CN1724154A - Catalyst for tailing gas purifying of natural gas engine and its preparation process - Google Patents
Catalyst for tailing gas purifying of natural gas engine and its preparation process Download PDFInfo
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- CN1724154A CN1724154A CN 200510018899 CN200510018899A CN1724154A CN 1724154 A CN1724154 A CN 1724154A CN 200510018899 CN200510018899 CN 200510018899 CN 200510018899 A CN200510018899 A CN 200510018899A CN 1724154 A CN1724154 A CN 1724154A
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- catalyst
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Abstract
A catalyst for cleaning the tail gas of natural-gas engine contains proportionally gamme-Al2O3, RE metal oxide, transition metal oxide, alkali-earth metal oxide and noble metal. Its advantages are low igniting temp and high high-temp stability.
Description
Technical field
The present invention relates to a kind of catalyst for tailing gas purifying of natural gas engine and preparation method thereof.
Background technology
In the past few decades, automobile is substantially based on petroleum based fuels, discharge during automobile engine work and contain toxic gases such as CO, CH, NOx in a large number, pollutant atmosphere greatly, though electric jet technology and the extensive use of three-element catalytic transformation technology also do not tackle the problem at its root at present; In recent years, people are in research and adopt various natural gases to replace the fuel of petroleum based fuels as automobile engine, oil liquefied gas (LPG) and compressed natural gas (CNG) have the storage efficiency height as engine replacing fuel, automobile dynamic quality is good, ratio of performance to price height, advantages such as disposal of pollutants is lower, LPG, CNG engine automobile will be the directions of automobile industry development, China is the country of a petroleum resources shortage, and natural gas resource is abundant, along with the construction of West-East National Gas Transmission Project, the development of gas-fueled vehicles has more realistic meaning.
Natural gas has compared with gasoline as motor vehicle fuel that some is different: 1. the natural gas composition mainly is a methane, and methane is the most dysoxidizable compound of hydrocarbon compound, is difficult to the methane gas conversion ratio that reaches high with the three-way catalyst of gasoline automobile; 2. the octane number height of natural gas, burning velocity is different from gasoline, and temperature height in the cylinder requires the tail gas reforming catalyst high temperature resistant, and changing capability is strong; 8. mixture strength is different from gasoline car during three-way catalyst maximum conversion efficient, and the former air-fuel ratio is near 17.1, and the latter is near 14.7; 4. ignition energy is higher than gasoline during combustion of natural gas.Therefore the tai-gas clean-up catalyst that requires natural gas to start has good low light-off temperature and high-temperature stability.
Summary of the invention
Purpose of the present invention just provides a kind of catalyst for tailing gas purifying of natural gas engine and manufacture method thereof.Catalyst has good low light-off temperature and high-temperature stability.
The present invention is achieved like this, and it is characterized in that containing in every liter of carrier following composition weight number to be: γ-Al
2O
350～120g, rare-earth oxide 8～20g, transition metal oxide 1～10g, alkaline earth oxide 0.5～5g, noble metal 0.5～1.5g, carrier are cordierite honeycomb ceramic, its important technological parameters is: the order number: 200～400 orders, bulk density: 0.5～0.75g/cm
3, water absorption rate: 17～25%.Rare-earth oxide is La
2O
3, CeO
2, Y
2O
3, Nd
2O
3In two kinds and two or more, transition metal oxide is ZrO
2, TiO
2, NiO, CoO, a kind of among the CuO and more than one, alkaline earth oxide are a kind of among BaO, SrO, CaO, the MgO and more than one, noble metal is: a kind of among Pt, Pd, the Rh and more than one.
Its preparation method is taked following processing step:
(1) gets quantitative rare earth soluble-salt (get in lanthanum, cerium, yttrium, the titanium salt more than two kinds and two kinds), transition metal salt (a kind of in zirconium, nickel, copper, titanium, the cobalt salt and more than one; A kind of in alkali salt Ba, Sr, Ca, the Mg salt and more than one) be made into about 25% distilled water solution, stir on the limit, the limit dropping ammonia, transferring PH is 9～12, generates precipitation, suction filtration, gets filter cake;
(2) in quantitative aluminium oxide (containing crystallization water 1-3), add dispersant and distilled water such as an amount of aluminium colloidal sol, polyvinyl alcohol, be made into the uniform sizing material that alumina content is 10-35%, the filter cake that step (1) is obtained adds, in ball mill ball milling 24-56 hour, obtain the combined oxidation aluminum slurry of uniform particle size (＜1 μ);
(3) honeycomb ceramic carrier that surface clean is clean, with the combined oxidation aluminum slurry coating that step (2) obtains, coating weight is the 10-20% of carrier, and is dry then, calcining
(4) carried noble metal: a, the quantitative chlorine palladium acid solution of preparation add complexing agent and competitive adsorbate, flood dry then, roasting with the carrier that has been coated with composite alumina; B, the quantitative chloroplatinic acid of preparation, rhodium chloride solution adds complexing agent and competitive adsorbate, the catalyst that obtains with a step floods, and is dry then, roasting, obtain catalyst, the noble metal ratio is Pd: Pt: Rh=10～8: 1～3: 0.5～1.5 in the catalyst.Complexing agent mainly contains ethylenediamine tetra-acetic acid, and disodium ethylene diamine tetraacetate, aminotriacetic acid, competitive adsorbate mainly contain carboxymethyl cellulose, silicon gel, bleaching earth.
The present invention is cheap, has good low light-off temperature, and high-temperature stability, is particularly suitable for doing the catalyst of tailing gas purifying of natural gas engine, has extensive market prospects.
The specific embodiment
Embodiment (one)
(1) get quantitative lanthanum nitrate, cerous nitrate, transition metal salt basic zirconium chloride, nickel nitrate, alkali salt barium nitrate are made into about 25% distilled water solution, and stir on the limit, the limit dropping ammonia, and transferring PH is 10, generates precipitation, suction filtration, gets filter cake;
(2) in aluminium oxide (containing 1 of the crystallization water), add aluminium colloidal sol, polyvinyl alcohol and distilled water, be made into alumina content and be 25% uniform sizing material, the filter cake that step (1) is obtained was added in the ball mill ball milling 40 hours, obtained the combined oxidation aluminum slurry of uniform particle size;
(3) honeycomb ceramic carrier that surface clean is clean is 1 liter, and the combined oxidation aluminum slurry that obtains with step (2) is coated with face, and coating weight is the 15% dry then of carrier, calcining;
(4) carried noble metal: a, the quantitative chlorine palladium acid solution of preparation add complexing agent ethylenediamine tetra-acetic acid and competitive adsorbate carboxymethyl cellulose, flood drying, roasting then with the carrier of coated composite alumina; B, get quantitative chloroplatinic acid, rhodium chloride solution adds complexing agent ethylenediamine tetra-acetic acid and competitive adsorbate carboxymethyl cellulose, the catalyst that obtains with a step floods, and is dry then, roasting, obtain catalyst, the noble metal ratio is Pd: Pt: Rh=9 in the catalyst: 2: 1.
Embodiment (two)
(1) get quantitative lanthanum nitrate, yttrium nitrate, transition metal salt zirconyl chloride, cobalt nitrate, the alkali salt strontium nitrate is made into about 25% distilled water solution, and stir on the limit, the limit dropping ammonia, transferring PH is 10, generates precipitation, suction filtration, gets filter cake;
(2) go into aluminium colloidal sol, polyvinyl alcohol and distilled water at aluminium oxide (containing 2 of the crystallizations water) central roll, be made into alumina content and be 15% uniform sizing material, the filter cake that step (1) is obtained was added in the ball mill ball milling 24 hours, obtained the combined oxidation aluminum slurry of uniform particle size;
(3) honeycomb ceramic carrier that surface clean is clean is 1 liter, and the combined oxidation aluminum slurry that obtains with step (2) is coated with face, and coating weight is 10% of a carrier, and is dry then, calcining;
(4) carried noble metal: a, the quantitative chlorine palladium acid solution of preparation add complexing agent disodium ethylene diamine tetraacetate and competitive adsorbate silicon gel, flood drying, roasting then with the carrier of coated composite alumina; B, get quantitative chloroplatinic acid, rhodium chloride solution, add complexing agent disodium ethylene diamine tetraacetate and competitive adsorbate silicon gel, the catalyst that obtains with a step floods, and is dry then, roasting, obtain catalyst, the noble metal ratio is Pd: Pe: Rh=10 in the catalyst: 1: 0.5, complexing agent was EDTA, and adsorbent is a carboxymethyl cellulose unexpectedly.
Embodiment (three)
(1) at quantitative yttrium nitrate, cerous nitrate, transition metal salt basic zirconium chloride, copper nitrate, alkali salt magnesium nitrate, strontium nitrate are made into about 30% distilled water solution, and stir on the limit, the limit dropping ammonia, transferring PH is 12, generates precipitation, suction filtration, gets filter cake;
(2) in aluminium oxide (containing 3 of the crystallizations water), adding aluminium colloidal sol, polyvinyl alcohol and distilled water mixes, be made into alumina content and be 25% uniform sizing material, the filter cake that step (1) is obtained was added in the ball mill ball milling 56 hours, obtained the combined oxidation aluminum slurry of uniform particle size;
(3) honeycomb ceramic carrier that surface clean is clean is 1 liter, and the combined oxidation aluminum slurry that obtains with step (2) is coated with face, and coating weight is 20% of a carrier, and is dry then, calcining;
(4) carried noble metal: a, the quantitative chlorine palladium acid solution of preparation add complexing agent aminotriacetic acid and competitive adsorbate bleaching earth, flood drying, roasting then with the carrier of coated composite alumina; B, get quantitative chloroplatinic acid, rhodium chloride solution adds complexing agent aminotriacetic acid and competitive adsorbate bleaching earth, the catalyst that obtains with a step floods, and is dry then, roasting, obtain catalyst, the noble metal ratio is Pd: Pe: Rh=8 in the catalyst: 3: 1.5.
The present invention has good activity and heat-resistant stability, and catalyst is after through 1050 ℃, 24 hours senile experiment, and (volumn concentration of CO is 1.35%, CH in simulation gas
4Content is 0.25%, and Nox content is 0.2%, O
2Content is 4.2%, CO
2Content is 6%, N
2Be diluent gas) detect down:
| Catalyst initiation temperature (T 50/ ℃) be | Catalyst is through 1050 ℃, 24 hours aging back initiation temperatures | |||||
| Catalyst | Co(T50/℃) | HC(T50/℃) | NOx(T50/℃) | CO(T50/℃) | HC(T50/℃) | NOx(T50/℃) |
| Embodiment one | 240 | 260 | 230 | 263 | 282 | 241 |
| Embodiment two | 243 | 265 | 240 | 255 | 280 | 236 |
| Embodiment three | 230 | 254 | 220 | 248 | 268 | 230 |
With the method for embodiment three, produce catalytic converter (φ 200 * 220), in the technique center working condition tests result of Yulin Diesel Engine Plant:
| The discharging composition | CO | HC | Nox |
| g/kw.h | 0.15 | 0.24 | 1.56 |
| Europe II standard is sex-limited | 4.0 | 1.1 | 7.0 |
Claims (4)
1, a kind of catalyst for tailing gas purifying of natural gas engine is characterized in that containing in every liter of carrier following composition weight number and is: γ-Al
2O
350～120g, rare-earth oxide 8～20g, transition metal oxide 1～10g, alkaline earth oxide 0.5～5g, noble metal 0.5～1.5g.
2, catalyst for tailing gas purifying of natural gas engine according to claim 1 is characterized in that rare-earth oxide is La
2O
3, CeO
2, Y
2O
3, Nd
2O
3In two kinds and two or more, transition metal oxide is ZrO
2, TiO
2, a kind of among NiO, CoO, the GuO and more than one, alkaline earth oxide is a kind of among BaO, SrO, CaO, the MgO and more than one, metal oxide containing precious metals is: a kind of among Pt, Pd, the Rh and more than one.
3, the described catalyst for tailing gas purifying of natural gas engine of a kind of claim 1 is characterized in that it takes following processing step:
(1) get quantitative rare earth soluble-salt, transition metal salt, alkali salt are made into about 25% distilled water solution, and stir on the limit, the limit dropping ammonia, and transferring PH is 9～12, generates precipitation, suction filtration is got filter cake;
(2) adding an amount of aluminium colloidal sol, polyvinyl alcohol dispersant and distilled water in quantitative aluminium oxide mixes, be made into the uniform sizing material that alumina content is 10-35%, the filter cake that step (1) is obtained adds, and in ball mill ball milling 24-56 hour, obtains the combined oxidation aluminum slurry of uniform particle size;
(3) honeycomb ceramic carrier that surface clean is clean, with the combined oxidation aluminum slurry coating that step (2) obtains, coating weight is the 10-20% of carrier, and is dry then, calcining;
(4) carried noble metal: a, the quantitative chlorine palladium acid solution of preparation add complexing agent and competitive adsorbate, flood dry then, roasting with the carrier that has been coated with composite alumina; B, the quantitative chloroplatinic acid of preparation, rhodium chloride solution adds complexing agent and competitive adsorbate, the catalyst that obtains with a step floods, and is dry then, roasting, obtain catalyst, the noble metal ratio is Pd: Pt: Rh=10～8: 1～3 in the catalyst: O.5～1.5.
4, catalyst for tailing gas purifying of natural gas engine according to claim 3 is characterized in that complexing agent is ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, aminotriacetic acid, and competitive adsorbate is carboxymethyl cellulose, silicon gel, bleaching earth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510018899 CN1724154A (en) | 2005-06-10 | 2005-06-10 | Catalyst for tailing gas purifying of natural gas engine and its preparation process |
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|---|---|---|---|
| CN 200510018899 CN1724154A (en) | 2005-06-10 | 2005-06-10 | Catalyst for tailing gas purifying of natural gas engine and its preparation process |
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| CN1724154A true CN1724154A (en) | 2006-01-25 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102003254A (en) * | 2010-11-18 | 2011-04-06 | 华东理工大学 | Catalytic converter for purifying exhaust of natural gas automobile |
| US8071498B2 (en) | 2006-04-21 | 2011-12-06 | Cataler Corporation | Exhaust gas purifying catalyst, method for recovering exhaust gas purifying catalyst, and catalyst system for exhaust gas purification |
| CN102580761A (en) * | 2011-12-16 | 2012-07-18 | 刘光文 | Electrospray SCR diesel engine tail gas catalyst |
| CN101619231B (en) * | 2008-06-30 | 2013-04-24 | 中国石油化工股份有限公司 | Fuel oil adsorption desulfurization adsorbent and method for preparing same |
| CN105435785A (en) * | 2015-12-04 | 2016-03-30 | 中自环保科技股份有限公司 | Sulphur-resistant natural-gas-exhaust purification catalyst and preparing method thereof |
| CN107999056A (en) * | 2017-12-13 | 2018-05-08 | 武汉理工大学 | The preparation method of support type Mg/Sn/W composite oxide catalysts |
| CN108855075A (en) * | 2018-06-20 | 2018-11-23 | 东莞诺维新材料科技有限公司 | A kind of preparation method of the oxidation catalyst for diesel vehicle |
-
2005
- 2005-06-10 CN CN 200510018899 patent/CN1724154A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8071498B2 (en) | 2006-04-21 | 2011-12-06 | Cataler Corporation | Exhaust gas purifying catalyst, method for recovering exhaust gas purifying catalyst, and catalyst system for exhaust gas purification |
| CN101421037B (en) * | 2006-04-21 | 2012-06-06 | 株式会社卡特勒 | Exhaust gas purifying catalyst, method for recovering exhaust gas purifying catalyst, and catalyst system for exhaust gas purification |
| CN101619231B (en) * | 2008-06-30 | 2013-04-24 | 中国石油化工股份有限公司 | Fuel oil adsorption desulfurization adsorbent and method for preparing same |
| CN102003254A (en) * | 2010-11-18 | 2011-04-06 | 华东理工大学 | Catalytic converter for purifying exhaust of natural gas automobile |
| CN102580761A (en) * | 2011-12-16 | 2012-07-18 | 刘光文 | Electrospray SCR diesel engine tail gas catalyst |
| CN102580761B (en) * | 2011-12-16 | 2014-03-05 | 刘光文 | Electrospray SCR diesel engine tail gas catalyst |
| CN105435785A (en) * | 2015-12-04 | 2016-03-30 | 中自环保科技股份有限公司 | Sulphur-resistant natural-gas-exhaust purification catalyst and preparing method thereof |
| CN105435785B (en) * | 2015-12-04 | 2018-02-06 | 中自环保科技股份有限公司 | A kind of resistant to sulfur natural gas tai-gas clean-up catalyst and preparation method thereof |
| CN107999056A (en) * | 2017-12-13 | 2018-05-08 | 武汉理工大学 | The preparation method of support type Mg/Sn/W composite oxide catalysts |
| CN108855075A (en) * | 2018-06-20 | 2018-11-23 | 东莞诺维新材料科技有限公司 | A kind of preparation method of the oxidation catalyst for diesel vehicle |
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Effective date of registration: 20060804 Address after: No. 999 Xuefu Road in Nanchang city Honggutan New District in Jiangxi Province Applicant after: Nanchang University Address before: No. 235 Nanjing East Road, Jiangxi, Nanchang, Nanchang University Applicant before: Chen Zhaoping Effective date of registration: 20060804 Address after: No. 999 Xuefu Road in Nanchang city Honggutan New District in Jiangxi Province Applicant after: Nanchang University Address before: No. 235 Nanjing East Road, Jiangxi, Nanchang, Nanchang University Applicant before: Chen Zhaoping Co-applicant before: Liu Guangwen |
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