CN100457238C - Catalyst for purifying IC engine tail gas and/or industrial waste gas - Google Patents
Catalyst for purifying IC engine tail gas and/or industrial waste gas Download PDFInfo
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- CN100457238C CN100457238C CNB981111556A CN98111155A CN100457238C CN 100457238 C CN100457238 C CN 100457238C CN B981111556 A CNB981111556 A CN B981111556A CN 98111155 A CN98111155 A CN 98111155A CN 100457238 C CN100457238 C CN 100457238C
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Abstract
The present invention provides a kind of integral redox catalyst with metal oxides and light rare earth element as main components and small amount of noble metal as well as its special preparation process. The catalyst is suitable for treatment of tail gas exhausted by vehicle and motor cycle, industrial organic waste gas and bad smell. The present invention features the utilization of metal oxides rather than rhodium as a noble metal; the special preparation process, which makes it possible for the catalyst with only 1-500 ppm noble Pt-Pd or Pr to reach catalytic performance superior to available catalyst with noble content one order higher; and the excellent performance of the catalyst in service life, space velocity, high temperature stability, and antitoxic property.
Description
The present invention relates to be used for the Catalysts and its preparation method of purifying automobile tail gas, motorcycle exhaust and/or industrial organic exhaust gas.
Along with developing of automobile industry, promoted technology and prosperity of economy, but the carbon monoxide in the automobile exhaust, hydrocarbon and oxynitrides have become the main source of atmosphere pollution, be environmental hazard maximum in the big city.The automobile exhaust catalysis technique is along with the enforcement of automobile emission regulation grows up.Facts have proved that for many years adopting catalyst that purified treatment is carried out in automobile exhaust is that a kind of vehicle emission pollution of controlling has an economic benefit and the most lasting method most, this technology obtains increasingly extensive concern and real application research in countries in the world.External catalyst adopts noble metal, with platinum, palladium, rhodium is primary raw material, also bring into use at present the additive of a small amount of rare-earth oxide, with performance and the reduction catalyst cost that improves catalyst, as patent of invention publication number CN1053899A as noble metal catalyst.Noble metal costs an arm and a leg and resource-constrained, and China's rare earth resources is abundant, cheap, but the performance of pure rare earth catalyst also exists many gaps with the noble metal catalyst ratio.Domestic catalyst research person is doing a lot of work aspect the rare earth catalyst research in conjunction with China's national situation, as patent of invention publication number CN1060793A, CN1129146A.It is (weight) principal component, the catalyst research that adds minute amount of noble metal that the present invention is intended to multivariant oxide and light rare earth.
The invention provides a kind of whole shape, multi-element metal oxide and light rare earth oxidation-reduction catalyst for (weight) principal component, interpolation minute amount of noble metal, and special catalyst preparation process.This catalyst is applicable to the discharging of administering automobile, motorcycle pollutant, and the purified treatment of industrial organic exhaust gas and stench.The present invention's characteristics: the reduction that at first is to substitute Noble Metal Rhodium with multi-element metal oxide, secondly, invent special preparation technology, make 1,000,000/ noble metal platinum-palladium or palladium, reach the noble metal catalyst that is higher than an order of magnitude consumption of the present invention and also want excellent catalytic performance to 5/10000ths; The 3rd, at aspects such as catalyst service life, air speed performance, heat-resistant stable and antitoxin thing abilities, leading domestic contribution is arranged all.
Catalyst of the present invention is a kind of catalyst that is used for purification of exhaust gases of internal combustion engines and/or industrial waste gas, it is a kind of whole shape, with multi-element metal oxide and light rare earth is the weight principal component, add the oxidation-reduction catalyst of minute amount of noble metal platinum-palladium or palladium, it is by (1) carrier, (2) binder course: the binder course slurry is attached on the carrier hole wall, and (3) two step method multi-element metal oxide A group: on binder course, multi-element metal oxide B organizes: on multi-element metal oxide A group; Or one-step method multi-element metal oxide AB group: on binder course, then the logical hydrogen of above-mentioned integral body is reduced and handle the gained major catalyst and constitute separately, or with by second carrier, constitute attached to the group of the multi-element metal oxide C on second carrier thing gained soot preparation block.
The catalyst of a kind of purifying automobile tail gas of the present invention, its composition comprises:
(1) honeycomb ceramic carrier: main component cordierite content＞90%, diameter or monolateral length≤260mm, hole order≤400 hole/inches
2, percent opening 35%-60%, specific area 0.5-2.0m
2/ g, bulk density 0.5-0.7g/cm
3, water absorption rate 21%-30%.
(2) binder course: binder course with the form of film attached on the honeycomb ceramic carrier hole wall, wherein contained metallic element can have the 4-8 kind, be selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal, the weight of binder course is the 3%-15% of honeycomb ceramic carrier weight.
(3) multi-element metal oxide A group: on binder course, wherein contained metallic element can have the 6-10 kind, be selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal 4%-15% that selected multiple metallic element gross weight is the binder course total weight of carrier.
(4) multi-element metal oxide B group: mainly attached on the multi-element metal oxide A group, wherein contained metallic element can have the 8-10 kind, be selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal, selected multiple metallic element gross weight is for containing (3) 2%-12% in interior binder course total weight of carrier.
Wherein preferred binder course metal oxide and metallic element are formed:
(1) metallic element of 2-4 kind metal oxide is selected from: cerium, boron, a water aluminium oxide, kaolin, and the percentage of its weight and honeycomb ceramic carrier weight is:
Cerium 0.1%-10%, a water aluminium oxide 3%-20%,
Boron 0.2%-3%, kaolin 1%-15%,
(2) have the metallic element of 2-6 kind metal oxide to be selected from again: in lanthanum, spectrum, neodymium, samarium, europium, barium, strontium, calcium, magnesium, lithium, rubidium, potassium, nickel, zinc, titanium, zirconium, vanadium, copper, chromium, manganese, cobalt, iron, aluminium, the silicon, the 0.01%-6% that selected multiple metallic element gross weight is a honeycomb ceramic carrier weight.
The metallic element of wherein preferred multi-element metal oxide A group:
The metallic element of (1) at least 4 kind of metal oxide is selected from: the metallic element of lanthanum, cerium, cobalt, titanium, strontium, manganese, 7 kinds of metal oxides of copper, and its weight with the percentage that contains the binder course total weight of carrier is:
La 0.1％-10％、 Sr 0.5％-8％、
Ce 0.5％-12％、 Mn 0.4％-10％、
Co 1％-8％、 Cu 0.1％-4％、
Ti 0.15％-12％，
(2) have the metallic element of 2-6 kind metal oxide to be selected from again: in praseodymium, neodymium, samarium, europium, barium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, vanadium, chromium, nickel, iron, palladium, the platinum, selected its weight of metallic element with the percentage that contains the binder course total weight of carrier is:
Pt, Pd 0.0001%-0.05%, all the other 0.05%-6%.
The metallic element of wherein preferred multi-element metal oxide B group:
(1) metallic element of lanthanum, cerium, iron, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-5％、 Fe 1％-10％、
Ce 0.2％-10％、 Pd 0.0001％-0.05％，
(2) have the metallic element of 4-6 kind metal oxide to be selected from again: in praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, copper, manganese, nickel, cobalt, the platinum, selected its weight of metallic element with the percentage that contains A group, binder course total weight of carrier is:
Pt 0.0001%-0.05%, all the other 0.05%-6%.
A kind of catalyst that purifies motorcycle exhaust of the present invention, its composition comprises:
(1) soot preparation block
(2) major catalyst
Its composition of soot preparation block:
(1) 200 hole/inch
2Ceramic honey comb is made second carrier, and all the other features are identical with aforementioned bearer.
(2) multi-element metal oxide C group, on the second carrier hole wall, wherein contained metallic element can have the 3-8 kind, be selected from lanthanum, cerium, praseodymium, neodymium, barium, strontium, calcium, magnesium, zinc, titanium, vanadium, chromium, copper, manganese, nickel, cobalt, iron, the palladium 1%-5% that selected multiple metallic element gross weight is second vehicle weight.
The metallic element of the binder course of its composition of major catalyst of purification motorcycle exhaust and multi-element metal oxide A group is identical with the catalyst of purifying automobile tail gas of the present invention, but the weight of binder course is the 5%-20% of honeycomb ceramic carrier weight; Multiple metal oxide B group, its preferred metallic element:
(1) metallic element of lanthanum, cerium, copper, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-10％、 Cu 0.1％-1.5％、
Ce 0.2％-6％、 Pd 0.0001％-0.05％，
(2) have the metallic element of 4-6 kind metal oxide to be selected from praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, iron, manganese, cobalt, nickel, the platinum again, selected its weight of metallic element with the percentage that contains A group, binder course total weight of carrier is:
Pt 0.0001%-0.05%, all the other 0.05%-8%.
The metallic element of the binder course of its composition of catalyst of a kind of purifying industrial organic waste gas of the present invention and multi-element metal oxide A group is identical with the catalyst of purifying automobile tail gas of the present invention, but carrier is the honeycomb pottery carrier of alumina granules bead or other specifications; Multi-element metal oxide B group, its preferred metallic element:
(1) metallic element of lanthanum, cerium, manganese, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-10％、 Mn 0.5％-10％、
Ce 0.1％-8％、 Pd 0.0001％-0.05％，
(2) have the metallic element of 4-6 kind metal oxide to be selected from praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, copper, nickel, iron, the cobalt again, selected its weight of metallic element is 0.05%-6% with the percentage that contains A group, binder course total weight of carrier.
The catalyst of a kind of purifying automobile tail gas of the present invention, the catalyst that purifies motorcycle exhaust, the catalyst preparation process of purifying industrial organic waste gas comprise:
(1) on the ceramic honey comb second carrier hole wall, adhere to multi-element metal oxide C group (only being used for the soot preparation block):
The nitrate of each metallic element correspondence in the preceding described multi-element metal oxide C group is mixed with mixed aqueous solution in the desired amount, with 200 hole/inches
2Ceramic honey comb second carrier block was flooded 30-60 minute therein, take out in 80-200 ℃ the baking dry 2-6 hour, 100-750 ℃ roasting 2-8 hour.
(2) on the honeycomb ceramic carrier hole wall, adhere to binder course:
The nitrate or the oxide of each metallic element correspondence are mixed with mixed liquor in the desired amount in the multi-element metal oxide that preceding described binder course is contained, became slurries in ball milling 18-24 hour, honeycomb ceramic carrier flooded 2-20 minute therein, take out in 80-200 ℃ of baking dry 2-4 hour, low-temperature bake 2-8 hour.
(3) on binder course, adhere to multi-element metal oxide A group:
The nitrate of each metallic element correspondence in the preceding described multi-element metal oxide A group is mixed with mixed aqueous solution in the desired amount, add complexing agent (Y), A solution 2-30 minute that will adhere to the carrier impregnation ormal weight of binder course, take out in 80-200 ℃ of baking dry 2-6 hour, low-temperature bake 2-8 hour.
(4) on multi-element metal oxide A group, adhere to multi-element metal oxide B group:
The nitrate of each metallic element correspondence in the preceding described multi-element metal oxide B group is mixed with mixed aqueous solution in the desired amount, with the B solution of the above-mentioned carrier impregnation ormal weight that has adhered to metal oxide A group 2-30 minute, take out in 80-200 ℃ of baking dry 2-6 hour, low-temperature bake 2-8 hour.
(5) the above-mentioned carrier that has adhered to multi-element metal oxide A group and multi-element metal oxide B group was fed hydrogen reducing 2-5 hour in 300-500 ℃ in reduction vessel.
Another kind of preparation method comprises:
(1) it is identical with aforementioned (1) to adhere to multi-element metal oxide C group (only being used for the soot preparation block) on the honeycomb ceramic carrier hole wall.
(2) it is identical with aforementioned (2) to adhere to binder course on the honeycomb ceramic carrier hole wall.
(3) adopt one-step method on binder course, to adhere to multi-element metal oxide AB group:
The nitrate of each metallic element correspondence in the preceding described multi-element metal oxide A group is mixed with mixed aqueous solution in the desired amount, the nitrate of each metallic element correspondence in the preceding described multi-element metal oxide B group is mixed with mixed aqueous solution in the desired amount, B group solution mixes in the A group solution, add complexing agent (Y) and form even phase AB group solution, the AB that will adhere to the carrier impregnation ormal weight of binder course organizes solution 2-30 minute, take out in 80-200 ℃ of baking dry 2-6 hour, low-temperature bake 2-8 hour.
(4) reduction is identical with aforementioned (5).
Dipping ormal weight solution among the preparation method is the special quantum infusion process, and the carrier that promptly contains binder course sucks whole ormal weight solution.The ormal weight of A group solution, B group solution, AB group solution is determined with the percentage that contains A group, binder course total weight of carrier according to its weight of A group metallic element and the percentage that contains the binder course total weight of carrier, its weight of B group metallic element.
Low-temperature bake temperature among the preparation method is 100-500 ℃.
Complexing agent described in the preparation method (Y) can be organic acid, as citric acid, hydroxysuccinic acid, gluconic acid or tartaric acid etc., and can cause catalytic active component to have the organic or inorganic complex salt of well loaded and distribution on carrier.
Can make three kinds of cleaning catalysts of the present invention through above step, wherein binder course improved effectively active component on carrier in conjunction with fastness; Rare earth multicomponent multi-element metal oxide A group, B group have good activity, heat endurance and thermal-shock resistance, and stronger anti-lead poisoning ability is arranged, and using under the relatively poor situation of doped fuel and vehicle condition, still can reach ten thousand kilometers of 3-5 service life; Minute amount of noble metal has improved the low temperature active of catalyst significantly, and the A-B composite catalyst is cheap, and its excellent CO, HC, NOx triple effect clean-up effect can compare favourably with pure noble metal platinum-rhodium catalyst.One of the catalyst composition of purification motorcycle exhaust soot gives a large amount of soots that produce when processing block blocks motorcycle initiating effectively, and soot is decomposed gasification; And prevent that oil gas from sticking on the major catalyst surface, avoids the major catalyst high temperature sintering; Make the charge air flow distributed uniform simultaneously, more help the redox of major catalyst pollutant.
The catalyst that makes by the present invention is contained in Wuxi City power and reaches in the JJX type purifying vehicle exhaust silencer that silencer company produces; repeatedly in the Second Automobile Works technique center, Tianjin Cera, each province's environmental monitoring station carried out a large amount of emission tests, be listed in State Bueau of Environmental Protection Vehicle Emission Control equipment quality supervision and inspection center below and carry out the strict result who detects.
Report number WTP-96-28
Test situation
15 operating modes discharging comparison test and idle exhaust emission comparison test are carried out on goddess's board JB6480F type automobile, at first carry out the test of former Che Shiwu operating mode emission testing and idle exhaust emission, pull down former car silencer then and change JJX type purifying vehicle exhaust silencer and carry out the test of 15 operating mode emission testings and idle exhaust emission again.
Test basis
GB11642-89 " light-duty vehicle exhaust contaminant method of testing "
GB4759-84 " exhaust silencer for internal-combustion engine measuring method "
GB/T3845-93 " measurement of gasoline car exhaust contaminant, idling method "
JB3743-84 " automobile engine method for testing performance "
Testing equipment
Exhaust gas analyzer U.S. MILTON ROY
Constant volume sampler CVS-103 Japan YANACO
Chassis dynamometer DCE-80 U.S. CLAYTON
Electric dynamometer FEB-DHC Japan is bright
The little open country of fuel consumption meter DF-312 Japan
Idling exhaust analyzer MEXA-324F Foshan Analyzer Factory
Result of the test
15 operating mode emission testing unit: g/ test
JJX type purifying vehicle exhaust silencer to three kinds of noxious emission clean-up effects that use doped fuel to discharge is: the HC purifying rate is 85.3%, the CO purifying rate is 81.9%, the NOx purifying rate is 86.6%.The HC+NOx purifying rate is 86%.The idle exhaust emission test
| CO(％) | HC(PPm) | |
| Former car | 2.8 | 1000 |
| The dress sample | 0.01 | 20 |
| Purifying rate | 99.6％ | 98％ |
Enumerate following examples (scope of the present invention is not had any restriction):
The weight ratio of any metal oxide what follows or metal nitrate, chlorate, can converse this metallic element in active component percentage by weight and the percentage of weight and honeycomb ceramic carrier weight or with the percentage that contains the binder course total weight of carrier.
Example 1
With 20 part of one water aluminium oxide
6 parts of kaolin
12 parts of aluminium glues
2 parts of V
2O
5
1 part of B
2O
3
0.5 part Fe (NO
3)
39H
2O
1.8 part Ce (NO
3)
36H
2O
50 parts of H
2O is mixed with mixed liquor, ball milling became slurries in 20 hours in ball grinder, and the honeycomb ceramic carrier of 200 holes/in2 is immersed in the slurries 5～20 minutes, took out the back and blew away surplus slurry with compressed air, in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings promptly obtained containing the binder course carrier in 6 hours.
To contain the immersion of binder course carrier contains:
5 parts of La (NO
3)
36H
2O
7.4 part Ce (NO
3)
36H
2O
10 parts of Co (NO
3)
26H
2O
2 parts of Ni (NO
3)
26H
2O
3.2 part Cu (NO
3)
23H
2O
5.6 part Zr (NO
3)
45H
2O
2.4 part Sr (NO
3)
2, 9.5 parts of TiCl
3(20%)
1.5 part Cr (NO
3)
39H
2O
1.5 the ormal weight A of part complexing agent (Y) group solution 20 minutes takes out in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings 5 hours make to contain the binder course carrier and adhere to composite metal oxide A group, it immersion are contained again:
6.2 part La (NO
3)
36H
2O
3.1 part Ce (NO
3)
36H
2O
30 parts of Fe (NO
3)
39H
2O
0.08 part Pd (NO
3)
22H
2O
1.8 part Zn (NO
3)
26H
2O
3.2 part Cu (NO
3)
23H
2O
1.1 part Ba (NO
3)
2
0.02 part PtCl
4Ormal weight B group solution 20 minutes, take out in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings 6 hours, make and adhere to composite metal oxide B group on the composite metal oxide A group, then in reduction vessel 300～500 ℃ fed hydrogen reducing 3 hours, make cleaning catalyst for tail gases of automobiles of the present invention.
Example 2
With 200 order/inches
2Honeycomb ceramic carrier immerses and contains:
1.25 part La (NO
3)
36H
2O
6 parts of Co (NO
3)
26H
2O
5 parts of Ni (NO
3)
26H
2O
0.02 part Pd (NO
3)
22H
2In the C of the O group solution 60 minutes, to take out in dry 3 hours of 80～160 ℃ of bakings, 100～400 ℃ of roastings 2 hours contain it immersion again
1.25 part La (NO
3)
36H
2O
6 parts of Co (NO
3)
26H
2O
5 parts of Ni (NO
3)
26H
2In the C of the O group solution 60 minutes, take out in dry 3 hours of 80～160 ℃ of bakings 500～750 ℃ of roastings 2～4 hours.The soot that makes in the motorcycle tail gas cleaning catalyst of the present invention gives processing block.
With example 1 similar just general
5 parts of La (NO
3)
36H
2O
7.4 part Ce (NO
3)
36H
2O
10 parts of Co (NO
3)
26H
2O
2 parts of Ni (NO
3)
26H
2O
10 parts of Mn (NO
3)
26H
2O (50%)
5.6 part Zr (NO
3)
45H
2O
2.4 part Sr (NO
3)
2
4.6 part Cr (NO
3)
39H
2O is mixed with A group solution.
With 6.2 parts of La (NO
3)
36H
2O
3.1 part Ce (NO
3)
36H
2O
11 parts of Cu (NO
3)
33H
2O
0.1 part Pd (NO
3)
22H
2O
40 parts of Mn (NO
3)
26H
2O (50%)
6 parts of LiNO
3
1.8 part Zn (NO
3)
26H
2O
0.01 part PtCl
4Be mixed with B group solution.
B group solution mixes A group solution, and add 1.5 parts of complexing agents (Y), to contain the ormal weight solution 20 minutes that the binder course carrier immerses the AB group, take out in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings 6 hours, make to contain the binder course carrier and adhere to composite metal oxide AB group, then in reduction vessel 300～500 ℃ fed hydrogen reducing 3 hours.Make the major catalyst in the motorcycle tail gas cleaning catalyst of the present invention.
Example 3 is similar with example 1, just will contain the immersion of binder course carrier and contain:
5 parts of La (NO
3)
36H
2O
7.4 part Ce (NO
3)
36H
2O
10 parts of Co (NO
3)
26H
2O
2 parts of Ni (NO
3)
26H
2O
3.2 part Cu (NO
3)
23H
2O
8.4 part Zr (NO
3)
45H
2O
3.8 part Sr (NO
3)
2
1.5 part Cr (NO
3)
39H
2O
1.5 the ormal weight aqueous solution of part complexing agent (Y) 20 minutes takes out in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings 5 hours make to contain the binder course carrier and adhere to composite metal oxide A group, it immersion are contained again
6.2 part La (NO
3)
36H
2O
3.1 part Ce (NO
3)
36H
2O
30 parts of Ni (NO
3)
26H
2O
0.15 part Pd (NO
3)
22H
2O
20.8 part Mn (NO
3)
26H
2O (50%)
8 parts of Cr (NO
3)
39H
2O
10 parts of Co (NO
3)
26H
2O
1 part of Rb NO
3Ormal weight B group solution 20 minutes, obtain in dry 3 hours of 80～160 ℃ of bakings, 200～500 ℃ of roastings 6 hours make and adhere to composite metal oxide B group on the composite metal oxide A group.In reduction vessel, 300～500 ℃ fed hydrogen reducing 3 hours then.Make purifying industrial organic waste gas catalyst of the present invention.
Claims (7)
1, a kind of catalyst that is used for purification of exhaust gases of internal combustion engines and/or industrial waste gas, it is characterized in that described catalyst is a kind of whole shape, with multi-element metal oxide and light rare earth is main components by weight percent, add the oxidation-reduction catalyst of minute amount of noble metal platinum-palladium or palladium, described catalyst is made of separately major catalyst or major catalyst constitutes with the soot preparation block again, wherein said major catalyst is by carrier, binder course and attached to the multi-element metal oxide A on binder course group thing, reduce to handle attached to the whole logical hydrogen of multi-element metal oxide B group thing on the A group thing layer again and form, or by carrier, binder course and one-step method are reduced to handle attached to the whole logical hydrogen of the group of the multi-element metal oxide AB on binder course thing and are formed; Wherein:
(1) carrier: honeycomb ceramic carrier: main component cordierite content＞90%, diameter or monolateral length≤260mm, hole order≤400 hole/inches
2, percent opening 35%-60%, specific area 0.5-2.0m
2/ g, bulk density 0.5-0.7g/cm
3, water absorption rate 21%-30%, or alumina granules bead;
(2) binder course: wherein contained metallic element has the 4-8 kind, is selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal, and the weight of binder course is the 3%-20% of vehicle weight, and selective metal oxide and metallic element comprise:
The metallic element of 2-4 kind metal oxide is selected from: cerium, boron, a water aluminium oxide, kaolin, and the percentage of its weight and vehicle weight is:
Cerium 0.1%-10%, a water aluminium oxide 3%-20%,
Boron 0.2%-3%, kaolin 1%-15%,
Have the metallic element of 2-6 kind metal oxide to be selected from again: in lanthanum, praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, lithium, rubidium, potassium, nickel, zinc, titanium, zirconium, vanadium, chromium, copper, manganese, cobalt, iron, aluminium, the silicon, the 0.01%-6% that selected multiple metallic element gross weight is a vehicle weight;
The nitrate or the oxide of each metallic element correspondence in the selected binder course multi-element metal oxide are mixed with mixed aqueous solution in the desired amount, became slurries, carrier is flooded, takes out dry, the roasting of baking more therein in ball milling 18-24 hour;
(3) multi-element metal oxide A group: wherein contained metallic element has the 6-10 kind, be selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal, selected multiple metallic element gross weight is the 4%-15% that contains the binder course total weight of carrier, and selective metallic element is:
The metallic element of at least 4 kinds of metal oxides is selected from: the metallic element of lanthanum, cerium, cobalt, titanium, strontium, manganese, 7 kinds of metal oxides of copper, and its weight with the percentage that contains the binder course total weight of carrier is:
La 0.1％-10％、 Sr 0.5％-8％、
Ce 0.5％-12％、 Mn 0.4％-10％、
Co 1％-8％、 Cu 0.1％-4％、
Ti 0.15％-12％，
There is the metallic element of 2-6 kind metal oxide to be selected from praseodymium, neodymium, samarium, europium, barium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, vanadium, chromium, nickel, iron, palladium, the platinum again, wherein palladium is essential element, and its weight of selected metallic element with the percentage that contains the binder course total weight of carrier is:
Pt, Pd 0.0001%-0.05%, all the other 0.05%-6%;
(4) multi-element metal oxide B group: wherein contained metallic element has the 8-10 kind, be selected from rare earth metal, alkali metal or alkaline-earth metal, the transition metal, selected multiple metallic element gross weight is to contain the 2%-12% of A group in interior binder course total weight of carrier;
(5) multi-element metal oxide AB group: the nitrate of each metallic element correspondence in the described multi-element metal oxide A group is mixed with mixed aqueous solution in the desired amount, the nitrate of each metallic element correspondence in the described multi-element metal oxide B group is mixed with mixed aqueous solution in the desired amount, B group solution mixes in the A group solution, adds complexing agent (Y) and forms even phase AB group solution; Described complexing agent (Y) is citric acid, hydroxysuccinic acid, gluconic acid or tartaric acid, the AB that will adhere to the carrier impregnation ormal weight of binder course organizes solution 2-30 minute, take out in 80-200 ℃ of baking dry 2-6 hour, obtained multi-element metal oxide AB and organize in low-temperature bake 2-8 hour;
(6) its composition of soot preparation block: 200 hole/inches
2Ceramic honey comb is made second carrier, multi-element metal oxide C group, on the second carrier hole wall, wherein contained metallic element can have the 3-8 kind, be selected from lanthanum, cerium, praseodymium, neodymium, barium, strontium, calcium, magnesium, zinc, titanium, vanadium, chromium, copper, manganese, nickel, cobalt, iron, the palladium 1%-5% that selected multiple metallic element gross weight is second vehicle weight.
2, according to the described catalyst of claim 1, it is characterized in that being used for the catalyst of purifying automobile tail gas, constitute separately by major catalyst, its:
(1) carrier: honeycomb ceramic carrier,
(2) binder course weight is the 3%-15% of vehicle weight,
(3) multi-element metal oxide B group, selective metallic element is:
The metallic element of lanthanum, cerium, iron, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-5％、 Fe 1％-10％、
Ce 0.2％-10％、Pd 0.0001％-0.05％，
There is the metallic element of 4-6 kind metal oxide to be selected from again: in praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, copper, manganese, nickel, cobalt, the platinum, selected metallic element, its weight with the percentage that contains A group, binder course total weight of carrier is:
Pt 0.0001%-0.05%, all the other 0.05%-6%.
3, according to the described catalyst of claim 1, it is characterized in that being used to purify the catalyst of motorcycle exhaust, constitute by soot preparation block and major catalyst, its:
(1) soot preparation block: with 200 hole/inches
2Ceramic honey comb make second carrier, multi-element metal oxide C group, on the second carrier hole wall, wherein contained metallic element has the 3-8 kind, be selected from: in lanthanum, cerium, praseodymium, neodymium, barium, strontium, calcium, magnesium, zinc, titanium, vanadium, chromium, copper, manganese, nickel, cobalt, iron, the palladium, the 1%-5% that selected multiple metallic element gross weight is second vehicle weight
(2) binder course weight is the 5%-20% of vehicle weight,
(3) multiple metal oxide B group, selective metallic element is:
The metallic element of lanthanum, cerium, copper, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-10％、 Cu 0.1％-1.5％、
Ce 0.2％-6％、 Pd 0.0001％-0.05％，
Have the metallic element of 4-6 kind metal oxide to be selected from again: in praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, iron, manganese, nickel, cobalt, the platinum, selected its weight of metallic element with the percentage that contains A group, binder course total weight of carrier is:
Pt 0.0001%-0.05%, all the other 0.05%-8%.
4, according to the described catalyst of claim 1, it is characterized in that being used for the catalyst of purifying industrial organic waste gas, constitute separately by major catalyst, its:
(1) carrier: select alumina granules bead or honeycomb ceramic carrier for use,
(2) binder course weight is the 3%-15% of total weight of carrier,
(3) multi-element metal oxide B group, selective metallic element is:
The metallic element of lanthanum, cerium, manganese, 4 kinds of metal oxides of palladium, its weight with the percentage that contains A group, binder course total weight of carrier is:
La 0.1％-10％、Mn 0.5％-10％、
Ce 0.1％-8％、Pd 0.0001％-0.05％，
Have the metallic element of 4-6 kind metal oxide to be selected from again: in praseodymium, neodymium, samarium, europium, barium, strontium, calcium, magnesium, rubidium, lithium, potassium, zirconium, zinc, titanium, vanadium, chromium, copper, iron, cobalt, the nickel, selected its weight of metallic element is 0.05%-6% with the percentage that contains A group, binder course total weight of carrier.
5, a kind of Preparation of catalysts method that is used for purification of exhaust gases of internal combustion engines and/or industrial waste gas as claimed in claim 1 is characterized in that described method comprises:
Make major catalyst
(1) adheres to binder course: the nitrate or the oxide of each metallic element correspondence in the selected binder course multi-element metal oxide are mixed with mixed aqueous solution in the desired amount, became slurries in ball milling 18-24 hour, carrier was flooded 2-20 minute therein, take out in 80-200 ℃ the baking dry 2-4 hour, 100-500 ℃ roasting 2-8 hour;
(2) adhere to multi-element metal oxide A group: the nitrate of each metallic element correspondence in the selected multi-element metal oxide A group is mixed with mixed aqueous solution in the desired amount, add complexing agent (Y), A solution 2-30 minute that will adhere to the carrier impregnation ormal weight of binder course, take out in 80-200 ℃ the baking dry 2-6 hour, 100-500 ℃ roasting 2-8 hour;
(3) adhere to multi-element metal oxide B group: the nitrate of each metallic element correspondence in the selected multi-element metal oxide B group is mixed with mixed aqueous solution in the desired amount, B solution 2-30 minute that will adhere to the carrier impregnation ormal weight of A group thing, take out in 80-200 ℃ the baking dry 2-6 hour, 100-500 ℃ roasting 2-8 hour;
(4) hydrogen reducing is handled: the carrier that will adhere to A group thing, B group thing fed hydrogen reducing 2-5 hour in 300-500 ℃ in reduction vessel;
Make the soot preparation block: multi-element metal oxide C is organized attached on second carrier, the nitrate of each metallic element correspondence is mixed with mixed aqueous solution in the desired amount in the selected multi-element metal oxide C group, the second carrier ceramic honey comb piece was flooded 30-60 minute therein, take out in 80-200 ℃ the baking dry 2-6 hour, 100-750 ℃ roasting 2-8 hour.
6, preparation method as claimed in claim 5, it is characterized in that adhering to A group thing, B organizes thing, adopt one-step method to adhere to multi-element metal oxide AB group: with the nitrate of each metallic element correspondence in selected A group thing, the B group thing, grouping in the desired amount is mixed with two groups of mixed aqueous solutions of A, B, B is organized solution to be mixed in the A group solution, add complexing agent (Y) and form even phase AB group solution, AB solution 2-30 minute that will adhere to the carrier impregnation ormal weight of binder course, take out in 80-200 ℃ the baking dry 2-6 hour, 100-500 ℃ roasting 2-8 hour.
7, according to claim 5 or 6 described preparation methods, it is characterized in that described dipping ormal weight solution is the special quantum infusion process, the carrier that has promptly adhered to binder course sucks whole ormal weight solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB981111556A CN100457238C (en) | 1998-02-22 | 1998-02-22 | Catalyst for purifying IC engine tail gas and/or industrial waste gas |
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| CNB981111556A CN100457238C (en) | 1998-02-22 | 1998-02-22 | Catalyst for purifying IC engine tail gas and/or industrial waste gas |
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| CN100457238C true CN100457238C (en) | 2009-02-04 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3845274B2 (en) * | 2001-06-26 | 2006-11-15 | ダイハツ工業株式会社 | Exhaust gas purification catalyst |
| CN100340327C (en) * | 2003-01-24 | 2007-10-03 | 中国矿业大学(北京) | Catalyst for managing NDx and carbon smoke in exhausts of diesel motor as well as its preparation |
| CN100343491C (en) * | 2004-06-02 | 2007-10-17 | 中国科学院金属研究所 | Electric direct heating type three-efficiency purifier for automobile exhaust |
| TWI409104B (en) * | 2004-07-15 | 2013-09-21 | Nikki Universal Co Ltd | A catalyst for purifying exhaust gas containing organic nitrides and a method for purifying the exhaust gas |
| CN100427208C (en) * | 2006-01-19 | 2008-10-22 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
| CN101444741B (en) * | 2009-01-04 | 2011-07-20 | 上海大学 | Preparation method of stainless steel carrier catalysts and coating process |
| CN102240560B (en) * | 2011-04-28 | 2013-05-01 | 北京化工大学 | Composite catalyst used for catalytic combustion of organic waste gas as well as preparation method and application thereof |
| WO2013123622A1 (en) * | 2012-02-24 | 2013-08-29 | Ding Yuntao | Ion treatment method for preventing carbon deposition on gasoline engine valve, fuel injection nozzle and spark plug |
| CN104981289A (en) * | 2013-02-08 | 2015-10-14 | 优美科触媒日本有限公司 | Catalyst for purifying NOX occlusion reduction-type exhaust gas and exhaust gas purification method using said catalyst |
| CN105736093B (en) * | 2016-03-02 | 2018-04-10 | 吴振华 | A kind of polynary nanometer rare earth catalyst tail gas cleaner for motor-driven vehicle and its manufacture method |
| CN106014583A (en) * | 2016-07-06 | 2016-10-12 | 世嘉宝科技（天津）有限公司 | Manufacturing method for catalysis ceramic tube and automobile exhaust purification device adopting tube |
| CN108947097B (en) * | 2017-05-27 | 2021-10-22 | 宝山钢铁股份有限公司 | Ozone biochemical coupling treatment method and device for leveling liquid wastewater |
| CN110295986A (en) * | 2019-07-03 | 2019-10-01 | 河北工业大学 | A kind of diesel engine exhaust gas treatment device and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1042092A (en) * | 1988-10-26 | 1990-05-16 | 中国科学院生态环境研究中心 | A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1042092A (en) * | 1988-10-26 | 1990-05-16 | 中国科学院生态环境研究中心 | A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof |
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