CN101474580A - Carrier for supporting catalyst in condition with high concentration of powder dust and flue gas as well as preparation method thereof - Google Patents
Carrier for supporting catalyst in condition with high concentration of powder dust and flue gas as well as preparation method thereof Download PDFInfo
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- CN101474580A CN101474580A CNA2009100247840A CN200910024784A CN101474580A CN 101474580 A CN101474580 A CN 101474580A CN A2009100247840 A CNA2009100247840 A CN A2009100247840A CN 200910024784 A CN200910024784 A CN 200910024784A CN 101474580 A CN101474580 A CN 101474580A
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Abstract
The invention discloses a carrier for carrying a catalyst under the smoke gas condition of heavy dust and a method for preparing the carrier. According to the technical scheme of the invention, the carrier for carrying the catalyst under the smoke gas condition of heavy dust comprises 75 to 97 percent of TiO2, 2 to 20 percent of fibre glass and 0 to 8 percent of rare earth oxide according to weight percentage. The carrier of the invention has high mechanical strength, can run under higher pressure, has strong wear strength, and can run under the smoke gas condition of heavy dust, thereby increasing the service life thereof; and the carrier is provided with favorable pore structure and specific surface, thereby providing a platform for the further step of preparing a favorable catalyst. The carrier can be optionally added with certain amount of rare earth oxide, thus the catalyst with the performances of low temperature, high activity, and the like can be prepared.
Description
Technical field
The invention discloses a kind of carrier that is used for catalyst under the load high-dust flue gas condition, the invention discloses a kind of preparation method of this carrier.
Background technology
At thermoelectricity NO
XThe control technology research aspect of polluting, as far back as the seventies in last century, developed country just begins situations such as emission level, coal characteristics, boiler type according to this country as Japan, Germany, the U.S. etc., has developed a series of SCR catalyst.At present, many R﹠D institutions of China or individual begin to use for reference foreign experience, at coal-fired ature of coal complexity, and the non-constant of back boiler smoke condition that causes burning, particularly a lot of high situations of project dust content are carried out the research of catalyst.Thereby develop a kind of catalyst of under the high-dust flue gas condition, moving of being adapted at.
Yet, current with TiO
2Deng composition is that main removal of nitrogen oxide catalyst mainly is that the metal salt solution that will contain active component is impregnated on the carrier of moulding, and the carrier of therefore developing the catalyst that moves under a kind of suitable Chinese high-dust flue gas condition will be the important breakthrough that catalyst is made.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of carrier that is adapted at the catalyst that moves under the Chinese high-dust flue gas condition is provided.
Another object of the present invention then provides a kind of preparation method of above-mentioned carrier.
According to technical scheme provided by the invention, the described carrier that is used for catalyst under the load high-dust flue gas condition comprises the TiO of 75%～97% weight percentage in this carrier
2, the content of glass fiber of 2%～20% weight percentage, the rare earth oxide of 0～8% weight percentage.
Described rare earth oxide is the oxide of lanthanum and/or the oxide of cerium.TiO in the described carrier
2Weight percentage be 85%～97%.The weight percentage of glass fibre is 2%～15% in the described carrier.The weight percentage of described carrier middle rare earth oxide is 0～5%.
Above-mentioned preparing carriers method comprises following steps:
A, take by weighing TiO
2, glass fibre and three kinds of raw material for standby of rare earth oxide, make TiO
2Weight accounts for 75%～97% in three kinds of raw material gross weights, glass fibre weight accounts for 2%～20% in three kinds of raw material gross weights, and rare earth oxide weight accounts for 0～8% in three kinds of raw material gross weights;
B, get TiO
2Also mix with rare earth oxide, with TiO
2The carboxymethyl cellulose of weight 8%～12%, TiO
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add TiO
2Weight 8%～16%, content is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.5～0.7g/cm
3The carrier blank;
F, with carrier blank under 50～70 ℃ of conditions dry 4～8 hours, under 100～120 ℃ temperature conditions dry 4～8 hours then;
G, the carrier blank that drying is good were calcined 8～15 hours under 250～300 ℃ of conditions, calcined 5～10 hours under 380～420 ℃ of conditions then, calcined 8～12 hours under 550～600 ℃ of conditions at last, obtained the carrier finished product.
Described lubricant is glycerine or stearic acid.Described TiO2 diameter of particle＜0.1mm.
Carrier mechanical strength height of the present invention can move under higher pressure; The carrier wear strength is strong, can under the flue gas condition of high dust, move, thus the service life of improving carrier; Carrier has good pore structure and specific surface, provides platform thereby make good catalyst for next step.This carrier adds a certain amount of rare earth oxide with selection, thereby can produce the catalyst of performances such as having low temperature, high activity.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
A, take by weighing the TiO of 75kg
2, 20kg glass fibre and three kinds of raw material for standby of 5kg lanthana, make TiO
2Weight accounts for 75% in three kinds of raw material gross weights, glass fibre weight accounts for 20% in three kinds of raw material gross weights, and lanthana weight accounts for 5% in three kinds of raw material gross weights;
B, get TiO
2Also mix with lanthana, with TiO
2The sesbania powder of the carboxymethyl cellulose of weight 6kg, 75kg adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add 6kg, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add glycerine as lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.5g/cm
3The carrier blank;
F, with carrier blank under 50 ℃ of conditions dry 8 hours, under 100 ℃ temperature conditions dry 4 hours then;
G, the carrier blank that drying is good were calcined 8 hours under 250 ℃ of conditions, calcined 5 hours under 380 ℃ of conditions then, calcined 8 hours under 550 ℃ of conditions at last, obtained the carrier finished product.
Gained carrier end properties parameter is:
Transverse strength is: ≧ 80N/cm
2
Longitudinal strength is: ≧ 230N/cm
2
Abrasion strength resistance is: ≦ 0.10%/kg-sand
Specific area is: ≧ 65m
2/ g
Pore volume is: 0.30ml/g～0.36ml/g.
Embodiment 2
A, take by weighing the TiO of 97kg
2, 2kg glass fibre and three kinds of raw material for standby of 1kg cerium oxide, make TiO
2Weight accounts for 97% in three kinds of raw material gross weights, glass fibre weight accounts for 2% in three kinds of raw material gross weights, and cerium oxide weight accounts for 1% in three kinds of raw material gross weights;
B, get TiO
2Also mix with cerium oxide, with carboxymethyl cellulose, the TiO of 11.64kg
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add 15.52kg, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add stearic acid as lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.7g/cm
3The carrier blank;
F, with carrier blank under 70 ℃ of conditions dry 4 hours, under 120 ℃ temperature conditions dry 4 hours then;
G, the carrier blank that drying is good were calcined 15 hours under 300 ℃ of conditions, calcined 10 hours under 420 ℃ of conditions then, calcined 12 hours under 600 ℃ of conditions at last, obtained the carrier finished product.
Gained carrier end properties parameter is:
Transverse strength is: ≧ 70N/cm
2
Longitudinal strength is: ≧ 210N/cm
2
Abrasion strength resistance is: ≦ 0.17%/kg-sand
Specific area is: ≧ 60m
2/ g
Pore volume is: 0.30ml/g～0.36ml/g.
Embodiment 3
A, take by weighing the TiO of diameter of particle＜0.1mm of 85kg
2, the glass fibre of 14.5kg, the cerium oxide of 0.25kg and three kinds of raw material for standby of lanthana of 0.25kg, make TiO
2Weight accounts for 85% in three kinds of raw material gross weights, glass fibre weight accounts for 14.5% in three kinds of raw material gross weights, and the rare earth oxide weight that is made of lanthana and cerium oxide accounts for 0.5% in three kinds of raw material gross weights;
B, get TiO
2, cerium oxide and lanthana and mix, with carboxymethyl cellulose, the TiO of 8.5kg
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add 8.5kg, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add glycerine as lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.6g/cm
3The carrier blank;
F, with carrier blank under 60 ℃ of conditions dry 6 hours, under 110 ℃ temperature conditions dry 6 hours then;
G, the carrier blank that drying is good were calcined 12 hours under 275 ℃ of conditions, calcined 7 hours under 400 ℃ of conditions then, calcined 10 hours under 580 ℃ of conditions at last, obtained the carrier finished product.
Gained carrier end properties parameter is:
Transverse strength is: ≧ 76N/cm
2
Longitudinal strength is: ≧ 220N/cm
2
Abrasion strength resistance is: ≦ 0.12%/kg-sand
Specific area is: ≧ 57m
2/ g
Pore volume is: 0.30ml/g～0.36ml/g.
Embodiment 4
A, take by weighing the TiO of diameter of particle＜0.1mm of 85kg
2, the glass fibre of 7kg and three kinds of raw material for standby of lanthana of 8kg, make TiO
2Weight accounts for 85% in three kinds of raw material gross weights, glass fibre weight accounts for 7% in three kinds of raw material gross weights, and lanthana weight accounts for 8% in three kinds of raw material gross weights;
B, get TiO
2Also mix with lanthana, with carboxymethyl cellulose, the TiO of 8.5kg
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add 8.5kg, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.55g/cm
3The carrier blank;
F, with carrier blank under 55 ℃ of conditions dry 7 hours, under 105 ℃ temperature conditions dry 5 hours then;
G, the carrier blank that drying is good were calcined 11 hours under 290 ℃ of conditions, calcined 6 hours under 410 ℃ of conditions then, calcined 9 hours under 560 ℃ of conditions at last, obtained the carrier finished product.
Gained carrier end properties parameter is:
Transverse strength is: ≧ 71N/cm
2
Longitudinal strength is: ≧ 210N/cm
2
Abrasion strength resistance is: ≦ 0.15%/kg-sand
Specific area is: ≧ 60m
2/ g
Pore volume is: 0.30ml/g～0.36ml/g.
Embodiment 5
A, take by weighing the TiO of diameter of particle＜0.1mm of 80kg
2, the glass fibre of 15kg and three kinds of raw material for standby of lanthana of 5kg, make TiO
2Weight accounts for 80% in three kinds of raw material gross weights, glass fibre weight accounts for 15% in three kinds of raw material gross weights, and lanthana weight accounts for 5% in three kinds of raw material gross weights;
B, get TiO
2Also mix with lanthana, with TiO
2The carboxymethyl cellulose of weight 8.8kg, TiO
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add 9.6kg, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add glycerine as lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.65g/cm
3The carrier blank;
F, with carrier blank under 65 ℃ of conditions dry 5 hours, under 106 ℃ temperature conditions dry 5 hours then;
G, the carrier blank that drying is good were calcined 9 hours under 260 ℃ of conditions, calcined 7 hours under 412 ℃ of conditions then, calcined 11 hours under 555 ℃ of conditions at last, obtained the carrier finished product.
Gained carrier end properties parameter is:
Transverse strength is: ≧ 85N/cm
2
Longitudinal strength is: ≧ 240N/cm
2
Abrasion strength resistance is: ≦ 0.08%/kg-sand
Specific area is: ≧ 53m
2/ g
Pore volume is: 0.30ml/g～0.36ml/g.
Claims (8)
1, a kind of carrier that is used for catalyst under the load high-dust flue gas condition is characterized in that: the TiO that comprises 75%～97% weight percentage in this carrier
2, the content of glass fiber of 2%～20% weight percentage, the rare earth oxide of 0～8% weight percentage.
2, carrier as claimed in claim 1 is characterized in that: described rare earth oxide is the oxide of lanthanum and/or the oxide of cerium.
3, carrier as claimed in claim 1 is characterized in that: TiO in the described carrier
2Weight percentage be 85%～97%.
4, carrier as claimed in claim 1 is characterized in that: the weight percentage of glass fibre is 2%～15% in the described carrier.
5, carrier as claimed in claim 1 is characterized in that: the weight percentage of described carrier middle rare earth oxide is 0～5%.
6, the described preparing carriers method of claim 1 comprises following steps:
A, take by weighing TiO
2, glass fibre and three kinds of raw material for standby of rare earth oxide, make TiO
2Weight accounts for 75%～97% in three kinds of raw material gross weights, glass fibre weight accounts for 2%～20% in three kinds of raw material gross weights, and rare earth oxide weight accounts for 0～8% in three kinds of raw material gross weights;
B, get TiO
2Also mix with rare earth oxide, with TiO
2The carboxymethyl cellulose of weight 8%～12%, TiO
2The sesbania powder of weight 8%～12% adds TiO
2In the mixture of glass fibre, stir;
C, in the mixture of step b, add TiO
2Weight 8%～16%, weight percentage is 5% citric acid solution, fully stirs the plasticity lotion that obtains mixing;
D, in the plasticity lotion that step c obtains, add lubricant;
E, the glass fibre that adding step a takes by weighing in the mixture of steps d, extruding bulk density with extruder after mixing is 0.5～0.7g/cm
3The carrier blank;
F, with carrier blank under 50～70 ℃ of conditions dry 4～8 hours, under 100～120 ℃ temperature conditions dry 4～8 hours then;
G, the carrier blank that drying is good were calcined 8～15 hours under 250～300 ℃ of conditions, calcined 5～10 hours under 380～420 ℃ of conditions then, calcined 8～12 hours under 550～600 ℃ of conditions at last, obtained the carrier finished product.
7, preparation method as claimed in claim 6 is characterized in that: described lubricant is glycerine or stearic acid.
8, preparation method as claimed in claim 6 is characterized in that: described TiO
2Diameter of particle＜0.1mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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|---|---|---|---|
| CN200910024784.0A CN101474580B (en) | 2009-02-13 | 2009-02-13 | Carrier for supporting catalyst in condition with high concentration of powder dust and flue gas as well as preparation method thereof |
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| CN101474580B CN101474580B (en) | 2014-04-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102725063A (en) * | 2009-12-16 | 2012-10-10 | 莱昂德尔化学技术公司 | Titania-containing extrudate |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN102755898A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Semiconductor control rectifier (SCR) denitration catalytic agent applicable to high ash-laden gas condition and preparation method thereof |
| CN102764644A (en) * | 2012-08-07 | 2012-11-07 | 江苏龙源催化剂有限公司 | Preparation process of elective catalytic reduction (SCR) denitration catalyst applicable to conditions of high calcium content and high sulfur content |
| CN103691489A (en) * | 2013-11-29 | 2014-04-02 | 湖北广净环保催化剂有限公司 | Denitration catalyst carrier for loading high-dust flue gas and preparation method thereof |
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| CN101284248B (en) * | 2008-05-16 | 2010-04-21 | 中国石化扬子石油化工有限公司 | Titanic dioxide shaping carrier modified by alkali-free glass fibre and preparation method thereof |
| CN100594978C (en) * | 2008-08-22 | 2010-03-24 | 中国石化扬子石油化工有限公司 | Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde |
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2009
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102725063A (en) * | 2009-12-16 | 2012-10-10 | 莱昂德尔化学技术公司 | Titania-containing extrudate |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN102755898A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Semiconductor control rectifier (SCR) denitration catalytic agent applicable to high ash-laden gas condition and preparation method thereof |
| CN102764644A (en) * | 2012-08-07 | 2012-11-07 | 江苏龙源催化剂有限公司 | Preparation process of elective catalytic reduction (SCR) denitration catalyst applicable to conditions of high calcium content and high sulfur content |
| CN102764644B (en) * | 2012-08-07 | 2014-05-07 | 江苏龙源催化剂有限公司 | Preparation process of elective catalytic reduction (SCR) denitration catalyst applicable to conditions of high calcium content and high sulfur content |
| CN103691489A (en) * | 2013-11-29 | 2014-04-02 | 湖北广净环保催化剂有限公司 | Denitration catalyst carrier for loading high-dust flue gas and preparation method thereof |
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| CN101474580B (en) | 2014-04-23 |
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Address after: No.6 Yongsheng Road, Yixing Economic Development Zone, Wuxi City, Jiangsu Province Patentee after: Guoneng Longyuan catalyst Jiangsu Co.,Ltd. Address before: 214151 No. 557 Hu Hu Road, Qian Qiao Town, Huishan District, Jiangsu, Wuxi Patentee before: JIANGSU LONGYUAN CATALYST Co.,Ltd. |