ 4% of the molecular sieve dry weight of subsequent coated.
9. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the carrier after the coating is kept
1 ~ 8h is aged under 0% ~ 50% drying rate.
10. the preparation method of the catalyst of removal NOx as described in claim 1, it is characterized in that: the temperature of the drying roasting is
450-600 DEG C, time 1-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811623580.4A CN109433255B (en) | 2018-12-28 | 2018-12-28 | Method for preparing NOx removal catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811623580.4A CN109433255B (en) | 2018-12-28 | 2018-12-28 | Method for preparing NOx removal catalyst |
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| CN109433255A true CN109433255A (en) | 2019-03-08 |
| CN109433255B CN109433255B (en) | 2022-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811623580.4A Active CN109433255B (en) | 2018-12-28 | 2018-12-28 | Method for preparing NOx removal catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548537A (en) * | 2019-06-25 | 2019-12-10 | 无锡威孚环保催化剂有限公司 | Preparation method of molecular sieve catalyst for removing nitrogen oxides |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869427A (en) * | 2010-03-11 | 2013-01-09 | 约翰逊马西有限公司 | Disordered molecular sieve supports for the selective catalytic reduction of nox |
| CN102950008A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN105413740A (en) * | 2015-11-06 | 2016-03-23 | 无锡威孚环保催化剂有限公司 | High-efficiency Fe-SCR integrated catalyst preparation method |
| CN107824217A (en) * | 2017-10-19 | 2018-03-23 | 中国汽车技术研究中心 | The preparation method of coating slurry and the preparation method of coating type Cu molecular sieve SCR catalysts |
-
2018
- 2018-12-28 CN CN201811623580.4A patent/CN109433255B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869427A (en) * | 2010-03-11 | 2013-01-09 | 约翰逊马西有限公司 | Disordered molecular sieve supports for the selective catalytic reduction of nox |
| CN102950008A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN105413740A (en) * | 2015-11-06 | 2016-03-23 | 无锡威孚环保催化剂有限公司 | High-efficiency Fe-SCR integrated catalyst preparation method |
| CN107824217A (en) * | 2017-10-19 | 2018-03-23 | 中国汽车技术研究中心 | The preparation method of coating slurry and the preparation method of coating type Cu molecular sieve SCR catalysts |
Non-Patent Citations (2)
| Title |
|---|
| 全国勘察设计注册工程师环保专业管理委员会、中国环境保护产业协会: "《注册环保工程师专业考试复习教材（第四版）大气污染防治工程技术与实践（上册）》", 31 March 2017, 中国环境出版社 * |
| 吴峰: "《环境化学实验》", 31 August 2014, 武汉大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548537A (en) * | 2019-06-25 | 2019-12-10 | 无锡威孚环保催化剂有限公司 | Preparation method of molecular sieve catalyst for removing nitrogen oxides |
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| CN109433255B (en) | 2022-03-18 |
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