CN105435777A - Preparation method for low-temperature catalyst applied to SCR (Selective Catalyst Reduction) - Google Patents
Preparation method for low-temperature catalyst applied to SCR (Selective Catalyst Reduction) Download PDFInfo
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- CN105435777A CN105435777A CN201410462780.1A CN201410462780A CN105435777A CN 105435777 A CN105435777 A CN 105435777A CN 201410462780 A CN201410462780 A CN 201410462780A CN 105435777 A CN105435777 A CN 105435777A
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Abstract
The invention provides a preparation method for a low-temperature catalyst applied to SCR (Selective Catalyst Reduction). The preparation method comprises the following steps: (1) mixing 28-35 parts of a metal modification solution, 15-35 parts of an ammonium metavanadate solution and 100-120 parts of a carrier slurry, also adding 4-7 parts of pore-forming fiber cotton, uniformly stirring at a constant temperature and removing water through steaming at the same time, and stopping stirring when the water content reduces to 30-32%; 2) putting a uniform bulk substance obtained in the step 2) in a constant-temperature enclosed container, standing for 18-24 h, and then putting in a vacuum extruder for molding; 3) putting the extrusion molded substance in a drying box, and drying at 50-70 DEG C for 100-120 h; and 4) calcining the dried product at 150-500 DEG C for 20-25 h, so as to obtain the final product. When the flue-gas temperature is 110 DEG C-230 DEG C, the catalyst prepared by employing the above preparation method for the low-temperature catalyst applied to SCR possesses the characteristics of high activity, sulfur resistance, good waterproof performance, high mechanical strength and the like.
Description
Technical field
The present invention relates to selective catalysis and transform SCR (SelectiveCatalystReduction) technology, particularly relate to a kind of low temperature catalyst preparation method for SCR.
Background technology
Along with the aggravation of environmental pollution, country is more and more tighter to the control of discharged nitrous oxides, the amount that stationary source based on coal-burning boiler discharges nitrogen oxide in air can obtain more and more stricter control, and the simple low-NO_x combustion technology that relies on cannot meet strict discharge standard.
Now most widely used is High-temperature scr catalyst, and temperature range, between 300 DEG C-420 DEG C, in thermal power plant's application, generally can only be selected high dirt to arrange, namely be arranged between boiler economizer and air preheater.On this position, catalyst has higher activity and anti-poisoning performance, but residing flue gas environmental condition is more severe, dust and heavy metal concentration high, wash away relatively serious to catalyst, catalyst is also poisoning than being easier to, blocking, this substantially reduces the service life of catalyst.If after catalyst is arranged on deduster, before desulfurizer, i.e. low dirt arrangement, in flue gas now, dust and content of beary metal reduce greatly, and catalyst decreases wearing and tearing, the danger of blocking, add catalyst service life.But the low dirt of catalyst is arranged and is required very high to the low temperature active of catalyst, and under low dirt arrangement condition, flue-gas temperature is generally between 110-230 DEG C, and this temperature range, traditional High-temperature scr catalyst does not almost have activity.
The low temperature catalyst of current commercial Application does not almost have, domestic and international researcher has also carried out a series of research, the most resistance to SO_2 of a small amount of low-temperature SCR catalyst developed and water repelling property poor, industrial requirement can not be met, therefore, the low-temperature SCR catalyst being applicable to thermal power plant and Industrial Stoves is researched and developed significant.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of low temperature catalyst preparation method for SCR.It has active high between flue-gas temperature 110 DEG C-230 DEG C, and sulfur resistive, water repelling property is good, mechanical strength high, to solve the catalyst Problems existing for SCR in prior art.
For a low temperature catalyst preparation method of SCR, it comprises the following steps:
1) by 28 ~ 35 parts of metal-modified solution, 15 ~ 35 parts of ammonium metavanadate solutions and 100 ~ 120 parts of carrier paste mixing constant temperature uniform stirrings, add the pore-creating cellucotton of 4-7 part simultaneously, boil off moisture while constant temperature uniform stirring, when moisture is down to 30-32%, stop stirring;
2) by step 1) the even dough that obtains puts into constant-temperature enclosed container and leaves standstill, and puts into vacuum-extruder shaping after 18-24 hour;
3) extrusion molding thing is put into drying box, individual hour of dry 100-120 under 50-70 DEG C of condition;
4) by desciccate at 150-500 DEG C of temperature lower calcination 20-25 hour, obtain final products.
Especially, the component of described metal-modified solution is: 3-5 part cerous nitrate, 6-8 part ammonium heptamolybdate, 2-3 part niobium oxalate, and 3-4 part antimony acetate is dissolved in the deionized water of 20 parts respectively.
Especially, the component of described ammonium metavanadate solution is: ammonium metavanadate 3-7 part, is dissolved in the aqueous solution of 12-17 part monoethanolamine, and aqueous ethanolamine concentration is 1-3g/ml.
Especially, the preparation process of described carrier paste is: take 160-180 part deionized water, 2.7-2.9 part lactic acid, 0.7-0.9 part polyvinyl alcohol, 0.4-0.6 part polyethylene glycol oxide, 0.3-0.5 part stearic acid, 0.5-0.8 part carboxymethyl cellulose joins in 250-300 part titanium tungsten silicon titanium dioxide and fully stirs, above-mentioned slurry is heated in whipping process, when temperature reaches 40 DEG C, add the ammoniacal liquor of 27-33 part 15%, continue heating and be stirred to 85 DEG C, then constant temperature 85 DEG C boils off moisture simultaneously, stops stirring when waiting moisture content of material to steam between 30-32%.
Compared with prior art, beneficial effect of the present invention is:
1) modified metal-oxide selected can well coexist, cooperation-removal nitrogen oxide, suppresses sulphur to transform, has possessed good water repelling property simultaneously.
2) owing to adding pore-creating fiber, greatly can increase the specific area of SCR catalyst, greatly improve the activity of catalyst.
3) nitrogen oxide can be removed the temperature range of 110 DEG C-230 DEG C, achieve the application breakthrough of SCR catalyst.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
(1) preparation of metal-modified solution: get 40g cerous nitrate and be dissolved in 200g deionized water, gets 60g ammonium heptamolybdate and is dissolved in 200g deionized water, gets 30g niobium oxalate and is dissolved in 200g deionized water, gets 30g antimony acetate and is dissolved in 200g water;
(2) preparation of ammonium metavanadate solution: weigh ammonium metavanadate 30g, is dissolved in the aqueous ethanolamine of 120g, and aqueous ethanolamine concentration is 2g/ml;
(3) preparation of carrier paste: weigh 1600g deionized water, 27g lactic acid, 7g polyvinyl alcohol, 4g polyethylene glycol oxide, 3g stearic acid, 5g carboxymethyl cellulose joins in 2500g titanium tungsten silicon titanium dioxide and fully stirs, heated slurry to 40 DEG C in whipping process, continue at this temperature to add the ammoniacal liquor that 270g concentration is 20%, Keep agitation is heated to 85 DEG C, keep this temperature and boil off moisture, wait material moisture steam to 30% time stop stir.
(4) ammonium metavanadate solution prepared by metal-modified solution step (1) prepared and step (2) joins in slurry prepared by step (3), add 40g pore-creating cellucotton simultaneously, moisture is boiled off while constant temperature uniform stirring, when moisture is down to 30%, stop stirring;
(5) the even dough that step (4) obtains is put into constant-temperature enclosed container to leave standstill, put into vacuum-extruder after 18 hours shaping;
(6) extrusion molding thing is put into drying box, drying box setting initial temperature 40 DEG C, heating rate controls, at 3 DEG C/h, to take out dried material after 120 hours;
(7) desciccate is put into the Muffle furnace that initial temperature is 100 DEG C, heating rate controls, at 4 DEG C/h, 24 hours, to obtain final products.
Embodiment 2
(1) preparation of metal-modified solution: get 50g cerous nitrate and be dissolved in 200g deionized water, gets 80g ammonium heptamolybdate and is dissolved in 200g deionized water, gets 20g niobium oxalate and is dissolved in 200g deionized water, gets 40g antimony acetate and is dissolved in 200g water;
(2) preparation of ammonium metavanadate solution: weigh ammonium metavanadate 50g, is dissolved in the aqueous ethanolamine of 150g, and aqueous ethanolamine concentration is 2.5g/ml;
(3) preparation of carrier paste: weigh 1800g deionized water, 28g lactic acid, 9g polyvinyl alcohol, 6g polyethylene glycol oxide, 5g stearic acid, 8g carboxymethyl cellulose joins in 3000g titanium tungsten silicon titanium dioxide and fully stirs, heated slurry to 40 DEG C in whipping process, continue at this temperature to add the ammoniacal liquor that 330g concentration is 15%, Keep agitation is heated to 85 DEG C, keep this temperature and boil off moisture, wait material moisture steam to 30% time stop stir.
(4) ammonium metavanadate solution prepared by metal-modified solution step (1) prepared and step (2) joins in slurry prepared by step (3), add 50g pore-creating cellucotton simultaneously, moisture is boiled off while constant temperature uniform stirring, when moisture is down to 30%, stop stirring;
(5) the even dough that step (4) obtains is put into constant-temperature enclosed container to leave standstill, put into vacuum-extruder after 20 hours shaping;
(6) extrusion molding thing is put into drying box, drying box setting initial temperature 40 DEG C, heating rate controls, at 3 DEG C/h, to take out dried material after 120 hours;
(7) desciccate is put into the Muffle furnace that initial temperature is 100 DEG C, heating rate controls, at 4 DEG C/h, 24 hours, to obtain final products.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (4)
1., for a low temperature catalyst preparation method of SCR, it is characterized in that, it comprises the following steps:
1) by 28 ~ 35 parts of metal-modified solution, 15 ~ 35 parts of ammonium metavanadate solutions and 100 ~ 120 parts of carrier paste mixing constant temperature uniform stirrings, add the pore-creating cellucotton of 4-7 part simultaneously, boil off moisture while constant temperature uniform stirring, when moisture is down to 30-32%, stop stirring;
2) by step 1) the even dough that obtains puts into constant-temperature enclosed container and leaves standstill, and puts into vacuum-extruder shaping after 18-24 hour;
3) extrusion molding thing is put into drying box, individual hour of dry 100-120 under 50-70 DEG C of condition;
4) by desciccate at 150-500 DEG C of temperature lower calcination 20-25 hour, obtain final products.
2. as claimed in claim 1 for the low temperature catalyst preparation method of SCR, it is characterized in that, the component of described metal-modified solution is: 3-5 part cerous nitrate, 6-8 part ammonium heptamolybdate, 2-3 part niobium oxalate, 3-4 part antimony acetate is dissolved in the deionized water of 20 parts respectively.
3., as claimed in claim 1 or 2 for the low temperature catalyst preparation method of SCR, it is characterized in that, the component of described ammonium metavanadate solution is: ammonium metavanadate 3-7 part, is dissolved in the aqueous solution of 12-17 part monoethanolamine, and aqueous ethanolamine concentration is 1-3g/ml.
4. as claimed in claim 1 for the low temperature catalyst preparation method of SCR, it is characterized in that, the preparation process of described carrier paste is: take 160-180 part deionized water, 2.7-2.9 part lactic acid, 0.7-0.9 part polyvinyl alcohol, 0.4-0.6 part polyethylene glycol oxide, 0.3-0.5 part stearic acid, 0.5-0.8 part carboxymethyl cellulose joins in 250-300 part titanium tungsten silicon titanium dioxide and fully stirs, above-mentioned slurry is heated in whipping process, when temperature reaches 40 DEG C, add the ammoniacal liquor of 27-33 part 15%, continue heating and be stirred to 85 DEG C, then constant temperature 85 DEG C boils off moisture simultaneously, stop when steaming between 30-32% Deng moisture content of material stirring.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944755A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Preparation method of low-temperature NH3-SCR sulfur-resistant denitration catalyst |
| CN106732531A (en) * | 2016-12-09 | 2017-05-31 | 大唐国际化工技术研究院有限公司 | A kind of SCR denitration and its production and use |
| CN108126692A (en) * | 2017-12-28 | 2018-06-08 | 凯龙蓝烽新材料科技有限公司 | Good automobile-used extruded type SCR denitration of a kind of low temperature active and preparation method thereof |
-
2014
- 2014-09-11 CN CN201410462780.1A patent/CN105435777A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944755A (en) * | 2016-05-24 | 2016-09-21 | 昆明理工大学 | Preparation method of low-temperature NH3-SCR sulfur-resistant denitration catalyst |
| CN106732531A (en) * | 2016-12-09 | 2017-05-31 | 大唐国际化工技术研究院有限公司 | A kind of SCR denitration and its production and use |
| CN108126692A (en) * | 2017-12-28 | 2018-06-08 | 凯龙蓝烽新材料科技有限公司 | Good automobile-used extruded type SCR denitration of a kind of low temperature active and preparation method thereof |
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