CN104923317B - Regeneration device and process of anti-aging catalyst for lean-burn natural gas truck - Google Patents
Regeneration device and process of anti-aging catalyst for lean-burn natural gas truck Download PDFInfo
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- CN104923317B CN104923317B CN201510316208.9A CN201510316208A CN104923317B CN 104923317 B CN104923317 B CN 104923317B CN 201510316208 A CN201510316208 A CN 201510316208A CN 104923317 B CN104923317 B CN 104923317B
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- reaction tube
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a regeneration device and process of an anti-aging catalyst for a lean-burn natural gas truck. The regeneration device comprises a reaction tube and a reaction furnace, wherein the reaction furnace is sleeved by the reaction tube; a gas inlet and a gas mixing chamber are formed in the gas inlet end of the reaction tube; a plurality of apertures are formed in the side wall of the gas mixing chamber; a slot allowing a thermocouple to be placed therein is formed in the gas outlet end of the reaction tube; a metal filter screen used for placing a catalyst is arranged in the reaction tube. The regeneration process comprises the following steps: at first, pretreating the anti-aging catalyst for the lean-burn natural gas truck and then placing the pretreated anti-aging catalyst in the regeneration device, charging a reaction gas including CH4, CO, NOX and CO2 into the reaction tube, charging O2, and heating up the reacting furnace to be 450-600 DEG C for 15-120 min when the mass ratio of CH4 to O2 is 1.35-1.55. The regeneration device is simple in structure and compact in design, the regeneration technological process steps are convenient to operate, the catalytic performance of the regenerated catalyst can be effectively improved, and a wide application prospect is achieved.
Description
Technical field
The present invention relates to a kind of renovation process of aging state lean-burn type natural gas automotive catalyst, belongs to catalyst preparation skill
Art field.
Background technology
At present, lean burn natural gas car quickly grows, and in China, lean-burn type natural gas vehicle accounts for the 70% of gas-fueled vehicles recoverable amount
More than.Although lean burn natural gas automobile has significantly discharge advantage and fuel economy, contain in its tail gas and be most difficult to oxygen
The catalyst of the hydro carbons-methane of change, the higher catalytic temperature of needs and catalysis activity.But lean burn natural gas engine tail gas temperature
Usually less than 600 DEG C of degree, and have very big to the activity of catalyst containing the material such as substantial amounts of vapor and sulfur dioxide in tail gas
Inhibitory action, particularly active component Pd in lean burn natural gas catalyst be easy to sulphur combination, cause catalyst activity reduction,
The requirement of national legislation durability can not be met.It has been investigated that, lean burn natural gas catalyst is easily aging by sulphur, even if CNG combustions
There is the sulfur content of 1ppm in gas, catalyst is also easy to be aging, it is final to have than relatively low conversion ratio.It is natural for lean-burn type
The present situation of gas automotive catalyst ageing resistace difference, many research institutions have carried out coating exploitation, it is therefore an objective to improve lean-burn natural
The hot sulphur ageing properties of water resistant of gas catalyst, meet emission regulation demands, and lean-burn type natural gas catalyst is needed using substantial amounts of
Precious metals pd and Pt, in general, in gas fuel is ensured on the premise of sulfur content, need to use 250g/ft3More than
Noble-metal-supported amount is only possible to meet the requirement of Abgasgesetz, and catalyst is with high costs and risk is larger.
The content of the invention
The invention aims to solve lean-burn type natural gas vehicle catalyst preparation high cost and ageing resistace is poor
Problem, there is provided a kind of aging state lean-burn type natural gas vehicle catalyst regeneration device and regeneration technology, urging after regeneration
Agent catalytic performance is good.
The present invention is adopted the following technical scheme that：A kind of aging state lean-burn type natural gas vehicle catalyst regeneration device, including
Reaction tube and reacting furnace, the reaction tube is sheathed in reacting furnace, and one end of the reaction tube is inlet end, the reaction tube
The other end is outlet side, and the inlet end is provided with air inlet, and one end of the air inlet is connected with gas mixing chamber, described
The other end of air inlet is connected by air inlet pipe with gas mixing tank, and the gas mixing chamber is arranged in reaction tube and gas is mixed
Some apertures are provided with the side wall for closing chamber, the port of export is provided with slot for placing thermocouple, sets in the reaction tube
Metal filter is equipped with for placing catalyst, between the catalyst and reaction tube wall asbestos layer is provided with.
Further, lower end 25～30cm of the metal filter apart from gas mixing chamber.
Further, the thermocouple top and the distance of metal filter are 2～10mm.
Used with the aging state lean-burn type natural gas vehicle that catalyst regeneration device is realized using aging state lean-burn type natural gas vehicle
Catalyst regeneration process, comprises the steps：
（1）The lean-burn type natural gas automotive catalyst of aging state is taken initially with compressed air purging surface and duct
Dust, the catalyst after purging is put in quartz tube furnace and is pre-processed, and is passed through N in quartz tube furnace first2, then
Quartz tube furnace is heated, temperature control is 150～200 DEG C, the heat time is 10～15min, stops heating, uses N2Blow
Sweeping makes in quartz tube furnace greenhouse cooling to 20～25 DEG C.
（2）The lean-burn type natural gas automotive catalyst of pretreated aging state is taken out from tubular quartz stove, asbestos are used
Parcel, on the metal filter inserted in reaction tube, the 5～10min of reacting gas being well mixed is passed through in reaction tube to guarantee
Atmosphere is stablized, with N in reaction tube2For Balance Air, then O is passed through in reaction tube2The content of each component in reacting gas is adjusted,
Wherein CH4And O2Between quality ratio be λ, after λ stablizes 1～2min, reacting furnace is heated, heating-up temperature be 450～
600 DEG C, the heat time is 15～120min；
（3）After reaction terminates, continue to be passed through N in reaction tube2Reaction tube is set to be cooled to 20～25 DEG C, then in reaction tube
In to process after aging state lean-burn type natural gas automotive catalyst carry out the test of each temperature spot conversion ratio and performance.
Further, the step（2）In N2 be High Purity Nitrogen of the purity more than or equal to 99.99%, air speed is controlled to 4000
～4500/h.
Further, the step（2）The size of λ value is 1.35～1.55.
Further, step（2）Reacting gas air speed in middle reacting furnace is 39960～40000/h.
Further, the step（2）Middle reacting gas need to be well mixed in gas mixing tank, the group in reacting gas
Dividing includes CH4、CO、NOXAnd CO2。
The regenerating unit simple structure of the present invention, compact to design, easy to use, regeneration technology process step is easy to operation,
The catalytic performance of the catalyst after regeneration can be effectively improved, the active ingredient of catalyst surface is not lost, is answered with extensive
Use prospect.
Description of the drawings
Fig. 1 is the structural representation of aging state lean-burn type natural gas vehicle catalyst regeneration device in the present invention.
Fig. 2 be embodiment one in regeneration technology process after lean-burn type natural gas automotive catalyst at different temperatures turn
Rate result.
Fig. 3 be embodiment two in regeneration technology process after lean-burn type natural gas automotive catalyst at different temperatures turn
Rate result.
Fig. 4 be embodiment three in regeneration technology process after lean-burn type natural gas automotive catalyst at different temperatures turn
Rate result.
Reference：Reaction tube 1, reacting furnace 2, air inlet 3, gas mixing chamber 4, metal filter 5, asbestos layer 6, gas outlet
7th, slot 8.
Specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in figure 1, a kind of aging state lean-burn type natural gas vehicle catalyst regeneration device, including reaction tube 1 and reaction
Stove 2, reaction tube 1 is sheathed in reacting furnace 2, and one end of reaction tube 1 is inlet end, and the other end of reaction tube is outlet side, air inlet
End is provided with air inlet 3, and one end of air inlet 3 is connected with gas mixing chamber 4, the other end of air inlet 3 by air inlet pipe and
Gas mixing tank connects, and gas mixing chamber 4 is arranged in reaction tube 1 and is provided with some apertures on the side wall of gas mixing chamber 4,
Metal filter 5 is provided with reaction tube for placing catalyst, the port of export is provided with slot 8 for placing thermocouple, thermocouple
The distance of top and metal filter 5 is 2～10mm, metal filter 5 apart from gas mixing chamber 25～30cm of lower end, catalyst with
Asbestos layer 6 is provided between reaction tube wall.
Embodiment one：Aging state lean-burn type natural gas vehicle catalyst regeneration process, comprises the steps：
（1）The lean-burn type natural gas automotive catalyst of aging state is taken initially with compressed air purging surface and duct
Dust, the catalyst after purging is put in quartz tube furnace and is pre-processed, and is passed through N in quartz tube furnace first2, to stone
English tube furnace carries out heating and temperature control for 150 DEG C, and the heat time is 10min, then stops heating, uses N2Purging makes quartz ampoule
Greenhouse cooling is to 20 DEG C in formula stove.N2For High Purity Nitrogen of the purity more than or equal to 99.99%, air speed is controlled to 4000/h.
（2）Catalyst is taken out from tubular quartz stove, is wrapped up with asbestos, on the metal filter inserted in reaction tube, to anti-
Ying Guanzhong is passed through the reacting gas 5min being well mixed and is stablized with guaranteeing atmosphere, and reacting gas mixes in gas mixing tank
Even, the component in reacting gas includes CH4、CO、NOXAnd CO2；With N in reaction tube2For Balance Air, then it is passed through in reaction tube
O2Adjust the content of each component in reacting gas, wherein CH4And O2Between the ratio of quality be λ, treat that λ is stable 1.35, heating
After 1min, reacting furnace is heated, heating-up temperature is 450 DEG C, and the heat time is 15min, and the air speed in reaction tube is
40000/h；
（3）After reaction terminates, continue to be passed through N in reaction tube2Reaction tube is set to be cooled to 20 DEG C, it is then right in reaction tube
Lean-burn type natural gas automotive catalyst after regeneration carries out the test of each temperature spot conversion ratio and performance.
Embodiment two：Aging state lean-burn type natural gas vehicle catalyst regeneration process, comprises the steps：
（1）The lean-burn type natural gas automotive catalyst of aging state is taken initially with compressed air purging surface and duct
Dust, the catalyst after purging is put in quartz tube furnace and is pre-processed, and is passed through N in quartz tube furnace first2, quartz
The temperature control of tube furnace is 175 DEG C, is heated, and the heat time is 12min, then stops heating, uses N2Purging makes quartz
Greenhouse cooling is to 25 DEG C in tube furnace.N2For High Purity Nitrogen of the purity more than or equal to 99.99%, air speed is controlled to 4200/h.
（2）Catalyst is taken out from tubular quartz stove, is wrapped up with asbestos, on the metal filter inserted in reaction tube, to anti-
Ying Guanzhong is passed through the reacting gas 8min being well mixed and is stablized with guaranteeing atmosphere, and reacting gas mixes in gas mixing tank
Even, the component in reacting gas includes CH4、CO、NOXAnd CO2；With N in reaction tube2For Balance Air, then it is passed through in reaction tube
O2Adjust the content of each component in reacting gas, wherein CH4And O2Between the ratio of quality be λ, treat that λ is stable 1.45, heating
After 2min, reacting furnace is heated, heating-up temperature is 600 DEG C, and the heat time is 30min, and the air speed in reaction tube is
40000/h；
（3）After reaction terminates, continue to be passed through N in reaction tube2Reaction tube is set to be cooled to 25 DEG C, it is then right in reaction tube
Lean-burn type natural gas automotive catalyst after regeneration carries out the test of each temperature spot conversion ratio and performance.
Embodiment three：Aging state lean-burn type natural gas vehicle catalyst regeneration process, comprises the steps：
（1）The lean-burn type natural gas automotive catalyst of aging state is taken initially with compressed air purging surface and duct
Dust, the catalyst after purging is put in quartz tube furnace and is pre-processed, and is passed through N in quartz tube furnace first2, quartz
The temperature control of tube furnace is 200 DEG C, is heated, and the heat time is 15min, then stops heating, uses N2Purging makes quartz
Greenhouse cooling is to 25 DEG C in tube furnace.N2For High Purity Nitrogen of the purity more than or equal to 99.99%, air speed is controlled to 4500/h.
（2）Catalyst is taken out from tubular quartz stove, is wrapped up with asbestos, on the metal filter inserted in reaction tube, to anti-
Ying Guanzhong is passed through the reacting gas 10min being well mixed and is stablized with guaranteeing atmosphere, and reacting gas mixes in gas mixing tank
Even, the component in reacting gas includes CH4、CO、NOXAnd CO2；With N in reaction tube2For Balance Air, then it is passed through in reaction tube
O2Adjust the content of each component in reacting gas, wherein CH4And O2Between the ratio of quality be λ, treat that λ is stable 1.55, heating
After 2min, reacting furnace is heated, heating-up temperature is 550 DEG C, and the heat time is 120min, and the air speed in reaction tube is
40000/h；
（3）After reaction terminates, continue to be passed through N in reaction tube2Reaction tube is set to be cooled to 25 DEG C, it is then right in reaction tube
Lean-burn type natural gas automotive catalyst after regeneration carries out the test of each temperature spot conversion ratio and performance.
Test result：
Choose respectively in fresh state catalyst, aging state catalyst and embodiment that before processing is regenerated in each embodiment and regenerate
Lean-burn type natural gas automotive catalyst afterwards carries out the test of each temperature spot conversion ratio and performance, the lean-burn type natural gas after regeneration
Automotive catalyst is activated state catalyst, as a result as shown in Fig. 2, Fig. 3 and Fig. 4.
As shown in Figure 2：450 DEG C of conversion ratios of fresh state catalyst are 100%, after aging, 450 DEG C of aging state catalyst
Conversion ratio drops to 74%, and after activating and regenerating, 450 DEG C of conversion ratios of activated state catalyst are 90%, and activated state catalyst is older
Change state 450 DEG C of conversion ratios of catalyst and improve 16%.
As shown in Figure 3：With the rising of temperature, activated state Catalyst Conversion is improved constantly, and is 350～450 in temperature
Under the conditions of DEG C, the conversion ratio of activated state catalyst is identical with the conversion ratio of fresh state catalyst, and at 450 DEG C, conversion ratio reaches
The conversion ratio of aging state catalyst under more than 99%, and significantly larger than equal temperature.
As shown in Figure 4：With the rising of temperature, conversion ratio is improved constantly, and conversion ratio is 95% under the conditions of 450 DEG C, slightly less than
The conversion ratio of fresh state catalyst.
Claims (7)
1. a kind of aging state lean-burn type natural gas vehicle catalyst regeneration device, it is characterised in that：Including reaction tube（1）And reaction
Stove（2）, the reaction tube（1）It is sheathed in reacting furnace, the reaction tube（1）One end be inlet end, the reaction tube（1）'s
The other end is outlet side, and the inlet end is provided with air inlet（3）, the air inlet（3）One end and gas mixing chamber（4）Phase
Connection, the air inlet（3）The other end be connected with gas mixing tank by air inlet pipe, the gas mixing chamber（4）It is arranged at
Reaction tube（1）Interior and gas mixing chamber（4）Side wall on be provided with some apertures, the port of export is provided with slot（8）For placing
Thermocouple, the reaction tube（1）Inside it is provided with metal filter（5）For placing catalyst, the catalyst and reaction tube（1）Wall
Between be provided with asbestos layer（6）.
2. aging state lean-burn type natural gas vehicle catalyst regeneration device as claimed in claim 1, it is characterised in that：The gold
Lower end 25～30cm of the category filter apart from gas mixing chamber.
3. aging state lean-burn type natural gas vehicle catalyst regeneration device as claimed in claim 1, it is characterised in that：The heat
Galvanic couple top is 2～10mm with the distance of metal filter.
4. the aging state lean-burn realized with catalyst regeneration device using the aging state lean-burn type natural gas vehicle described in claim 1
Type natural gas vehicle catalyst regeneration process, it is characterised in that：Comprise the steps：
（1）The lean-burn type natural gas automotive catalyst of aging state is taken initially with compressed air purging surface and the ash in duct
Dirt, the catalyst after purging is put in quartz tube furnace and is pre-processed, and is passed through N in quartz tube furnace first2, it is then right
Quartz tube furnace is heated, and temperature control is 150～200 DEG C, and the heat time is 10～15min, stops heating, uses N2Purging
Greenhouse cooling is made in quartz tube furnace to 20～25 DEG C；
（2）The lean-burn type natural gas automotive catalyst of pretreated aging state is taken out from tubular quartz stove, is wrapped up with asbestos,
On the metal filter inserted in reaction tube, the 5～10min of reacting gas being well mixed is passed through in reaction tube steady to guarantee atmosphere
It is fixed, with N in reaction tube2For Balance Air, then O is passed through in reaction tube2Adjust the content of each component in reacting gas, wherein CH4
And O2Between quality ratio be λ, after λ stablizes 1～2min, reacting furnace is heated, heating-up temperature be 450～600 DEG C,
Heat time is 15～120min；
（3）After reaction terminates, continue to be passed through N in reaction tube2Reaction tube is set to be cooled to 20～25 DEG C, it is then right in reaction tube
Aging state lean-burn type natural gas automotive catalyst after process carries out the test of each temperature spot conversion ratio and performance；
The step（2）The size of λ value is 1.35～1.55；Component in reacting gas includes CH4、CO、NOXAnd CO2。
5. aging state lean-burn type natural gas vehicle catalyst regeneration process as claimed in claim 4, it is characterised in that：The step
Suddenly（2）In N2For High Purity Nitrogen of the purity more than or equal to 99.99%, air speed is controlled to 4000～4500/h.
6. aging state lean-burn type natural gas vehicle catalyst regeneration process as claimed in claim 4, it is characterised in that：The step
Suddenly（2）Reacting gas air speed in middle reacting furnace is 39960～40000/h.
7. aging state lean-burn type natural gas vehicle catalyst regeneration process as claimed in claim 4, it is characterised in that：The step
Suddenly（2）Middle reacting gas need to be well mixed in gas mixing tank.
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| CN201510316208.9A CN104923317B (en) | 2015-06-10 | 2015-06-10 | Regeneration device and process of anti-aging catalyst for lean-burn natural gas truck |
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|---|---|---|---|
| CN201510316208.9A CN104923317B (en) | 2015-06-10 | 2015-06-10 | Regeneration device and process of anti-aging catalyst for lean-burn natural gas truck |
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| CN104923317B true CN104923317B (en) | 2017-05-10 |
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| CN109647318A (en) * | 2019-01-07 | 2019-04-19 | 江苏大学 | A kind of reacting furnace based on NTP regeneration of deactivated catalyst |
| CN114618391A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Solid catalyst filling assembly and filling method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909104A (en) * | 2012-09-26 | 2013-02-06 | 广东电网公司电力科学研究院 | Thermal regeneration method and device of SCR (selective catalytic reduction) denitration catalyst |
| CN103638991A (en) * | 2013-11-18 | 2014-03-19 | 广东电网公司电力科学研究院 | Composite apparatus for generating SCR denitrification catalyst and testing activity of catalyst before and after regeneration |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909104A (en) * | 2012-09-26 | 2013-02-06 | 广东电网公司电力科学研究院 | Thermal regeneration method and device of SCR (selective catalytic reduction) denitration catalyst |
| CN103638991A (en) * | 2013-11-18 | 2014-03-19 | 广东电网公司电力科学研究院 | Composite apparatus for generating SCR denitrification catalyst and testing activity of catalyst before and after regeneration |
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