CN108067299A - A kind of method that SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template - Google Patents
A kind of method that SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template Download PDFInfo
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- CN108067299A CN108067299A CN201611023926.8A CN201611023926A CN108067299A CN 108067299 A CN108067299 A CN 108067299A CN 201611023926 A CN201611023926 A CN 201611023926A CN 108067299 A CN108067299 A CN 108067299A
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- ammonium hydroxide
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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
- B01J29/7003—A-type
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- 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
- 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
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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Abstract
The present invention relates to a kind of methods that SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template, template tetraethyl ammonium hydroxide (TEA) is mixed with NaOH first, it incorporates in suitable water and obtains mixed solution, then added in LTA molecular sieves as silicon source and silicon source in mixed solution, lasting stirring is until obtaining homogeneous gel；Gel is transferred in autoclave, for a period of time, room temperature cools down crystallization after the completion of crystallization, and solid product is recovered by filtration, and is washed with deionized, dry at a certain temperature, roasts to get to SCR catalyst.Template used is not only cheap, and alleviates the pollution to environment；Thus the small pore molecular sieve catalyst further prepared not only has excellent NH3SCR activity, and solid phase yield is high, greatly reduces production cost.
Description
Technical field
The invention belongs to catalyst technical field, more particularly to one kind is synthesized using tetraethyl ammonium hydroxide as template
The method of SCR catalyst.
Background technology
NH3- SCR (Selective Catalytic Reduction, SCR) technology is at present in the world using the widest
General NOx removal technology, principle are with NH3It is harmless N by NOx selective catalytic reduction as reducing agent2And it discharges.
The key of SCR technology is to develop the catalyst system of efficient stable, to adapt to the various application environments such as diesel vehicle, steamer, industry.
At present, the NH of industrial applications3- SCR catalyst is mainly V2O5-WO3(MoO3)/TiO2Catalyst.The catalyst extensively should
For stationary source coal-fired flue gas denitration, and have been incorporated into exhaust gas from diesel vehicle control field.But there are still one for the catalyst
Itself it can not overcome the problems, such as a bit, for example, operation temperature window is relatively narrow, high high-temp stability is poor and the easy a large amount of N of generation2O and make
Into N2Selectivity reduces.
In recent years, the catalyst with porous structure is since catalytic activity is high, N2Selective good, excellent heat stability resists
The advantages that HCs poisoning capabilities are strong and receive significant attention.In order to reduce production cost, researchers have carried out a series of researchs,
Explore template cheap and easy to get.Research find benzyl trimethyl amine (BTMA), N- alkyl -1,4- diazabicyclooctane sun from
Son, multi-ring alkyl amine cation, N, N- lupetidines and choline chloride for finding recently etc. can serve as single template
Synthesize SCR catalyst, but all there is the problems such as expensive or solid phase low yield for these templates.Therefore, valency is developed
The new type formwork agent that lattice are cheap, solid phase yield is high, has very important significance for its large-scale promotion application.
The content of the invention
For the deficiencies in the prior art, the present invention provides one kind using tetraethyl ammonium hydroxide (TEA) as template
The method that agent synthesizes SCR catalyst, template used is not only cheap, and alleviates the pollution to environment.
Realize the object of the invention technical solution be：
A kind of method that SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template, it is characterised in that：Including following
Step：
(1) tetraethyl ammonium hydroxide with NaOH is mixed, add in suitable water, obtain mixed solution；Then by LTA molecules
Sieve is added in above-mentioned mixed solution, and lasting stirring is until obtaining homogeneous gel；
(2) gel being transferred in reaction kettle, crystallization, crystallization completes postcooling, and solid product is recovered by filtration, washing,
It is dry, roast to get to SCR catalyst.
Moreover, the silica alumina ratio of the LTA molecular sieves is 1~20.
Moreover, the molar ratio of the tetraethyl ammonium hydroxide and NaOH are 0.2~1.
Moreover, H2O is 10~40 with NaOH molar ratios.
Moreover, the crystallization temperature is 100~170 DEG C.
Moreover, the crystallization time is 1~7 day.
Moreover, the calcination temperature is 500~600 DEG C.
Compared with prior art, the present invention has the following advantages and protrude effect：
1st, the present invention uses nontoxic and cheap TEA as template, so as to alleviate the pollution to environment, and with tetrem
Base ammonium hydroxide as template instead of expensive N, N, N- trimethyl adamantane ammonium hydroxide (TMAdA) template, significantly
Production cost is reduced, which has great role in terms of reducing production cost and improving molecular sieve crystallinity.
2nd, a small amount of water has only been used in preparation process of the present invention, thus the production of a large amount of waste water can be avoided in production process significantly
It is raw.
3rd, the SCR catalyst crystallinity and solid phase yield that the present invention synthesizes are all very high, are conducive to promote and apply on a large scale.
The SCR catalyst excellent heat stability synthesized by the present invention, catalytic activity are high.
Specific embodiment
The detailed content of the present invention is told about by the following examples, and it is the convenience for understanding to provide embodiment, is definitely not
The limitation present invention.
Embodiment one：SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template, step is as follows：
First, 16.8296g templates tetraethyl ammonium hydroxide (TEAOH, 35wt%) and 1.6004g NaOH solids are mixed
It closes；Then, the commercially available LTA of 12.9874g is taken to be added in mixture and are used as silicon source and silicon source；Lasting stirring is until obtaining homogeneous
Gel；
Gel is transferred in stainless steel, the autoclave with teflon lined, in a static condition,
160 DEG C of hydrothermal crystallizings 3 days；The gel proportions of the system are：SiO2/0.033 Al2O3/0.2 TEAOH/0.2 NaOH/5 H2O。
It treats after reaction, product is filtered, is then washed with deionized by room temperature cooling, and the dry 12h at 100 DEG C, finally,
55 DEG C of roasting temperature 5h in air, finally obtain SCR catalyst.
Embodiment two：Using tetraethyl ammonium hydroxide as template synthesize SCR catalyst, basic step as in the first embodiment,
Simply crystallization condition is crystallization 3 days at 140 DEG C, finally obtains SCR catalyst.
Embodiment three：Using tetraethyl ammonium hydroxide as template synthesize SCR catalyst, basic step as in the first embodiment,
Simply crystallization condition is crystallization 4 days at 160 DEG C, finally obtains SCR catalyst.
Example IV：Using tetraethyl ammonium hydroxide as template synthesize SCR catalyst, basic step as in the first embodiment,
The LTA the present embodiment for being intended only as silicon source and silicon source selects AV-20, molar ratio SiO2/Al2O3=6 finally obtain SCR catalyst.
To sum up, crystallization temperature and crystallization time all have an impact grain size and crystallinity, the purity of synthesis.Improve crystallization
Temperature and extension crystallization time are conducive to the generation of SCR catalyst；When crystallization temperature is 150 DEG C, and crystallization time is 6 days,
Epigranular, the SCR catalyst of high-purity can be synthesized.
The invention is not limited in above-mentioned specific embodiment, above-mentioned specific embodiment is only schematical,
Rather than it is restricted, those of ordinary skill in the art are not departing from the situation of present inventive concept under the enlightenment of the present invention
Under, many variations can also be made, these are belonged within the protection of the present invention.
Claims (7)
- A kind of 1. method that SCR catalyst is synthesized using tetraethyl ammonium hydroxide as template, it is characterised in that：Including following step Suddenly：(1) tetraethyl ammonium hydroxide with NaOH is mixed, add in suitable water, obtain mixed solution；Then LTA molecular sieves are added Enter into above-mentioned mixed solution, lasting stirring is until obtaining homogeneous gel；(2) gel is transferred in reaction kettle, crystallization, crystallization completes postcooling, and solid product is recovered by filtration, washes, does Dry, roasting is to get to SCR catalyst.
- 2. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：The silica alumina ratio of the LTA molecular sieves is 1~20.
- 3. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：The molar ratio of the tetraethyl ammonium hydroxide and NaOH are 0.2~1.
- 4. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：H2O is 10~40 with NaOH molar ratios.
- 5. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：The crystallization temperature is 100~170 DEG C.
- 6. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：The crystallization time is 1~7 day.
- 7. synthesizing the method for SCR catalyst using tetraethyl ammonium hydroxide as template according to claim 1, feature exists In：The calcination temperature is 500~600 DEG C.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419477A (en) * | 2000-04-26 | 2003-05-21 | 埃克森美孚化学专利公司 | Rejuvenating SAPO and/or ALPO molecular sieve with anhydrous liquid or vapor |
| CN104028299A (en) * | 2014-06-19 | 2014-09-10 | 中国石油大学(北京) | Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof |
| CN105236440A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent |
| CN105312083A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum-phosphorous molecular sieves, and preparation methods and applications thereof |
| CN105833899A (en) * | 2016-04-28 | 2016-08-10 | 浙江弗沙朗能源股份有限公司 | Preparation method for SCR catalyst for purifying oxynitride in motor vehicle exhaust |
| CN105879904A (en) * | 2016-04-28 | 2016-08-24 | 浙江弗沙朗能源股份有限公司 | Preparation method of SCR catalyst |
-
2016
- 2016-11-14 CN CN201611023926.8A patent/CN108067299A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419477A (en) * | 2000-04-26 | 2003-05-21 | 埃克森美孚化学专利公司 | Rejuvenating SAPO and/or ALPO molecular sieve with anhydrous liquid or vapor |
| CN104028299A (en) * | 2014-06-19 | 2014-09-10 | 中国石油大学(北京) | Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof |
| CN105312083A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum-phosphorous molecular sieves, and preparation methods and applications thereof |
| CN105236440A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent |
| CN105833899A (en) * | 2016-04-28 | 2016-08-10 | 浙江弗沙朗能源股份有限公司 | Preparation method for SCR catalyst for purifying oxynitride in motor vehicle exhaust |
| CN105879904A (en) * | 2016-04-28 | 2016-08-24 | 浙江弗沙朗能源股份有限公司 | Preparation method of SCR catalyst |
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Application publication date: 20180525 |